Condensed-Matter and Materials Physics: Basic Research For Tomorrow's Technology (1999)

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Condensed-Matter and Materials Physics:

Basic Research for Tomorrow's
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Condensed-Matter and Materials Physics: Basic Research for Tomorrow's Technology
Condensed-
Matter and
Materials
Physics
Basic Research for Tomorrow’s
Technology
Committee on Condensed-Matter and Materials Physics

Board on Physics and Astronomy
Commission on Physical Sciences, Mathematics, and Applications
National Research Council
NATIONAL ACADEMY PRESS

Washington, D.C. 1999
Copyright National Academy of Sciences. All rights reserved.

NOTICE: The project that is the subject of this report was approved by the Governing Board of the
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International Standard Book Number 0-309-06349-3

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COMMITTEE ON CONDENSED-MATTER
AND MATERIALS PHYSICS
VENKATESH NARAYANAMURTI, Harvard University, Chair

JAMES B. ROBERTO, Oak Ridge National Laboratory, Vice Chair
GABRIEL AEPPLI, NEC Research Institute
J. MURRAY GIBSON, University of Illinois, Urbana-Champaign
STEVEN GIRVIN, Indiana University
MARK KETCHEN, IBM T.J. Watson Research Center
EDWARD J. KRAMER, University of California, Santa Barbara
JAMES S. LANGER, University of California, Santa Barbara
CHERRY ANN MURRAY, Lucent Technologies, Bell Laboratories
V. ADRIAN PARSEGIAN, National Institutes of Health
PAUL S. PEERCY, SEMI/SEMATECH
JULIA M. PHILLIPS, Sandia National Laboratories
ROBERT C. RICHARDSON, Cornell University
FRANS SPAEPEN, Harvard University
KATEPALLI R. SREENIVASAN, Yale University
DONALD C. SHAPERO, Director

DANIEL F. MORGAN, Program Officer (until June 1, 1998)
KEVIN D. AYLESWORTH, Program Officer (as of September 7, 1998)
iii

BOARD ON PHYSICS AND ASTRONOMY
ROBERT C. DYNES, University of California, San Diego, Chair

ROBERT C. RICHARDSON, Cornell University, Vice Chair
STEVEN CHU, Stanford University
VAL FITCH, Princeton University
IVAR GIAEVER, Rensselaer Polytechnic Institute
JOHN HUCHRA, Harvard-Smithsonian Center for Astrophysics
R.G. HAMISH ROBERTSON, University of Washington
KATHLEEN TAYLOR, General Motors Research and Development Center
J. ANTHONY TYSON, Lucent Technologies, Bell Laboratories
GEORGE WHITESIDES, Harvard University
DONALD C. SHAPERO, Director

ROBERT L. RIEMER, Associate Director
KEVIN D. AYLESWORTH, Program Officer
NATASHA CASEY, Senior Administrative Associate
GRACE WANG, Project Assistant
iv

COMMISSION ON PHYSICAL SCIENCES, MATHEMATICS,

AND APPLICATIONS
PETER M. BANKS, Environmental Research Institute of Michigan, Co-chair

W. CARL LINEBERGER, University of Colorado, Co-chair
WILLIAM BROWDER, Princeton University
LAWRENCE D. BROWN, University of Pennsylvania
MARSHALL H. COHEN, California Institute of Technology
RONALD G. DOUGLAS, Texas A&M University
JOHN E. ESTES, University of California, Santa Barbara
JERRY P. GOLLUB, Haverford College
MARTHA HAYNES, Cornell University
JOHN L. HENNESSY, Stanford University
CAROL JANTZEN, Westinghouse Savannah River Company
PAUL KAMINSKI, Technovation, Inc.
KENNETH H. KELLER, University of Minnesota
MARGARET G. KIVELSON, University of California, Los Angeles
DANIEL KLEPPNER, Massachusetts Institute of Technology
JOHN KREICK, Sanders, a Lockheed Martin Company
MARSHA I. LESTER, University of Pennsylvania
M. ELISABETH PATÉ-CORNELL, Stanford University
NICHOLAS P. SAMIOS, Brookhaven National Laboratory
CHANG-LIN TIEN, University of California, Berkeley
NORMAN METZGER, Executive Director


Preface
In the spring of 1996, the National Research Council’s Board on Physics and
Astronomy established the Committee on Condensed-Matter and Materials Phys-
ics to prepare a scholarly assessment of the field as part of the new survey of
physics, Physics in a New Era, that is now in progress. This assessment has five
objectives.
1. Identify future opportunities and priorities in the field.

2. Articulate the fundamental scientific challenges in the field.
3. Assess related infrastructure, institutional, resource, and educational issues.
4. Provide evidence of the societal impact of the field.
5. Provide a forum for coordinated community-wide communications with
federal agencies, policy makers, and the public.
The committee was composed of individuals whose backgrounds reflect the

diversity of the field and its close connections with related branches of science,
including chemistry, biology, and engineering. The field spans research environ-
ments from principal investigators carrying out benchtop studies in universities
to large collaborations carrying out experiments at major national facilities. It
also spans the forefronts of many-body theory, the behavior of complex materials
and fluids, and the design of semiconductor devices and circuits. Condensed-
matter and materials physics research is carried out in various institutional set-
tings, including university, government, and industrial research laboratories.
In the course of the study, the committee held two workshops on research
frontiers and policy issues. These workshops brought together leading research-
vii

viii PREFACE
ers in the field as well as leading policy makers from government, industry, and
universities. The committee met several times to plan its work, debate the issues,
and formulate its report. An early output of the study was the report The Physics
of Materials: How Science Improves Our Lives, a short, colorful, and easy-to-
read pamphlet illustrating how research in the field affects our daily lives. The
committee generated several progress reports and held public forums at materi-
als-related meetings of the American Physical Society and the Materials Re-
search Society. The committee also sought input from the general science and
engineering communities. We are particularly grateful to our colleagues in biol-
ogy, chemistry, and materials and electrical engineering for their support and
help in carrying out this study.
The committee would like to thank Donald C. Shapero, Daniel F. Morgan,
and Kevin D. Aylesworth from the Board on Physics and Astronomy for their
efforts throughout the course of this study. Special thanks also to Arthur
Bienenstock, who served on the committee until the fall of 1997, when he as-
sumed responsibilities at the Office of Science and Technology Policy. The
committee gratefully acknowledges the contributions of the following individuals
who provided material or particular advice that influenced its study: David
Abraham, Eric J. Amis, Bill Appleton, Meigan Aronson, David Aspnes, John
Axe, Arthur P. Baddorf, Samuel Bader, A. Balazs, N. Balsara, Troy Barbee, F.
Bates, Bertram Batlogg, Robert Behringer, Jerzy Bernholc, Arthur Bienenstock,
Jörg Bilgram, Howard Birnbaum, Stephen G. Bishop, Steve Block, Lynn A.
Boatner, Eberhardt Bodenschatz, Greg Boebinger, William Boettinger, Bill
Brinkman, R. Bubeck, David Cannell, Federico Capasso, G. Slade Cargill, John
Carruthers, Robert Cava, Robert Celotta, David Ceperley, Paul Chaikin, Albert
Chang, S.S. (Leroy) Chang, Eric Chason, Daniel Chemla, Shiyi Chen, S. Cheng,
B. Chmelka, Alfred Cho, John R. Clem, Daniel Colbert, Piers Coleman, George
Crabtree, George Craford, Harold Craighead, Roman Czujko, Elbio Dagatto,
Adriaan de Graaf, Satyen Deb, Patricia Dehmer, Cees Dekker, David DiVincenzo,
Russ Donnelly, Robert Doremus, J. Douglas, Mildred S. Dresselhaus, Bob
Dunlap, J. Dutcher, Bob Dynes, Robert Eisenstein, Chang-Beom Eom, Evan
Evans, Ferydoon Family, Matthew P.A. Fisher, Zachary Fisk, Paul Fleury, Mike
Fluss, Judy Franz, Jean Fréchet, Glenn Fredrickson, Hellmut Fritsche, William
Gallagher, E. Giannelis, Allen M. Goldman, Jerry Gollub, Matt Grayson, P.
Green, G. Grest, Peter Grüter, Richard Hake, Thomas Halsey, Donald Hamann,
Christopher Hanna, Bill Harris, Beverly Hartline, Kristl Hathaway, Lance
Haworth, Frances Hellman, George Hentschel, Jan Herbst, Pierre Hohenberg,
Susan Houde-Walter, Evelyn Hu, Robert Hull, David Huse, Eric Isaacs, Nikos
Jaeger, Adam B. Jaffe, Sungho Jin, David Johnson, James Jorgensen, Malvin H.
Kalos, A. Karin, Marc Kastner, Efthimios Kaxiras, Jeffrey Koberstein, Carl C.
Koch, Kei Koizumi, J. Kornfield, Mark Kryder, Max Lagally, David V. Lang,
Robert Laudise, G. Leal, Manfred Leiser, Ross Lemons, Joseph Levitzky, Peter
Levy, David Litster, T. Lodge, Gabrielle Long, Steven Louie, Michael

PREFACE ix
Lowenberg, Tom Lubensky, C. Macosko, Richard Martin, Denis McWhan, Jim

Meindl, Jim Merz, Burkhard Militzer, Andrew Millis, S. Milner, David Moncton,
Jagadeesh Moodera, Donald Murphy, M. Muthukumar, Sidney Nagel, Al Narath,
David Nelson, Jeff Nelson, Robert J. Nemanich, Robert Newnham, K.L. Ngai,
William Oosterhuis, Stuart Parkin, Seevak Parpia, Michelle Parrinello, Kumar
Patel, Eva Pebay-Peyroula, Stephen J. Pennycook, V. Percec, Pierre Petroff, Tom
Picraux, Gary Prinz, Itamar Procaccia, Peter Pusey, R. Ramesh, R. Register,
James Rice, Kevin Robbie, Mark Robbins, Jack Rowe, Michael Rowe, John M.
Rowell, M. Rubinstein, Jack Rush, Robert Schafrik, Hans Scheel, Sheldon
Schultz, Lyle Schwartz, Pabitra Sen, James Sethna, Don Shaw, K. Shull, Jerry
Simmons, John Slonczewski, James Speck, Gene Stanley, Galen Stucky, Harold
Swinney, Bruce Taggart, Andrew Taylor, Philip Taylor, Zlatko Tes̆anovi, Iran
Thomas, Carl V. Thompson, David Tirrell, Matt Tirrell, Robert Trew, Ruud
Tromp, Jeffrey Tsao, Dan Tsui, David Turnbull, Paul Umbanhowar, Priya
Vashishta, Stephan von Molnar, Jim Voytuk, James Warren, John Weaver, Eicke
Weber, Tom Weber, David Weitz, Steven White, Hollis Wickman, John Wilkins,
Ellen D. Williams, Stan Williams, T. Witten, Horst Wittmann, Victor Yakhot,
Sidney Yip, Andrew Zangwill, Richard Zare, Z. Zhang, and Thomas Zipperian.
The committee also thanks Janet Overton, who edited the final production draft
of the report.
The committee’s work was supported by grants from the U.S. Department of
Commerce, the U.S. Department of Energy, and the National Science Founda-
tion. The committee thanks them for their support.

Acknowledgment of Reviewers
This report has been reviewed by individuals chosen for their diverse per-
spectives and technical expertise, in accordance with procedures approved by the
National Research Council’s (NRC’s) Report Review Committee. The purpose
of this independent review is to provide candid and critical comments that will
assist the authors and the NRC in making the published report as sound as
possible and to ensure that the report meets institutional standards for objectivity,
evidence, and responsiveness to the study charge. The contents of the review
comments and the draft manuscript remain confidential to protect the integrity of
the deliberative process. We wish to thank the following individuals for their
participation in the review of this report:
Phillip W. Anderson, Princeton University,

Steven Chu, Stanford University,
Esther Conwell, University of Rochester,
Robert Dynes, University of California, San Diego,
Val Fitch, Princeton University,
Paul Fleury, University of New Mexico,
Jerry P. Gollub, Haverford College,
David Moncton, Argonne National Laboratory,
Thomas Russell, University of Massachusetts, Amherst, and
Thomas Theis, IBM T.J. Watson Research Center.
Although the individuals listed above have provided many constructive com-
ments and suggestions, the responsibility for the final content of this report rests
solely with the authoring committee and the NRC.

Contents
Executive Summary 1
Overview 5
Introduction, 5
A New Era, 7
The Science of Modern Technology, 8
New Materials and Structures, 10
Novel Quantum Phenomena, 11
Nonequilibrium Physics, 15
Complex Fluids and Macromolecular and Biological Systems, 17
New Tools for Research: From the Benchtop to the
National Laboratory, 19
Findings and Recommendations, 24
Research Infrastructure, 25
Major Facilities, 26
Partnerships, 27
Education, 28
Research Themes, 29
1 Electronic, Optical, and Magnetic Materials and Phenomena:

The Science of Modern Technology 31
Electronic Materials and Phenomena, 38
Materials and Physics That Drive Today’s Technology, 38
Challenges, Priorities, and Frontiers of Electronic Materials and
Phenomena, 55
xi

xii CONTENTS
Optical Materials and Phenomena, 56

Materials and Physics That Drive Today’s Technology, 56
Challenges, Priorities, and Frontiers of Optical Materials and
Phenomena, 75
Science and Technology of Magnetism, 75
Technology Pull, 76
The Physics of Magnetism, 82
Major Outstanding Materials and Physics Questions and Issues in
Magnetism, 89
Future Directions and Research Priorities, 90
Major Outstanding Scientific and Technological Questions, 92
Priorities, 92
2 New Materials and Structures 93

Complex Oxides, 98
Electroceramics, 106
New Forms of Carbon, 109
Nanoclusters, 114
Thin Films, Surfaces, and Interfaces, 120
Artificially Structured Materials, 126
Materials Properties by Design: Complexity, 132
Synthesis and Processing: Control, 135
Physics: Understanding, 135
Technology: Relevance, 135
Outstanding Scientific Questions, 136
Research Priorities, 136
3 Novel Quantum Phenomena 137

Superfluidity and Superconductivity, 140
Bose-Einstein Condensation in Atom Traps, 145
Quantum Spin Chains and Ladders, 148
The Quantum Hall Effect, 155
Composite Particles, 158
Edge States, 160
Magnetic Order of Spins and Pseudospins, 162
Summary, 166
4 Nonequilibrium Physics 168

Pattern Formation and Turbulence in Fluid Dynamics, 170
Nonequilibrium Phenomena in Fluids, 170
Pattern Formation, 171

CONTENTS xiii
Turbulence, 173
Processing and Performance of Structural Materials:
Metallurgical Microstructures, 176
Processing and Performance of Structural Materials: Solid Mechanics, 178
Brittle and Ductile Solids, 180
Instabilities in Dynamic Fracture, 180
Polymers and Adhesives, 183
Friction, 184
Granular Materials, 187
Length Scales, Complexity, and Predictability, 189
Further Prospects for the Future, 190
Nonequilibrium Phenomena in the Quantum Domain, 190
Nonequilibrium Phenomena in Biology, 191
5 Soft Condensed Matter: Complex Fluids, Macromolecular Systems,

and Biological Systems 194
Complex Fluids, 197
Liquid Crystals and Microemulsions, 197
Colloidal and Macromolecular Interactions, 200
Polyelectrolytes, 202
Polysaccharides, 203
Macromolecules and Macromolecular Films, 204
Phase Separation and Ordering in Thin Polymer Films, 204
New Macromolecular Materials, 205
Structural Polymers: Controlling Properties of New Polymers
from Old Monomers, 210
Biological Connections, 211
Biological Systems, 211
Two Traditions of Learning Must Merge to Allow Systematic
Progress, 212
Physics and Structural Biology, 213
Molecular Conformation and Protein Folding, 215
Single-Molecule Motions and Mechanics, 215
Molecular Association, 219
Consequences of the Human Genome Project and Other Genome
Determinations, 221
Directions and Priorities, 222
Priorities, 223
6 New Tools for Research 225

Atomic Visualization Through Microscopy, 227
Atomic Structure, 229

xiv CONTENTS
Electronic Structure, 231

Nanoproperties of Materials, 231
Atomic Manipulation, 233
Conclusions, 234
Neutron Scattering, 234
The Past Decade, 235
The Next Decade, 242
Synchrotron Radiation, 244
The Past Decade, 247
The Reinvention of Traditional Condensed-Matter Experiments, 253
Man-Made Extreme Conditions, 255
Matter at Very Low Temperatures, 256
Matter at Very High Pressures, 257
Matter in Large Magnetic Fields, 260
Computational Materials Physics, 262
Progress in Algorithms, 264
Computational Physics in a Teraflop World, 267
Quantum Computers, 269
Outstanding Scientific Questions, 272
Priorities, 273
7 Changes in the R&D Landscape 274

From the Cold War to the Global Economy, 274
A Decade of Change, 275
Condensed-Matter and Materials Physics Today, 282
Measuring Performance and Economic Impacts, 284
8 The Next Decade 288

Making the Right Investments, 288
Human Capital, 289
Facilities and Infrastructure, 290
Redefining Roles and Relationships, 295
Role of Research Universities, 296
Role of Government Laboratories, 297
Interactions with Industry, 298
The Importance of Partnerships, 299
Integrating Research and Education, 302
A Research Strategy for Condensed-Matter and Materials Physics, 303
Discovery, 304
Scientific Themes, 304
Excellence with Relevance, 307

Condensed-
Matter and
Materials
Physics


Executive Summary
Condensed-matter and materials physics plays a central role in many of the

scientific and technological advances that have changed our lives so dramatically
in the last 50 years. Condensed-matter and materials physics gave birth to the
transistor, the integrated circuit, the laser, and low-loss optical fibers so important
to the modern computer and communications industries. The years ahead prom-
ise equally dramatic advances, making this an era of great scientific excitement
for research in the field. Communicating this excitement and ensuring further
progress are the main goals of this report.
In the decade since the last major assessment of the field, important results
and discoveries have come rapidly and from unexpected directions. These results
and discoveries have made possible advances that range from new experimental
tools for atomic-scale manipulation and visualization, to the creation of new
synthetic materials (such as buckyballs and high-temperature superconductors),
to new physical phenomena such as giant magnetoresistance and the fractional
quantum Hall effect. An enormous increase in computing power has yielded
qualitative changes in visualization and simulation of complex phenomena in
large-scale many-atom systems. Progress in synthesis, visualization, manipula-
tion, and computation will continue to have an impact on many areas of research
spanning different length scales from atomic to macroscopic. Strong impact may
also be expected in “soft” condensed-matter physics, particularly where it inter-
faces with biology and chemistry.
The priorities of society are shifting from military security to economic well-
being and health. Changing societal priorities, in turn, create shifting demands
on condensed-matter and materials physics. Among these demands are an

2 CONDENSED-MATTER AND MATERIALS PHYSICS
improved public understanding of science, better education of scientists and engi-

neers for today’s employment marketplace, and new contributions to the nation’s
industrial competitiveness.
There are four key challenges facing condensed-matter and materials physics:
• The intellectual vitality of the field must be nurtured, particularly by

facilitating the research of individual investigators and small teams in areas that
cross disciplinary boundaries.
• A state-of-the-art facilities infrastructure is essential for competitive re-
search; such an infrastructure requires the creation of laboratory-scale micro-
characterization facilities at universities and large-scale facilities at national
laboratories.
• Efforts must be enhanced in research universities to improve integration
of condensed-matter and materials physics education and research, particularly at
the boundaries of disciplines, and to prepare flexible and adaptable physicists for
the future.
• New modes of cooperation among universities, colleges, government
laboratories, and industry need to be developed that will ensure the connection
between the field and the needs of society and to ensure preservation of the fertile
innovative climate of major industrial laboratories that have played a dominant
role in condensed-matter and materials physics research.
In this report the committee makes a number of recommendations for steps

to be taken to meet these challenges. They are outlined here and discussed more
extensively in the Overview and in further detail in each of the chapters.
For the overall research effort to address the full range of problems facing
the field, a hierarchy of approaches is necessary. The core of the research effort
in condensed-matter and materials physics is in the work of individual investiga-
tors and small research groups. Some of the most innovative and creative devel-
opments originate in this mode of research. At the next levels, larger groups,
centers, and entire laboratories cooperate on significant problems, aided by pro-
gressively more-complex instrumentation and facilities. Theoretical work and
benchtop experiments are usually done by individual investigators. Small-scale
centers located in universities and government laboratories play an essential role
in a number of areas including microcharacterization, processing, synthesis, and
state-of-the-art instrumentation development. The highest level in the hierarchy
is exemplified by major facilities, including synchrotron light sources, centers for
neutron-scattering research, and laboratories for high magnetic field studies.
These major facilities address a broad range of problems. An area of particularly
rapid growth is found in the use of these major facilities, particularly synchrotron
light sources, in understanding soft condensed matter and biological systems. A
key facilities problem is the critical gap in U.S. capabilities in the area of neutron
sources.

EXECUTIVE SUMMARY 3
The different modes of research—benchtop experiments, larger collabora-

tions, and so on—are evolving steadily. The work carried out in these varied
modes is complex and diverse and continuously expanding to encompass an
increasing number of disciplines. The committee has paid special attention to
describing the forefronts of condensed-matter and materials physics research in
conjunction with a small number of research themes. These themes are discussed
in some detail in the Overview and reappear in each of the chapters. Throughout
this study the themes of new experimental and computational capabilities, the
ability to address problems of increasing complexity, and the importance of
relationships with other fields are interwoven with discussion of subdisciplines of
condensed-matter and materials physics. One of the subdisciplines that has cap-
tured the imagination of theorists and experimenters alike is the structure and
properties of materials at reduced dimensionality—for example, in planar struc-
tures. Developing large-scale integrated circuits depends on understanding the
behavior of semiconductors in such configurations, so the potential for impact is
apparent.
A number of actions are required to maintain and enhance productivity in the
field of condensed-matter and materials physics. These actions involve each
level of the hierarchy of research modalities and the interactions among the
various levels and the various performers. The principal recommendations of the
committee are summarized here:
• The National Science Foundation, the U.S. Department of Energy, the

U.S. Department of Defense, and other agencies that support condensed-matter
and materials physics research should continue to nurture the core research at the
heart of the field. The research areas described in the Overview provide a guide
to the scientific arenas at the forefront of this work.
• The agencies that support and direct research should plan for increased
investment in modernizing the condensed-matter and materials physics research
infrastructure at universities and government laboratories.
• The National Science Foundation should increase its investment in state-
of-the-art instrumentation and fabrication capabilities, including centers for in-
strumentation R&D, nanofabrication, and materials synthesis and processing at
universities. The Department of Energy should strengthen its support for such
programs at national laboratories and universities.
• The insufficiency of neutron sources in the United States should be ad-
dressed in the short term by upgrading existing neutron-scattering facilities and in
the long term by the construction of the Spallation Neutron Source.
• Support for operations and upgrades at synchrotron facilities, including
research and development on fourth-generation light sources, should be strength-
ened.
• The broad use of synchrotron and neutron facilities across scientific disci-
plines and sectors should be considered when establishing agency budgets.

• Federal agencies should provide incentives for formation of partnerships

among universities and government and industrial laboratories that carry out
research in condensed-matter and materials physics.
• Universities should endeavor to enhance their students’ understanding of
the role of knowledge integration and transfer as well as knowledge creation.

Overview
INTRODUCTION
Condensed-matter and materials physics is the branch of physics that studies
the properties of the large collections of atoms that compose both natural and
synthetic materials. The roots of condensed-matter and materials physics lie in
the discoveries of quantum mechanics in the early part of the twentieth century.
Because it deals with properties of matter at ordinary chemical and thermal
energy scales, condensed-matter and materials physics is the subfield of physics
that has the largest number of direct practical applications. It is also an intel-
lectually vital field that is currently producing many advances in fundamental
physics.
Fifty years ago the transistor emerged from this area of physics. High-
temperature superconductivity was discovered by condensed-matter physicists,
as were the fascinating low-temperature states of superfluid helium. Scientists in
this field have long-standing interests in electronic and optical properties of
solids and all aspects of magnetism and magnetic materials. They investigate the
properties of glasses, polymeric materials, and granular materials as well as
composites, in which diverse constituents are combined to produce entirely new
substances with novel properties.
Condensed-matter and materials physics has played a key role in the techno-
logical advances that have changed our lives so dramatically in the last 50 years.
Driven by discoveries in condensed-matter and materials physics, these advances
have brought us the integrated circuit, magnetic resonance imaging (MRI), low-
loss optical fibers, solid-state lasers, light-emitting diodes, magnetic recording
disks, and high-performance composite materials. These in turn have led to the

spectacular growth of modern computer and telecommunications industries and,

consequently, to the information revolution.
For many years after the invention of the transistor, the major intellectual
challenge facing researchers in condensed-matter and materials physics was to
understand the physical properties of nearly perfect single crystals of elements,
simple compounds, and alloys. Most of these materials occur in some form in
nature. On a basis of increased knowledge and powerful new synthesis tech-
niques, today’s condensed-matter and materials physics is directed toward creat-
ing entirely new classes of materials—so-called “artificially structured” materi-
als—that do not exist in nature and whose sizes reach all the way down to the
atomic domain. At the same time, a growing number of researchers are using
new theoretical and experimental tools to extend our understanding to much more
complex forms of matter—high-temperature superconductors, multicomponent
magnetic materials, semicrystalline polymers, and glasses. These tools are, in
turn, giving greater insight into more complex phenomena like the fracture of
solids and the continuous transition from liquid to glass in the process of cooling.
Ever in view in current condensed-matter and materials physics are research op-
portunities presented by dramatic progress in the biological sciences. Condensed-
matter and materials physicists are working with biological scientists to develop
a new field of “physical biology” in which physics-based techniques and ap-
proaches are applied to the study of biological materials and processes.
Indeed, condensed-matter and materials physics is distinguished by its ex-
traordinary interdependence with other science and engineering fields. It is a
multifaceted and diverse interdisciplinary field, strongly linked to other science
and engineering disciplines that both benefit from and contribute to its successes.
Important examples of this collaboration include fullerenes (physics and chemis-
try), macromolecules (physics, chemistry, and biology), structural alloys (physics
and materials engineering), and silicon technology (physics and electrical engi-
neering). Condensed-matter and materials physics also has strong interrelation-
ships to other branches of physics. Prominent examples include Bose-Einstein
condensation (with atomic physics) and the fractional quantum Hall effect (el-
ementary-particle physics). Its practitioners include those who discover and
develop new materials, those who seek to understand such materials at a funda-
mental level through experiments and theoretical analysis, and those who apply
the materials and understanding to create new devices and technologies. This
work is done in universities, in industry, and in government laboratories. Ad-
vances in basic research inspire new ideas for applications, and applications-
driven technological advances provide tools that enable new fundamental inves-
tigations. Technological advances provide new tools such as synchrotrons,
neutron sources, electron microscopes, computers, and scanning-probe micro-
scopes. These new tools are leading to new advances in the fundamental under-
standing of materials and to a wide-ranging impact on other fields—biology,
chemistry, environmental sciences, and engineering.

OVERVIEW 7
A NEW ERA
The world of condensed-matter and materials physics is entering a new era.
Extraordinary advances in instrumentation are providing access to the world of
atoms and molecules on an unprecedented scale. Powerful new experimental
tools, from national synchrotron and neutron facilities to bench-scale atomic-
probe microscopes, are opening up new windows for visualizing and manipulat-
ing materials on the atomic scale. Applications range from nanofabrication of
electronic devices to probing the secrets of superconductivity and protein folding.
These changes are far-reaching. Many research areas, previously inaccessible,
are yielding to new and unanticipated advances in atomic-scale synthesis, charac-
terization, and visualization.
Advances in computational power have made it possible, for the first time, to
simulate the behavior of complex materials systems and large assemblies of atoms.
As a result, numerical simulation is approaching parity with laboratory experiments
and analytic theory in many areas of condensed-matter and materials physics re-
search. Based on benchmarks provided by experimentation, and enlightened by a
proper consideration of theory, the new computational tools provide synergy to
accelerate the understanding of ever more-complex systems. Again, this is a quali-
tative change—with each new generation of computational power, opportunities
are emerging that could only be imagined a few years earlier.
The combined power of the new experimental tools and computational ad-
vances are having an enormous impact on condensed-matter and materials phys-
ics, particularly in those areas where the ability to span length scales from the
atomic to macroscopic is of fundamental importance, that is, where the properties
of atoms and molecules—especially quantum phenomena—become relevant to
large-scale phenomena. This new capability to span length scales is bringing the
world of atoms and molecules closer to the world of our experience, from the
mysteries of quantum mechanics, to the mechanical properties of materials, to the
self-assembly of biological systems. Many of these problems, which underlie
technological innovation and revolution, could not have been addressed on a
fundamental basis even a few years ago.
The developments described in this report present a condensed-matter and
materials physics profoundly different than it has been at any other time in
history. The ability to control and manipulate atoms, to observe and simulate
collective phenomena, to treat complex materials systems, and to span length
scales from atoms to our everyday experience, provides opportunities that were
not even imagined a decade ago. These developments underlie current progress
in condensed-matter and materials physics and provide tremendous optimism for
the future vitality of the field. They also underlie a new unity in science. Ad-
vances in condensed-matter and materials physics increasingly interface with and
relate to nearly all areas of science and engineering, including atomic and mo-
lecular physics, particle physics, materials science, chemistry, biology, and com-

putational sciences. The next decade will bring extraordinary benefits from this
unity, especially as the new capabilities in condensed-matter and materials phys-
ics bridge the gap between physics and biology, revealing the molecular-physics
basis of biological phenomena.
THE SCIENCE OF MODERN TECHNOLOGY

The information age owes its rapid growth to technological advances that
depend on progress in science. Scientific understanding of fundamental phenom-
ena has been closely tied to the development of materials with special properties
as carriers and controllers of electrical current, light waves, and magnetic fields.
Equally important is understanding, on both fundamental and quantitative levels,
the processes that enable cost-competitive manufacturing of devices and systems
based on these materials for the rapidly changing electronics and telecommunica-
tions industries.
Silicon is the foundation of today’s integrated circuit technology. The sci-
ence and technology of this material have built on each other, leading to progres-
sively smaller, faster, and more-complex devices. In turn, semiconductor fabrica-
tion technology has enabled the construction of exotic quantum devices that are
essentially man-made two-dimensional atoms. A range of new insights into the
behavior of large collections of electrons have come from studying electron
behavior in these devices. As these circuits continue to develop, doubling their
speed and power every 18 months in accordance with the empirical Moore’s
Law, they march farther into the quantum domain where new physical phenom-
ena arise that must be understood and controlled to ensure continuing progress.
Compound semiconductors such as gallium arsenide, gallium nitride, and
others are essential to the field of telecommunications. They have characteristics
that enable the production of electronic and optoelectronic devices with excep-
tional performance characteristics. They also underlie the solid-state laser tech-
nology that converts digital electronic signals into optical signals that travel great
distances on fiber-optic cable. The development of lasers at the right wavelengths
is essential to minimize losses and to enable the amplification of the signal by
purely optical (nonelectronic) means. A particularly exciting recent development
is the gallium nitride laser, which produces blue light suitable for next-generation
optical storage systems. Another important development is vertical-cavity sur-
face-emitting lasers, which will bring the mass-production advantages of inte-
grated circuits to diode lasers. Their geometry will enable chip-to-chip optical
interconnects in future generations of integrated circuits.
Fiber-optic cable, an extraordinary product of optical materials research,
enables the transmission of information by modulation of light waves traveling in
a glass fiber. Because light, the carrier of the information, has a frequency of at
least 1014 Hz (much higher than ordinary radio waves), the rate of information
transmission achievable with fiber optics is extremely high. The mechanisms that

OVERVIEW 9
scatter light in these fibers had to be understood in great detail before it was
possible to develop today’s low-loss fibers that enable a signal to travel 800 km
(500 miles) before it is attenuated. Modern optical fibers are so perfect that the
dominant loss mechanism is the scattering of light by density fluctuations frozen
in when the fiber is cooled to become a glass. Fiber-optic amplifiers have been
developed that greatly extend the reach of these systems. A great challenge is to
develop an inexpensive interface that will bring fiber information links to the
home user. Optics enables data storage in compact disks, in the new high-
capacity digital video disks (DVDs), and high-density storage systems now in
development. To continue this progress, materials scientists must develop com-
mercially manufacturable solid-state lasers that emit blue light. Optics is also
essential to display, printing, and copying technologies. Optics is playing an
increasingly important role in the telecommunications revolution. Further re-
search into the properties of materials for fiber-optic amplifiers, fast optical
switches, and many other optical technologies will be necessary for future ad-
vances in information technologies.
Magnetism has presented physics with some of its most challenging theoreti-
cal problems and also with some of its most important applications. Driven by the
need for progressively more data-storage capacity, the science of magnetism has
yielded new technology for the devices that read and write data on computer disk
drives. Using the recently discovered phenomenon of giant magnetoresistance,
technologists have found ways to fabricate read/write heads that have allowed
development of these devices to keep pace with rapid improvements in integrated
circuitry. Progress in magnetic materials has also yielded a new class of small
motors and new transformer core materials for power distribution. And magneto-
electronic devices have moved from the laboratory to applications with amazing
speed. Among the sensors based on these new technologies are superconducting
quantum interference devices (SQUIDs) that enable the detection of minuscule
magnetic fields emitted by the human brain and heart, and magnetic force micro-
scopes that can image magnetic properties with nearly atomic-scale resolution.
As integrated circuitry becomes ever smaller and closer to the realm of
quantum physics, new ways of constructing the logic functions that are the build-
ing blocks of these circuits may be discovered. It may even become possible to
develop a new form of logic circuitry that exploits the properties of the strange
world of quantum mechanics. Until then, a number of challenges face the manu-
facturers of information systems. The tiny aluminum (and recently, copper) lay-
ers that connect the logic devices and their insulating glassy sheaths may have to
be replaced with something better in order to continue increasing speed. Optical
interconnections may play a role. Will some new way of producing digital
switches, the building blocks of computer logic, emerge? Can optical technology
be developed so that the essential functions of the communications network (such
as switching, now carried out electronically) can all be carried out with optical
devices? Will the key information technologies be reducible to the atomic-size

scale? Can the complex physics and chemistry of current and future materials be
mastered to enable us to meet this grand challenge?
NEW MATERIALS AND STRUCTURES

The effort to develop new materials and new configurations of matter, driven
largely by the potential for innovation that such novelties make possible, has led
to the creation of structures that have turned out to be microphysics laboratories
on the atomic scale. Some of these new materials and structures have provided
the environment for completely unexpected phenomena to emerge. A few
examples include high-temperature superconductors, organic superconductors,
buckyballs and related structures, and giant magnetoresistance materials.
High-temperature superconductors are superconducting above the boiling
point of liquid nitrogen. Before the discovery of superconductivity in this class
of materials, the effort to increase the superconducting transition temperature
(Tc) of materials focused on painstaking efforts to combine various metals into
superconducting alloys. This effort seemed to hit a brick wall at about 23 de-
grees above absolute zero—too low for widespread applications outside of re-
search. Unlike conventional superconductors, the new high-temperature materi-
als are not metals but ceramics, which one would expect to be insulators. The
fact that they conduct electricity at all is quite surprising. These materials have a
complicated perovskite crystal structure (like many naturally occurring miner-
als) with planes of copper and oxygen atoms. At the right temperatures, these
planes can function as superconductors. These ceramics are much more complex
than most of the materials previously studied in condensed-matter physics. There
are many possible permutations and combinations of constituents, making these
materials difficult to prepare and characterize. Because of the short range of
superconducting correlations, the materials are extremely sensitive to defects,
which adds to the difficulty. Notwithstanding the complexity, high-Tc supercon-
ducting films have already found application in the SQUID devices described
above.
The discovery of high-Tc superconducting materials has had a profound
influence on researchers in condensed-matter physics. The classic paradigm in
the field was to seek systems that exhibit some special simplification as an aid to
understanding the physics of solids, even the simplest of which are fairly compli-
cated. But the emergence of startling properties in materials with more complex
composition and structure has convinced researchers that admitting higher com-
plexity to the field of study can also offer the possibility of new and unexpected
phenomena and insights in all areas of condensed-matter and materials physics.
One effect of the study of high-Tc materials was a renewed interest in complex
perovskites. That, in turn, led to the discovery that the electrical resistance of
lanthanum manganate can be extremely sensitive to the presence of magnetic
fields. This effect, known as “colossal magnetoresistance,” is of great interest

OVERVIEW 11
because of its potential application to read data from a new generation of ultra-
high-density magnetic storage disks.
Until recently, carbon was thought to exist in only two crystal structures—
diamond and graphite. The discovery of new crystalline structures, generically
called “buckminsterfullerenes,” was a great surprise. Variations of these struc-
tures can have amazing properties, including forms with a tensile strength 100
times that of steel.
The name “buckminsterfullerene” was chosen because the structure of the
first one discovered resembles that of a geodesic dome. Their properties depend
primarily on this special shape. The structure can be imagined by starting with a
two-dimensional hexagonal lattice of carbon atoms found in graphite. If penta-
gons are substituted for some of the hexagons, the surface develops positive
curvature and can be made to close on itself, forming a soccer-ball structure (a
“buckyball”) or various other possible shapes, including tubes. These tubes can
vary from metallic to semiconducting, depending on their geometry. By exposing
fullerene molecules (C60) to alkali or alkaline-earth metal vapors, organic super-
conductors can be prepared.
These examples have all been startling breakthroughs. But amazing out-
comes can also result from the steady, evolutionary development of the proper-
ties of materials as some property is refined past previous technological barriers.
For example, steady improvements in the purity of semiconductor materials used
in high-frequency applications such as cellular phones eventually led to the fab-
rication of quantum-dot structures. These structures, fabricated on the quantum-
size domain, have energy states similar to those of atoms but with optical and
electronic properties that can be tailored for a wide variety of applications.
Several themes and challenges are apparent—the role of molecular geometry
and reduced dimensionality, the synthesis and processing and understanding of
more complex materials, tailoring the composition and structure of materials on
very small scales, and incorporation of new materials and structures in existing
technologies. Progress in these areas holds the promise of further startling break-
throughs, yielding materials with unexpected and useful properties and extending
the understanding of condensed-matter and materials physics.
NOVEL QUANTUM PHENOMENA

Perhaps the most important lesson learned from studying the physics of
systems that contain many particles is that when the number of particles in the
system is large enough, entirely new phenomena can appear. These new behav-
iors of the whole system may not have any obvious relationship to the properties
of the individual particles, but rather may arise from collective or cooperative
behavior of all the particles. Such phenomena are often referred to as “emergent
phenomena” because they emerge as the complexity of a system grows with the
addition of more particles.

In some materials, at sufficiently low temperatures, small motions of the

crystal lattice create interactions among the electrons that cause them to pair in
such a way that they form an electron liquid that no longer experiences friction
when it flows. Thus, because the flow of electrical current experiences no resis-
tance in such materials, they are known as “superconductors.” Superconductivity
is a good example of a quantum emergent phenomenon. Its existence was unan-
ticipated when only the properties of individual atoms were considered.
A rich variety of other new effects emerge when large ensembles of atoms
are brought together. The length scale of an atom is about 1 Å, and typical
quantum energy levels of the electrons in atoms are in the range of 1 to 10
electron volts (eV). As atoms are assembled in a solid, and more collective effects
emerge, length scales become larger and energy scales become smaller. It is
often convenient to view such systems not in terms of their building blocks, but
rather in terms of “elementary excitations” that may have properties very differ-
ent from those of the electrons and atoms that compose the system. As it becomes
possible to make materials and have more and more control over their structure,
impurities, and imperfections, collective excitations at smaller and smaller en-
ergy scales have been observed. These excitations sometimes have bizarre prop-
erties, such as carrying a charge that is a fraction of the electron charge.
Because these emergent phenomena present new and unexpected properties,
it can be said that one of the new frontiers of condensed-matter physics is at low
energies and at length scales large compared to atoms. By contrast, in elemen-
tary-particle physics, the frontier is at increasingly higher energies and shorter
length scales.
A particularly fascinating emergent phenomenon occurs in helium at very
low temperatures. Helium has an integer spin, so it is not bound by the Pauli
exclusion principle. As a result, many helium atoms can all occupy the same
quantum state, and this effect actually occurs at very low temperatures. In a
manner somewhat analogous to the loss of electrical resistivity in superconduc-
tivity, liquid helium at very low temperatures loses all viscosity. It can flow
without resistance through very small orifices and climb up the walls of its
containers. This phenomenon is called “superfluidity.” The general phenomenon
whereby many integer-spin particles occupy the lowest energy state is called
“Bose-Einstein condensation,” after Bose and Einstein, who first described the
statistical behavior of ensembles of quantum-mechanical particles with integer
spin.
Physicists were surprised to learn that helium-3 atoms can also exhibit super-
fluidity. Helium-3 is a half-integral spin atom, so it must obey the Pauli exclusion
principle, and it should not be able to undergo Bose-Einstein condensation. But
two helium-3 atoms can pair up to make a particle with integer spin, and that
composite particle can then undergo condensation. This phenomenon is similar to
the way electrons in a superconducting solid form pairs. Helium-3 forms a super-
fluid only at very low temperatures because the particles of which it is formed

OVERVIEW 13
are, themselves, only weakly bound together. Creating the super-low-tempera-

ture environment necessary to achieve superfluidity in helium-3 was an amazing
experimental tour de force. The discovery of superfluidity enabled by these ex-
perimental techniques was awarded the 1996 Nobel Prize for physics. (Table O.1
lists Nobel Prizes awarded for research related to condensed-matter and materials
physics.) The mechanism involved may have analogies to those responsible for
high-Tc superconductivity.
An even more extreme form of Bose-Einstein condensation was recently
achieved by the atomic physics community when alkali metal (such as sodium)
vapor was held in an atomic trap and cooled to temperatures within a few
microdegrees of absolute zero. The gas is very dilute and the atoms are far apart,
but the atoms behave coherently and can be directed in a laser-like beam. This
incredibly difficult experiment is at the outermost reaches of the low-energy,
large-distance quantum frontier.
These achievements have built bridges among the condensed-matter, atomic-
physics, and quantum-optics communities because condensation phenomena are
important in all of these areas. For example, optical lasers depend on the ability to
place a large ensemble of atoms in the same excited energy state. The atoms then
decay in a collective, coherent transition to a lower energy state, releasing coher-
ent light in the process.
An issue at the forefront of condensed-matter theory concerns quantum spin
chains and ladders. Quantum spins are typically associated with magnetic di-
poles. Magnets are simply solids in which the atomic spins in the crystal lattice
and their associated magnetic dipoles are all pointing in the same direction. An
important consequence of the discovery of high-Tc superconductors has been
progress in learning how to synthesize compounds that have spins arranged in
unusual configurations. Among these configurations are two-dimensional planes,
one-dimensional chains, and other more complex structures such as ladders. The
synthesis of these and other new families of organic and inorganic compounds
has reinvigorated the study of quantum magnetism. The role of magnetism in
high-Tc superconductors is among the outstanding questions in this area.
Probably the most remarkable collective phenomenon discovered in the latter
half of the twentieth century is the quantum Hall effect. The ordinary Hall effect
arises when electric current passes through a semiconductor film in the presence of
a magnetic field perpendicular to the plane of the film. The current-bearing elec-
trons moving in a magnetic field experience a force perpendicular to both the
magnetic field and the direction of motion. As a result, electrons are pushed to one
side of the film, which creates a transverse electric field and a voltage across the
film. The more current is passed through the film, the greater the voltage. The ratio
of the applied current to this voltage has the units of a conductance (or inverse
electrical resistance) and is called the “Hall conductance.”
If this experiment is carried out at high magnetic fields and low tempera-
tures, quantum mechanics comes into play and the Hall conductance becomes

14
TABLE O.1 Nobel Prizes Awarded for Research Related to Condensed-Matter and Materials Physics Since 1986
Year Field Citation Laureates
1986 Physics For design of the first electron microscope (Ruska) and the Ernst Ruska, Gerd Binnig, and Heinrich Rohrer
scanning-tunneling microscope (Binnig and Rohrer)
1987 Physics For discovery of superconductivity in ceramic materials Johannes Georg Bednorz and Karl A. Müller
1991 Physics For discovery of methods for studying order phenomena in Pierre-Gilles de Gennes
complex forms of matter, particularly liquid crystals and
polymers
1994 Physics For development of neutron-scattering techniques for Clifford G. Shull and Bertram N. Brockhouse
studies of condensed matter
1996 Chemistry For the discovery of fullerenes Harold Kroto, Robert Curl Jr., and Richard E. Smalley
1996 Physics For the discovery of superfluidity in helium-3 David M. Lee, Douglas D. Osheroff, and Robert C.
Richardson
1997 Physics For development of methods to cool and trap atoms with Steven Chu, Claude Cohen-Tannoudji, and
laser light William D. Phillips
1998 Chemistry For development of the density-functional theory (Kohn) Walter Kohn and John A. Pople
and computational methods in quantum chemistry (Pople)
1998 Physics For discovery of a new form of quantum fluid with Robert B. Laughlin, Horst L. Störmer, and
fractionally charged excitations Daniel C. Tsui

CONDENSED-MATTER AND MATERIALS PHYSICS
OVERVIEW 15
quantized in precise integer multiples of the fundamental constant e2/h where e is

the charge of the electron and h is Planck’s constant. It is remarkable that this
universal result is completely independent of all microscopic details of the sample
such as the density and types of impurities, the precise value of the magnetic
field, etc. Among the consequences of this extraordinary phenomenon is that it is
possible to make a high-precision measurement of the fine-structure constant
(which expresses the strength of electromagnetic forces) and also to realize a
highly reproducible standard of electrical resistance. This phenomenon is used in
standards laboratories throughout the world to maintain the unit of electrical
resistance (the ohm).
An even more surprising phenomenon occurs with samples of very high
purity at very low temperatures and in very high magnetic fields. In these condi-
tions it is possible to observe a Hall effect in which the conductivity is a fraction
of e2/h—for example, (1/3)e2/h. Physicists were quite startled by this observa-
tion. It turns out to result from the formation of quasiparticles whose effective
charge is one-third (or various other rational fractions) of the electron’s charge.
These quasiparticles are a collective mode of a quantum fluid. The low-energy
excitations of this weird fluid consist of vortices bound to a fraction of an electron
charge. These objects have been recently observed by direct measurement of
their charge and by tunneling experiments in which an electron added to the
system breaks up into three excitations, each with one-third of the electron’s
charge. This discovery, which earned the 1998 Nobel Prize in Physics (see Table
O.1), offers a whole universe of intriguing possibilities for experimental and
theoretical exploration of new collective modes.
NONEQUILIBRIUM PHYSICS
Nonequilibrium physics is the study of systems that are out of balance with
their surroundings. They may be changing their states as they are heated or
cooled, deforming as a result of external stresses, or generating complex or even
chaotic patterns in response to forces imposed on them. Examples include water
flowing under pressure through a pipe, a solid breaking under stress, or a snow-
flake forming in the atmosphere.
Understanding nonequilibrium phenomena is of great practical importance
in such diverse areas as optimizing manufacturing technologies, designing
energy-efficient transportation, processing structural materials, or mitigating the
damage caused by earthquakes. At the same time, the theory of nonequilibrium
phenomena contains some of the most challenging and fundamental problems in
physics. A central theme in this field is that the physics of ordinary materials and
processes is a rich source of inspiration for basic research.
Because nonequilibrium physics touches on such a wide range of different
areas of science and technology, it is an important channel through which physics
makes contact with other disciplines. For example, its concepts help explain

galaxy formation, climate change, and—perhaps most important—some of the

physical mechanisms that underlie biological phenomena. Indeed, the most char-
acteristic property of living systems may be their ability to maintain their extraor-
dinarily complex nonequilibrium states for extended periods of time. Because of
the variety of the different disciplines involved, each with its own culture and
approach to research, continued progress in nonequilibrium physics will depend
in large measure on the ability of institutions and scientists to bridge the culture
gaps that separate their different communities.
Much progress has been made in the last decade. For example, we now have
a detailed understanding of how complex patterns emerge in many apparently
simple hydrodynamic, metallurgical, and chemical situations. Pattern-forming
systems are intrinsically unstable against small perturbations and often exhibit
chaotic motion; it is now possible to understand how this happens in some cases.
The extreme sensitivity to small perturbations shown by many of these systems
makes it difficult to predict or control their behavior.
This field is very large and only a few topics have been selected in this report
to illustrate the major issues. These include pattern formation and turbulence in
fluid flow, processing and performance of structural materials, and some topics in
solid mechanics, specifically, friction, fracture, granular materials, and polymers
and adhesives. The chapter on nonequilibrium physics also includes brief discus-
sions of nonequilibrium phenomena in the quantum and biological domains, and
yet briefer remarks about nonequilibrium complexity and limits of predictability.
To convey some of the flavor of the field, the committee mentions just a few of
those topics in the paragraphs that follow.
A beautiful example of pattern formation in fluid dynamics is provided by
Rayleigh-Benard convection. If a fluid is heated very gently from below, the heat
diffuses slowly up through the liquid and is dissipated at the upper surface with-
out any flowing motion of the fluid. But if the heat is turned up, the fluid starts to
convey the thermal energy upward by convection. That is, the lower, hotter layers
of fluid begin to rise in plumes to the top. The hot plumes hit the top of the fluid,
cool, and then sink back. If the fluid is spread out (like gravy in a sauce pan, for
example), convection cells may appear and arrange themselves over the surface
of the liquid in a regular pattern of squares or hexagons. This phenomenon is
commonly seen in the kitchen. Theoretically, the behavior of such a fluid is
completely described by a set of well-known equations (named after Navier and
Stokes) derived directly from Newton’s laws of motion. Indeed, this theory works
quite well in practice until the driving force—in this case, the heat—is turned up
so high that the fluid motion becomes turbulent. Although there is no reason to
believe that the Navier-Stokes equations lose their validity with turbulent flows,
solving the equations in the turbulent domain is a much harder theoretical prob-
lem. It is important in many areas of both basic and applied research. Here, too,
modern experimental techniques, computer simulations, and new analytic ap-
proaches are enabling progress.

OVERVIEW 17
One classic nonequilibrium problem in materials physics is fracture in sol-

ids. How does one characterize a material that is prone to fracture? We usually
describe such a solid as brittle, as opposed to ductile; but what does that distinc-
tion mean at the microscopic level? What is the role of crystal structure, and how
do amorphous or glassy materials differ from crystals in their failure mecha-
nisms? Some progress in addressing these issues has been achieved through
computer simulation and modeling, especially in engineering applications where
the primary interest has been in predicting failure criteria. It is much harder,
however, to predict what happens after failure begins. How do fractures propa-
gate, and how can propagation be controlled or modified? Progress in answering
these questions would have far-reaching consequences.
The science of friction is another example of a classic part of materials
research that is becoming amenable to physical understanding on a microscopic
basis. Friction is related to fracture dynamics because, in many ways, two solid
surfaces sliding past each other look like a propagating shear crack. Friction is a
rich class of phenomena with a variety of underlying mechanisms. When two
imperfect surfaces slide past each other, friction is produced by the cohesion and
decohesion of atomic-scale contact points that are strongly coupled to the defor-
mation modes of the material. Novel techniques, including atomic-scale probe
microscopies, are giving new insight into the dynamic details of these processes.
Although progress in these areas of long-standing interest is very promising,
it is likely that the next major frontier in nonequilibrium physics will be in the
area of biological materials and phenomena. Optical tweezers and other physics-
based probes are enabling molecular-scale observation of biological processes.
Forces between cellular membranes can be measured, and the physical mecha-
nisms whereby proteins are formed and transported within a cell can be observed.
The cell provides a rich new universe of complex nonequilibrium phenomena for
study by physicists. The rewards to society of detailed physical understanding of
fundamental life processes could be enormous.
COMPLEX FLUIDS AND MACROMOLECULAR

AND BIOLOGICAL SYSTEMS
Big molecules have bumpy or sticky places that enable them to assemble
themselves into regular or functional arrangements that are extremely sensitive to
varied environments and conditions of formation. In artificial preparations these
assemblies can form “complex fluids” whose morphology is easily modulated by
changing temperature, dilution, or electrical currents.
Digital watches and portable computer monitors depend on this modulation
in their liquid-crystal displays. The structure, and hence the optical properties, of
the liquid crystal can be altered by small voltages applied across the fluid. Flash-
light batteries now come with liquid-crystal testers that respond to the heat gener-
ated by a resistor. An inexpensive fever thermometer can be made from a plastic

strip that contains liquid crystals; it is accurate enough to indicate a normal

reading or to signal the need for a more accurate measurement by a digital
thermometer (which will itself use a liquid-crystal display). Because these liquid
crystals are so sensitive, their use consumes very little power.
Complex fluids occur in bewildering variety. To describe and control the
different liquid phases, theorists are developing new concepts of molecular orga-
nization. With progressively better understanding of the rules of formation, these
fluids can be used to construct new kinds of materials with unusual topologies.
Extremely light and strong aerogels, used in insulation for example, have a huge
surface area trapped in a relatively small volume.
Polysaccharides are a class of materials that form complex fluids that are
important to industry. In this class are the xanthan, guar gums, and carra-
geenan essential to modern food preparation and stabilization. Xanthan, used in
salad dressing, is so stable and controllable that it can even be used in an oil field
to stimulate petroleum recovery. Such materials have a wide range of viscous and
elastic properties. A better understanding of the relationship between their struc-
ture and properties should lead to many new materials and applications.
Polyolefins, another class of complex fluids, are produced in large quanti-
ties—about as much annually by weight as steel. These molecules, formed into
long-chain polymers, have many uses such as less-expensive alternatives to ny-
lon. With the aid of new catalysts, it became possible during the past decade to
put monomers like ethylene onto the chain in a highly controlled way to create
synthetic materials with a range of properties such as hardness and ductility. The
techniques of physics have great potential to characterize these materials and to
elucidate the relationship between the process by which they were prepared and
their final structure and properties.
Living systems create macromolecules with an enviable degree of specificity
and startling properties. A strand of spider silk, for example, can have a greater
tensile strength than a steel wire of the same diameter. If the physics governing
the synthesis, processing, and related properties of such materials could be under-
stood, it might open up the possibility of new classes of supermaterials. There is
an opportunity for physicists to learn from biologists in this and other areas.
There are many other areas where useful insights have come from a physics-
based approach to objects or to phenomena that traditionally have been in the
domain of biology. Among these are protein-protein interactions, molecular mo-
tors, protein folding, photosynthesis, and nerve action. Modern molecular biol-
ogy would not be the same without the physics-based facilities that have played
key roles in these developments. By determining the structure of very large and
complicated biological molecules at the atomic scale of resolution, physics is
having a significant impact on biology.
Most structure determination is done via x-ray diffraction from crystallized
material. Intense tunable x-ray sources allow these determinations on small
samples. The premier facility where this is done is the Advanced Photon Source

OVERVIEW 19
(APS) at the Department of Energy’s Argonne National Laboratory. Because of

the brightness of this source and the time structure of its output, it is even possible
to do time-resolved studies of changes in the configuration of biological mol-
ecules and aggregate structures. Biologists are the fastest growing class of users
at the Advanced Photon Source. These physics-based facilities may turn out to
be a great venue for creative interactions between physicists and biologists.
Because of its sensitivity to atomic motions and light (low-Z) atoms, neutron
scattering is an important tool for studying large biological molecules. Neutrons
are particularly sensitive to the vibrational modes that provide clues to the dy-
namical behavior of large molecules. Biological molecules are made mostly of
carbon, hydrogen, nitrogen, and oxygen; neutrons are particularly good probes of
such light elements, providing information that is complementary to that obtained
with x-ray sources. Although neutron sources in the United States are very
active, the dearth of high-intensity sources here is an obstacle to progress in this
area; this obstacle will be removed when the Spallation Neutron Source comes
online in 2005.
Physics has come to define the language for the study of protein folding, in
which a linear chain of complex biological molecules arranges itself into the
compact tangles that proteins adopt in living systems. Like structure determina-
tion, observation of the dynamics of folding depends on the availability of in-
tense, tunable x-ray sources.
There are reasons to be optimistic about the ability of physicists to provide
understanding of very complex materials and to engage in productive collabora-
tions with biologists and chemists in the study of increasingly complex molecules
and systems. Considering the potential for outcomes that will benefit humanity, it
makes sense to look for mechanisms to promote this collaboration.
A number of the general recommendations in this report address the need for
collaboration. Applying these recommendations to actual efforts to encourage
collaboration between physicists and life scientists is a special challenge. Among
the efforts that may work particularly well to bring biologists and physicists to-
gether are interdisciplinary workshops, summer schools with laboratories for scien-
tists at all career stages (including nascent Ph.D.s), new cross-disciplinary courses
(biologists need to learn some physics, physicists need to learn some chemistry
and biology, and so on), inclusion of new biology-related material in introductory
physics courses, and new texts that mix both physics and biology frameworks. The
National Institutes of Health should continue to take the lead in this area, working
with the National Science Foundation and the Department of Energy.
NEW TOOLS FOR RESEARCH: FROM THE BENCHTOP

TO THE NATIONAL LABORATORY
The arsenal of research tools for condensed-matter and materials physics
includes a wide variety of experimental equipment. This equipment enables the

creation of extreme environments in which to explore the behavior of matter and

the synthesis of materials with extraordinary properties. It also provides new
“eyes” to observe and new “hands” to manipulate at the atomic scale. Examples
of such equipment range from benchtop-scale atomic-force microscopes used by
individual investigators, to storage rings the size of a small town that generate the
x-rays used by collaborative research groups with many members.
These experimental tools enable new insights into systems of recognized
importance and the exploration of completely new regimes. One example of
scientific progress that depended on modern instruments of research involved
unraveling the properties of the high-Tc superconductors. Developing today’s
understanding of these materials depended on the use of experimental tools:
• Neutron diffraction was used to determine atomic coordinates.

• Synchrotron radiation was used to determine the electronic structure.
• Electron microscopy made it possible to determine the microstructure.
• Neutron scattering was used to determine magnetic order.
• High magnetic fields and high pressures were used to gain understanding
of charge transport.
Many of these studies were performed at large- or medium-scale facilities.

Although large facilities are critical to condensed-matter and materials phys-
ics, another theme that pervades this report is the importance of atomic-scale
observation and manipulation. Two of the most important tools for this purpose
are the scanning-tunneling microscope and the transmission electron microscope.
The equipment is on the small-to-medium scale.
Scanning-tunneling microscopes work by placing a probe that is sharp, on an
atomic scale, so close to the sample that the quantum wave function of the
electron allows it to jump the gap. By scanning this probe over the sample, using
sophisticated positioning technology, the surface can be mapped atom by atom.
The resolution is far better than anything that can be achieved with light waves,
because the wavelength of light is thousands of times too large to visualize atoms.
Various kinds of scanning-probe microscopes are now commonly available, in-
cluding instruments that can examine chemical reactivity, magnetism, optical
absorption, mechanical response, and other properties. A particularly promising
development is the imaging of molecules, including rather large ones that play a
role in biological processes.
Scanning-tunneling microscopes can go beyond measuring structures to actu-
ally creating them by positioning individual atoms. In principle, it is possible to
create any structure to test our understanding of the physics of devices at this scale.
One of the challenges in this area is to learn to control the stability of atomic-scale
structures. In general, individual atoms placed on a surface will not stay put unless
the temperature is extremely low. Another challenge is that, if this technique is ever
to lead to practical devices, it would have to be much faster than it is now.

OVERVIEW 21
Electron microscopes, which use beams of electrons to probe the sample, are
able to penetrate below the surface. They have much higher resolution than
optical microscopes because of the shortness of the electron wavelength. Instru-
ments with 1-Å resolution have been demonstrated. Development of electron
microscopes has occurred primarily in Europe and Japan. These instruments
show great promise for reconstructing three-dimensional structures of biologi-
cal interest as well as for studying the properties of amorphous and disordered
materials.
We can be sure that improved brightness, spectroscopy, and resolution in
electron microscopes will allow more precise determination of structure and
composition in ultra-small volumes of materials, even when these are embedded
below the surface. This will have a continuing major impact on the microstruc-
tural study of all materials, for example, identifying interfacial structures, solving
important problems of support effects on small clusters, and understanding the
structural basis of adhesion and fracture in materials. These new capabilities will
require a significant reinvestment in infrastructure and increased investment in
instrumental research and development.
An equally important theme is that, to a growing degree, significant ad-
vances in a number of sciences depend on large national facilities. The United
States has been particularly strong in the development of synchrotron radiation
sources. These sources depend on the fact that when an electron is accelerated, it
gives off light. The most sophisticated (third-generation) synchrotron radiation
source in the United States is the Advanced Photon Source (APS) at Argonne
National Laboratory. The APS uses devices called “undulators” that wiggle an
electron beam by passing it through an array of powerful magnets to generate
tunable beams of very high intensity x-rays. The power and controllability of the
x-rays from the APS have made possible a new generation of experiments that
have resolved structures with unprecedented precision.
The technology now being developed for a fourth generation of light sources
may be eight orders of magnitude more powerful than even the APS and will
have pulse lengths less than a picosecond. These devices, called “free electron
lasers,” use undulators configured so that the radiation given off bathes the elec-
tron beam and stimulates further emission of radiation in a process closely analo-
gous to the operation of a laser. If past experience is a guide, the greater intensity
and coherence that these devices will one day offer will lead to new classes of
experiments and new insights into the structure of materials.
Synchrotron radiation is being used to conduct research in a number of areas.
Inelastic x-ray scattering has provided unique information about the dynamics of
fluids and glasses. Photoemission experiments have provided much information
about the electronic structure of solids, which is essential to understanding the
physical details of the operation of semiconductor devices and integrated circuits.
X-ray studies of disordered systems have given insight into inorganic glasses and
biological structures. Information can be obtained about chemical states and

environments of individual atoms in the structure of disordered systems. Struc-

tural changes associated with the functioning of metalloproteins in processes like
nitrogen fixation, photosynthesis, and respiration can be observed.
The most rapidly growing and arguably the most important use of synchro-
tron radiation is in protein crystallography, in which the structure of biologically
important proteins is determined. Crystallography of big molecules using syn-
chrotrons is the primary source of insight into three-dimensional biological
structures. Biologists are just scratching the surface of the possibilities. Approxi-
mately two-thirds of all new structures published in Science and Nature in 1995
used synchrotron radiation, and the number is growing. Progress in this area in
the next 10 years should be breathtaking, both in its intellectual scope and its real-
world implications. Pharmaceutical companies are pursuing a “drugs-by-design”
approach to relating the structure of complex molecules to their function and
activity in biological systems; this approach has the potential to revolutionize the
industry.
Another area in which the use of synchrotron radiation has been of benefit
involves providing the means for researchers in the life sciences to understand the
workings of a variety of biological structures:
• Scientists now understand how muscle contraction works at the molecu-

lar level.
• Scientists now know how living cells mobilize energy.
• Scientists understand how nitrogen-fixing bacteria work.
• Scientists have learned the structure of ribozyme, a catalytic form of
RNA.
• Scientists have determined plant and animal viral structures.
One of the key factors that enabled these results was that both the physics
community and the sponsoring agencies (primarily the Department of Energy)
adopted a philosophy that synchrotron facilities are national resources that should
be designed and implemented to serve all the branches of science. That has meant
investing resources in making the machines and experimental facilities reliable,
predictable, and easily used by researchers unfamiliar with accelerator facilities.
It has meant providing the human infrastructure necessary to support such users.
It has meant husbanding the special institutional arrangements necessary to make
such users successful. Nonphysicist users are now in the majority at most syn-
chrotron facilities.
Neutron scattering is a technique particularly sensitive to spin states and
low-atomic-weight atoms. It is therefore particularly well suited for the study of
magnetism, high-Tc materials, polymers, and biological materials. The major
research facilities for neutron scattering in the United States have been the De-
partment of Energy’s high-flux reactors at Brookhaven National Laboratory and
at Oak Ridge National Laboratory, the Department of Commerce’s reactor at the

OVERVIEW 23
National Institute of Standards and Technology, and accelerator-based pulsed

sources at Argonne National Laboratory and Los Alamos National Laboratory.
These facilities have not kept pace with developments in Europe, and in the last
decade, leadership decisively passed to the Institute Laue-Langeven reactor facil-
ity in France and the ISIS pulsed facility in the United Kingdom. Among the
recent successes of neutron scattering has been the demonstration that the high-Tc
superconductors have a common feature—nearly square planar arrays of copper
and oxygen atoms. Neutron scattering also was used to image vortex lattices in
high-Tc superconductors. These studies gave evidence for two of the most impor-
tant new ideas about superconductivity. The first is that solids can become super-
conducting by mechanisms analogous to those responsible for superfluidity of
helium-3. The second is that vortices in superconductors can have intricate phase
diagrams. Structural information about the perovskite manganites that exhibit
“colossal magnetoresistance” has also come from neutron scattering.
So far we have discussed strategies for research that involves using powerful
tools to probe the structure of matter, to visualize what is happening at the atomic
and molecular levels. Another strategy that has proved effective in flushing out
new insights is placing matter in extreme conditions of temperature, pressure, or
magnetic field. A recurring theme of this study has been exploration of what
might be called the “low-energy frontier.” One aspect of this frontier is extremely
low temperatures. In this regime, very gentle, low-energy effects such as super-
conductivity and superfluidity begin to emerge; but these effects are washed out
by the chaotic thermal motion of the atoms and electrons at higher temperatures.
An experimental tour de force of the last decade was the discovery of collective
nuclear spin order at nanokelvin temperatures in elemental copper.
The rapidly growing capability of computers for experimental control, visu-
alization, and numerical simulation is having a significant impact on condensed-
matter and materials physics. Computers used to be viewed not as part of the
instrumentation armamentarium but as something outside it. But that may be
changing. Modern computers and their associated visualization capabilities are
now so powerful, they are beginning to provide “virtual laboratories” that offer
new ways to acquire physical insight by exploring the effects of varying physical
parameters. Real physical experiments will always be necessary, but computa-
tion may provide a virtual experimental space that will greatly speed up decisions
about what kinds of experiments to do and where to look for new phenomena.
A major event of the decade for individual-researcher laboratories has been
the development of scanning-probe microscopes as routine, off-the-shelf analyti-
cal tools. The technologies involved hold the promise of control and manipula-
tion of surface materials at the atomic scale as well as study of large molecules in
fine detail.
On the intermediate scale of infrastructure, there have been three important
developments: greater access to electron microscopes and related equipment, the
exploitation of university-based microfabrication centers, and reinvigoration of

the U.S. high-field magnet research through the establishment of the National
High-Field Magnet Laboratory.
The establishment of third-generation synchrotron light sources at Lawrence
Berkeley National Laboratory and at Argonne National Laboratory and the deci-
sion to construct the new Spallation Neutron Source (SNS) have dominated the
decade as far as large national facilities are concerned. It is particularly crucial to
move forward with construction of the SNS to make the United States competi-
tive in neutron-scattering studies. Once the SNS is commissioned at Oak Ridge
National Laboratory, U.S. researchers can begin the process of recapturing the
lead in the use of neutrons to study structure and spins in superconductors, poly-
mers, and other materials.
We can confidently predict a rapid growth in knowledge and understanding
of biological materials and living organisms resulting from the exploitation of the
Advanced Photon Source by the biology community. That progress will be accel-
erated once the SNS becomes operational. The extensive deployment of various
microscopies in many laboratories can be expected to implement great strides in
understanding surface physics.
The rapid pace of development of research at various scales has depended
on accelerator science and research on the physics of smaller instrumentation.
This work has had to be parasitic on various enterprises, despite the fact that
advances in scientific equipment propel science forward in great leaps. How
much better could we exploit the leverage that instrumentation research has if
we were to recognize it as an important enterprise worthy of planned invest-
ment! The institutional frameworks for such investments clearly depend on
scale, but there are natural environments at each level. Expertise in tomorrow’s
beam physics, for example, partly resides at the major centers of high-energy
physics research, but development for low-energy applications will likely
occur elsewhere. The materials research science and engineering centers are
one set of obvious potential homes for intermediate-scale instrumentation
development.
FINDINGS AND RECOMMENDATIONS

Condensed-matter and materials physics is entering an era of great excite-
ment and anticipation as powerful new experimental and computational capabili-
ties are brought to bear on some of the most fundamental scientific and technical
challenges of our time. Underlying these challenges is the knowledge that drives
the information revolution, modern materials technology, and biotechnology en-
abled by understanding of the molecular basis of life. We have seen astounding
developments over the past decade such as buckyballs and carbon nanotubes,
high-temperature superconductivity, giant and colossal magnetoresistance, and
large-scale quantum phenomena. The next decade, enriched by powerful new
research tools, promises to be even more extraordinary.

OVERVIEW 25
New capabilities for condensed-matter and materials physics research include

spectacular advances in the atomic-scale characterization and manipulation of ma-
terials, computer simulations of large interacting systems, and the ability to relate
properties and phenomena from molecular- to macroscopic-length scales. These
new capabilities are uniting the worlds of atomic-scale behavior and macroscopic
phenomena in ways that provide avenues for understanding and designing materi-
als and processes from the atoms up. In turn, this new understanding holds the
promise of breakthroughs at a time when the limits of incremental progress are
being tested in materials-based technologies ranging from integrated circuits and
magnetic storage devices to the synthesis of advanced polymers to the performance
of materials under extreme conditions. Perhaps the greatest impact will be felt at the
interface between biology and physics, where the convergence of condensed-
matter and materials physics and molecular biology is expected to drive important
advances in the fundamental understanding of biological processes.
Condensed-matter and materials physics faces critical challenges in realizing
this future. Investments in facilities and research infrastructure are essential to
provide a world-class research environment and to enable breakthrough opportu-
nities. Partnerships across disciplines and among universities, government labo-
ratories, and industry are essential to leverage resources and strengthen interdis-
ciplinary research and connections to technology. Finally, special attention must
be given to condensed-matter and materials physics education to ensure the avail-
ability of intellectual capital to sustain the vitality of the field and its contribu-
tions to society.
Research Infrastructure
The United States has a strong foundation of research groups and small-scale
centers located in universities and government laboratories. Centers play an es-
sential role in a number of areas including microcharacterization, processing,
synthesis, and state-of-the-art instrumentation development. Research groups and
centers are a crucial reservoir of expertise. They also play an important institu-
tional role by providing a meeting ground for research and development person-
nel in industry and students and researchers in universities and government labo-
ratories. Centers bring together the problem-definition capabilities of industry
with the educational role of the universities and the research missions of govern-
ment laboratories. As a result, leading-edge research capabilities are applied to
important areas of microcharacterization, processing, synthesis, and instrumenta-
tion. Centers also bring a long-term commitment to applying intellectual excel-
lence to research problems and to developing expertise in the next generation of
researchers in these essential areas of study.
The role that small-scale centers now play has been fostered also in major
industrial research laboratories as well as by the research strategy of the Depart-
ment of Defense. But the burden now falls much more heavily on research groups

and small centers in universities and government laboratories. Therefore, it is

appropriate to strengthen this part of the nation’s research infrastructure. Addi-
tional support, long-term commitments, and oversight structures that involve all
the interested parties (universities, government laboratories, and industry) are
necessary to accomplish this fortification.
Recommendations for Upgrading the Infrastructure

• The National Science Foundation, the U.S. Department of Energy, the
U.S. Department of Defense, and other agencies that support condensed-matter
and materials physics research should continue to nurture the core research at the
heart of the field. The research areas described in the Overview provide a guide
to the scientific arenas at the forefront of this work.
• The agencies that support and direct research should plan for increased
investment in modernizing the condensed-matter and materials physics research
infrastructure at universities and government laboratories.
• The National Science Foundation should increase its investment in state-
of-the-art instrumentation and fabrication capabilities, including centers for in-
strumentation R&D, nanofabrication, and materials synthesis and processing at
universities. The Department of Energy should increase its support for such
programs at national laboratories and universities.
Major Facilities
The emergence of national synchrotron and neutron facilities has revolution-
ized our understanding of the atomic-scale structure and dynamics of materials.
The nation is fortunate to have world-class facilities for synchrotron research.
However, the situation is strikingly different for neutrons, where we find our-
selves with fewer facilities than those judged inadequate by national review
committees more than a decade ago. Many of the advances in structural biology,
polymers, magnetic materials, and superconductivity depend on access to state-
of-the-art neutron-scattering facilities. Without a new neutron source, the nation
cannot be competitive in these and other areas of enormous scientific and techno-
logical significance. This is an urgent and immediate need, and the committee
strongly recommends construction of the Spallation Neutron Source (SNS). Up-
grades at existing neutron-scattering facilities are also essential to sustaining
neutron-scattering research in the United States during SNS construction as well
as to strengthen the field and provide broad access to the user community.
Over the past decade there has been an explosion in the use of synchrotron
facilities. A great success of these facilities has been the rapid growth in their use
across the broad spectrum of science. At national synchrotron facilities biolo-
gists are attacking the structure of biological molecules, chemists are improving
drug designs, and environmental scientists are following the migration of envi-

OVERVIEW 27
ronmental pollutants, all alongside materials researchers. In fact, life scientists

are the fastest growing user community at national synchrotron facilities and
currently occupy more than 25 percent of available beam time. This large influx
of users from other scientific disciplines is remarkably productive and is creating
a healthy scientific melting pot, but it is also straining the ability of the facilities
to respond. Modest investments at existing synchrotron facilities can greatly
expand current capabilities and help alleviate this problem. On the horizon are
fourth-generation light sources that offer enormous gains in intensity and coher-
ence over existing sources. The committee recommends upgrades at existing
synchrotron facilities and research and development to explore possible options
for fourth-generation sources.
Recommendations for Major Materials Research Facilities

• The insufficiency of neutron sources in the United States should be ad-
dressed in the short term by upgrading existing neutron-scattering facilities and in
the long term by the construction of the Spallation Neutron Source.
• Support for operations and upgrades at synchrotron facilities, including
research and development on fourth-generation light sources, should be strength-
ened.
• The broad use of synchrotron and neutron facilities across scientific disci-
plines and sectors should be considered when establishing agency budgets.
Partnerships
Condensed-matter and materials physics is becoming increasingly interre-
lated with other fields of science and technology, with important links to many
disciplines including other branches of physics, chemistry, materials science,
biology, and engineering. At the same time, the field has advanced to the point
where it is often impractical and sometimes impossible to assemble in one place
all of the intellectual resources and specialized equipment for a given research
project. Continued progress in the field depends on establishing effective part-
nerships across disciplines and among universities, government laboratories, and
industry. These partnerships enable cross-disciplinary research, leverage re-
sources, and provide awareness of technological drivers and potential applica-
tions. The extraordinary scientific and technological success of the major indus-
trial laboratories over the past half-century resulted from their ability to integrate
long-term fundamental research, cross-disciplinary teams involving experimen-
talists and theorists, materials synthesis and processing, and a strategic intent.
Virtual elements of this fertile ground exist in potential partnerships among uni-
versities, government laboratories, and industry. Federal R&D agencies should
encourage partnerships that recreate this environment in appropriate subfields of
condensed-matter and materials physics.

Recommendations for Research and Development Partnerships

• Federal agencies should provide incentives for formation of partnerships
among universities and government and industrial laboratories that carry out
research in condensed-matter and materials physics.
These research and development partnerships should be encouraged in order

to:
— Optimize the use of infrastructure and facilities,
— Enable cross-disciplinary research,
— Improve university and government laboratory appreciation of industry
priorities and needs,
— Share the risks and returns of long-term research, and
— Assemble teams that can recreate the fertile research environment of the
large industrial research laboratories of the past half-century.
These partnerships should be fostered by:
— Making resources available through special programs that stimulate part-

nerships,
— Developing effective protocols for resolving intellectual property issues
in cooperative research,
— Encouraging university and government laboratory internships and sab-
baticals in industry, and
— Requiring partners to have a stake in the partnership (e.g., for universi-
ties and government laboratories, the partnership should add value to core mis-
sions).
Education
Intellectual capital is probably the single most important investment for
science and technology. Intellectual capital in condensed-matter and materials
physics occupies a special place in the national economy, underpinning many of
the technological advances that drive economic growth. The U.S. system of
graduate education, research universities, government and industrial laboratories,
and national facilities for condensed-matter and materials physics is a major
reason for rapid progress in research and technological applications. Maintaining
this progress requires continued commitment to strengthening these institutions.
In addition, condensed-matter and materials physics must play a crucial role in
engaging undergraduates in research and improving their understanding of sci-
ence and technology. Making investments to develop the human capital essential
for leadership in condensed-matter and materials physics and related technolo-
gies will pay rich dividends to the nation. Successful accomplishment of these

OVERVIEW 29
objectives will also help the larger field of physics to adjust to a new role in
which economic security becomes the dominant justification for national invest-
ments in research.
Recommendations for Education

• Universities should endeavor to enhance their students’ understanding of
the role of knowledge integration and transfer as well as knowledge creation.
• Universities should develop ways to bring the excitement and creativity
of research and discovery into education at an earlier stage.
• University departments should consider new professional degree programs
that link undergraduate physics education with, for example, engineering-
oriented disciplines.
• Universities should foster joint academic appointments across depart-
ments to break down disciplinary barriers. Campuses should experiment with the
creation of “virtual departments” to aid intellectual restructuring to better achieve
their research and education missions in changing times.
• Universities need to expand existing programs that enable undergraduates
to have research experiences in faculty laboratories or summer internships in
industry or at national laboratories.
• Universities should recognize the importance of knowledge integration
and transfer in addition to knowledge creation.
• Applied physics departments and programs should link to industrial liai-
son programs, which generally are strong in colleges of engineering.
• Agencies, particularly the National Science Foundation, should provide
incentives for action in these areas.
RESEARCH THEMES
Throughout this study the themes of new experimental and computational
capabilities, the ability to address problems of increasing complexity, and the
importance of relationships with other fields pervade the subdisciplines of
condensed-matter and materials physics (see Box O.1). These themes provide a
sense of vitality and optimism for the future of condensed-matter and materials
physics. Maintaining scientific excellence, a long-term perspective, and a world-
class environment for research are essential. Investing in facilities, encouraging
partnerships, integrating research and education, and encouraging discovery are
critical elements. But where is the field headed? Although it is often dangerous to
predict the future in science, the committee identified 10 areas that span and
underpin the subdiscipline-specific scientific priorities of condensed-matter and
materials physics as described in the body of this report. These areas, listed in
Box O.1, encompass the committee’s view of the high-level strategic priorities
that have emerged from the internal dynamics of the field and that are likely to

BOX O.1 Strategic Scientific Themes in Condensed-Matter

and Materials Physics
• The quantum mechanics of large, interacting systems

• The structure and properties of materials at reduced dimensionality
• Materials with increasing complexity in composition, structure, and function
• Nonequilibrium processes and the relationship between molecular and me-
soscopic properties
• Soft condensed matter and the physics of large molecules, including biolog-
ical structures
• Controlling electrons and photons in solids on the atomic scale
• Understanding magnetism and superconductivity
• Properties of materials under extreme conditions
• Materials synthesis, processing, and nanofabrication
• Moving from empiricism toward predictability in the simulation of materials
properties and processes
characterize condensed-matter and materials physics research over the next

decade.
Condensed-matter and materials physics lies at the heart of revolutionary
advances in broad areas of science and technology. The next decade promises
exciting new discoveries and technology impacts as powerful new capabilities in
synchrotron and neutron research, atomic-scale visualization, nanofabrication,
computing, and many other areas probe the secrets of materials and materials-
related phenomena. This is a new era. Vast new arenas, ranging from subtle
quantum phenomena, to macromolecular science, to the realm of complex mate-
rials, are increasingly accessible to fundamental study. It is a time of exceptional
opportunity to perform pioneering research at the technological frontier—a fron-
tier enabled by advances in condensed-matter and materials physics.

1
Electronic, Optical, and Magnetic Materials
and Phenomena:
The Science of Modern Technology
Important and unexpected discoveries have been made in all areas of con-
densed-matter and materials physics in the decade since the Brinkman report.1
Although these scientific discoveries are impressive, perhaps equally impressive
are technological advances during the same decade, advances made possible by
our ever-increasing understanding of the basic physics of materials along with
our increasing ability to tailor cost-effectively the composition and structure of
materials. Today’s technological revolution would be impossible without the
continuing increase in our scientific understanding of materials, phenomena, and
the processing and synthesis required for high-volume, low-cost manufacturing.
The technological impact of such advances is perhaps best illustrated in the areas
of condensed-matter and materials physics discussed in this chapter, which will
examine selected examples of electronic, magnetic, and optical materials and
phenomena that are key to the convergence of computing, communication, and
consumer electronics.
Technology based on electronic, optical, and magnetic materials is driving
the information age through revolutions in computing and communications. With
the miniaturization made possible by the invention of the transistor and the inte-
grated circuit, enormous computing and communication capabilities are becom-
ing readily available worldwide. These technological capabilities, which enabled
the information age, are fundamentally changing how we live, interact, and trans-
act business. Semiconductors provide an excellent demonstration of the strong
1National Research Council [W.F. Brinkman, study chair], Physics Through the 1990s, National
Academy Press, Washington, D.C. (1986).
31

interplay between and interdependence of science and technology. Perhaps

in no other area are advances in technology more closely linked to advances in
understanding.
This chapter is not intended to be comprehensive; rather, it seeks to illustrate
the pivotal role of condensed-matter and materials research in providing the
understanding required to develop enabling technologies. At the same time, the
development of these new technologies has greatly expanded the tools and capa-
bilities available to scientists and engineers in all areas of research and develop-
ment, ranging from basic research in physics and materials to other areas of
physics and to such diverse fields as medicine and biotechnology. The examples
discussed also make evident the importance of long-term, sustained research in
realizing the benefits to society of improved scientific understanding of materials
(see Figure 1.1).
The Era of Change

COMPUTERS
TECHNOLOGY
Giant Magnetoresistance - 1990s
I business and scientific
computers, personal computers,
optical and magnetic storage,
liquid crystal displays
Large-Scale Computation - 1970s
Semiconductor Diode Laser - 1970s COMMUNICATIONS
Optical Fibers -
Laser -
1970s
1961s
M information superhighway,
cellular phones, satellite
Integrated Circuit - 1959s communications, high-capacity
Transistor - 1947s fiber-optic cables
Telephony - 1876s
P NATIONAL SECURITY
advances in communication,
command, and control,
SCIENTIFIC sensors, weapons systems
FOUNDATIONS A ENERGY
photovoltaics, sensors,
Correlated Electron States - 1980s light-weight motors, high-
Scanning Tunneling Microscopy - 1980s performance transformers
BCS Theory of Superconductivity - 1957s
Electron Microscopy -
Electronic States in Crystals -
1930s
1920s
C TRANSPORTATION
automotive electronics, sensors,
avionics, air-traffic control
Wave Nature of the Electron - 1927s
Quantum Mechanics - 1920s ENTERTAINMENT
X-ray Diffraction -
Superconductivity -
Magnetoresistance -
1911s
1911s
1856s
T consumer electronics
MEDICINE
lasers, medical imaging, sensors
FIGURE 1.1 Incorporation of major scientific and technological advances into new
products can take decades and often follows unpredictable paths. Illustrated here are
some selected technologies supported by the foundations of electronic, photonic, and
magnetic phenomena and materials. These technologies have enabled breakthroughs in
virtually every sector of the economy. The two-way interplay between foundations and
technology is a major driving force in this field. The most recent fundamental advances
and technological discoveries have yet to realize their potential.

ELECTRONIC, OPTICAL, AND MAGNETIC MATERIALS AND PHENOMENA 33
Although technological advances today are most often associated with the
information age or communications and the computing revolution, impressive
advances continue to be made across a broad spectrum of technologies and scien-
tific disciplines (see Box 1.1). For example, progress in condensed-matter and
materials physics has led to advances in biology, medicine, and biotechnology.
New tissue diagnostics based on diffusing light probes use understanding
borrowed directly from the physics of carrier transport in mesoscopic random
materials. The development of new optical microscopies, such as two-photon
confocal, optical coherence, and near-field optical microscopy, together with the
widespread use of optical tweezers, have started a revolution in the observation
and manipulation of submicrometer-sized objects in cell biology, in new forms of
spectroscopic endoscopy, and in gene sequencing techniques. The emergence of
high-power solid-state lasers and solid-state detectors and the widespread use of
fiber optics make new optical approaches for diagnostics, dentistry, and surgery
increasingly easy. A new form of magnetic resonance imaging enabled by semi-
conductor laser pumping of spin-polarized xenon gas has allowed the three-
dimensional mapping of lung function. The generation of femtosecond pulses of
light by the use of new solid-state lasers has begun another revolution in our
understanding of the subpicosecond dynamics of biological molecules on the
important frontiers of molecular signal processing and protein folding. Although
not covered in detail here, such advances in the use of optics in medicine and
biology are discussed in detail in another National Research Council report.2 In
addition, semiconductor and other solid-state lasers or enhanced solid-state de-
tector arrays, offshoots from condensed-matter physics, are enabling major ad-
vances in the fields of atomic and molecular physics, physical chemistry, high-
energy physics, and astrophysics. New optical materials and phenomena are also
responsible for a number of advances in the technologies associated with print-
ing, copying, video and data display, and lighting.
In the realm of magnetic materials, the loss of cobalt in the 1980s because of
political unrest in Zaire prompted an intense research effort to find cobalt-free
bulk magnetic materials. This led to major advances in creating magnetic struc-
tures from neodymium and iron, which had superior properties and lower cost
compared with cobalt alloys for electric motors and similar applications requiring
magnets with high permanent magnetization. These new magnets, which are
achieved through complex alloys and even more complex processing sequences,
are vastly expanding the industrial use of bulk magnetic materials.
Advances in magnetic materials and their applications are not limited to bulk
materials with high permanent magnetization and magnetic materials used in
information storage. Improvements in soft bulk magnetic materials play an im-
portant role in transformers used in the electric power distribution industry. In-
2National Research Council [C.V. Shank, study chair], Harnessing Light: Optical Science and
Engineering for the 21st Century, National Academy Press, Washington, D.C. (1998).

BOX 1.1 The Science of Information-Age Technology
The predominant semiconductor technology today is the silicon-based inte-

grated circuit. The silicon integrated circuit is the engine that drives the information
revolution. For the past 30 years, this technology has been dominated by Moore’s
Law: that the density of transistors on a silicon integrated circuit doubles about
every 18 months.* Moore’s Law articulates the increased functionality-per-unit
cost that is the origin of the information revolution. Today’s computing and com-
munications capability would not be possible without the phenomenal 25 to 30
percent per year exponential growth in capability per unit cost since the introduc-
tion of the integrated circuit in about 1960. That sustained rate of progress has
resulted in high-density memories with 64 million bits on a chip and complex, high-
performance logic chips with more than 9 million transistors on a chip. This trend
is projected to continue for the next several years (see Figures 1.1.1 and 1.1.2).
If the silicon integrated circuit is the engine that powers the computing and
communications revolution, optical fibers are the highways for the information age.
Although fiber optics is a relatively recent entrant into the high-technology arena,
its impact is enormous and growing. Fiber is now the preferred technology for
transmission of information over long distances. There are already approximately
30 million km of fiber installed in the United States and an estimated 100 million km
worldwide. In part because of the faster than exponential growth of connections to
the Internet, optical fiber is being installed worldwide at an accelerated rate of
PROCESSING POWER ON SINGLE CHIP

10,000
DSPC6202
1,000 Pentium II
DSP16110
Processing Power ( MIPS )
Pentium Pro
100 Pentium
DSP16A
DSP16
10 486
386
DSP1620
1 DSP1
286
0.1
1976 1980 1984 1988 1992 1996 2000
YEAR
FIGURE 1.1.1 Computing power versus time in microprocessors. (Courtesy of
Intel.)
*Moore’s Law, first articulated by Gordon Moore of Intel Corporation, is not a

statement of physics. It is a statement that the industry will perform the R&D
necessary and supply capital investment at the rate required to achieve this
doubling rate.

Key foundations of the

modern silicon semiconductor industry
Microprocessor 1971 ,,,,,,,,

Dynamic Random Access Memory (DRAM) 1967 .,,,,,,,,
Epitaxial diffused transistor 1960 ,,,,,,,,,,
MOSFET device 1959 ,,,,,,,,,,,
Patents on the integrated circuit 1959 ,,,,,,,,,,,,
Stabilization of silicon surface by oxide 1959 ,,,,,,,,,,,,,
Doping by ion implantation 1954 ,,,,,,,,,,,,,,
Zone refining 1950 ,,,,,,,,,,,,,,,
p-n junction theory 1948 ,,,,,,,,,,,,,,,,
Minority carrier injection - Bipolar transistor 1947 ,,,,,,,,,,,,,,,,
Energy barrier between semiconductor and metal , 1939 ,,,,,,,,,,,,,,,,,,
Semiconductor band structure - Gap critical to ,mmmmmmmmm
conductivity and concept of doping 1931 ,,,,,,,,,,,,,,,,,,,,
Concept of the field-effect transistor 1926 ,,,,,,,,,,,,,,,,,,,,,
Discovery of the electron 1897 ,,,,,,,,,,,,,,,,,,,,,,
FIGURE 1.1.2 History of semiconductor technology.
more than 20 million km per year—more than 2,000 km per hour, or around Mach
2. In addition, the rate of information transmission down a single fiber is increasing
exponentially by a factor of 100 every decade. Transmission at 2.5 terabits per
second has been demonstrated in the research laboratory, and the time lag be-
tween laboratory demonstration and commercial system deployment is about 5
years. The analog of Moore’s Law for fiber transmission capacity, which serves as
a technology roadmap for lightwave systems, is shown in Figure 1.1.3. Figure
1.1.4 summarizes the history of optical communications technology.
Compound semiconductor diode lasers provide the laser photons that trans-
port information along the optical information highways. Semiconductor diode la-
sers are also at the heart of optical storage and compact disc technology.
In addition to their use in very high-performance microelectronics applications,
compound semiconductors have proven to be an extremely fertile field for advanc-
ing our understanding of fundamental physical phenomena. Exploiting decades of
basic research, we are now beginning to be able to understand and control all
aspects of compound semiconductor structures, from mechanical through elec-
tronic to optical, and to grow devices and structures with atomic layer control, in a
few specific materials systems. This capability allows the manufacture of high-
performance, high-reliability, compound semiconductor diode lasers that can be
modulated at gigahertz frequencies to send information over the fiber-optic net-
works. High-speed semiconductor-based detectors receive and decode this infor-
mation. These same materials provide the billions of light-emitting diodes sold
annually for displays, free-space or short-range high-speed communication, and
numerous other applications. In addition, very high-speed, low-power compound
semiconductor electronics play a major role in wireless communication, especially
for portable units and satellite systems.
Another key enabler of the information revolution is low-cost, low-power, high-
density information storage that keeps pace with the exponential growth of com-

BOX 1.1 Continued
3000
*
1000
*
300
100
30
Capacity (Gb/s)
10
Experimental
1
Single Channel (ETDM)
Multi-Channel (WDM)
Single Channel (OTDM)
0.3 WDM + OTDM
WDM + Polarization Mux
* WDM + OTDM
WDM
0.1
Commercial
Single Channel (ETDM)
0.03 Multi-Channel (WDM)
80 82 84 86 88 90 92 94 96 98 2000
Year
FIGURE 1.1.3 Exponential growth in data transmission rate in fibers. (Courtesy

of Bell Laboratories, Lucent Technologies.)
puting and communication capability. Both magnetic and optical storage are in
wide use. Recently, the highest performance magnetic storage/readout devices
have begun to rely on giant magnetoresistance (GMR), a phenomenon that was
discovered by building on more than a century of research in magnetic materials.
Although Lord Kelvin discovered magnetoresistance in 1856, it was not until the
early 1990s that commercial products using this technology were introduced (see
Figure 1.1.5). In the past decade, our understanding of condensed matter and
materials converged with advances in our ability to deposit materials with atomic-
level control to produce the GMR heads that were introduced in workstations in
late 1997. It is hoped that with additional research and development, spin valve
and colossal magnetoresistance (CMR) technology may be understood and ap-
plied to workstations of the future. This increased understanding, provided in part

Commercial amplified undersea system 1995

Er-doped fiber optical amplifier 1987 .
Fiber loss reduced to 0.15 dB/km @ 1500 nm 1985
Semiconductor quantum well laser 1973 ,
Commercial lightwave communications 1971
Distributed feedback concept 1971
,,
Silica optical fiber with less than 20 dB/km loss 1970
Room temperature CW double heterojunction
laser diode 1970
Observation of amplification in fibers 1964 fhlprst
III-V semiconductor injection laser diode 1962
Observation and theory of non-linear optics 1961
Pulsed ruby laser 1960
Observation of maser 1954
Theory of stimulated emission 1917
Glass waveguide 1870
youo
FIGURE 1.1.4 History of optical communications technology.
IBM ships first GMR head 1997
Magnetic Tunnel Junctions at room temperature 1995

(10% at 200 Oe at 295K)
CMR observed at room temperature 1994
IBM ships first MR head 1991
Record Room Temperature GMR in sputtered Co/Cu 1991

(70% at 10 kOe at 295K)
GMR observed in sputtered polycrystalline multilayers 1989

(Fe/Cr, Co/Ru, . . .)
Giant MR (GMR) observed at low temperature
in MBE-Grown single crystal Fe/Cr structures 1988
(80% at 20 kOe at 4.2K)
Magnetic tunnel valve (MTV) 1973

(14% at 4.2K)
Large MR observed in ultra-perfect single

crystal Fe whiskers at low temperatures 1968
Very large MR in La-Ca-Mn-O perovskites

in large fields below room temperature 1955
(now described as Colossal MR or CMR)
Anisotropic MR (AMR) observed in soft magnetic alloys 1930

(4% in <1 Oe at room temperature in permalloy)
Lord Kelvin first observes MR in magnetic metals 1856
FIGURE 1.1.5 History of magnetoresistance. (Courtesy of IBM Research.)

BOX 1.1 Continued
by our increased computational ability arising from the increasing power of silicon
integrated circuits, coupled with atomic-level control of materials, led to exponen-
tial growth in the storage density of magnetic materials analogous to Moore’s Law
for transistor density in silicon integrated circuits (see Figure 1.1.6).
100
Spin-valve
Giant MR Heads
Areal Density, Gbits/in 2
10
Magnetoresistive
1 Heads
0.1
0.01
1985 1990 1995 2000 2005
Year
FIGURE 1.1.6 “Moore’s Law” for magnetic storage: logarithm of storage density
versus time. (Courtesy of IBM Research.)
creases in the magnetic permeability and decreases in the losses by incremental

improvements in amorphous metglass leads to decreases in the losses suffered in
transmission and distribution. Magnetoelectronics, an emerging area based on
advances in the understanding of the properties and processing of magnetic mate-
rials, shows promise for future applications.
Despite the numerous recent discoveries and technological advances in the under-
standing and use of magnetic materials, our fundamental understanding of magnetism
remains remarkably incomplete. Some of the basic questions and important chal-
lenges in magnetism facing the scientific community are discussed in this chapter.
ELECTRONIC MATERIALS AND PHENOMENA
Materials and Physics That Drive Today’s Technology
Silicon Technology
As noted in the introduction, semiconductor technology is the key enabler of
the information age. The science of materials as a specific discipline is a relatively

modern development. The physics and materials science of semiconductors is an

even more recent development. Metals and ceramics were commercially impor-
tant materials when the transistor was demonstrated about 50 years ago. Despite
the fact that the science of semiconductors is relatively new compared to that of
metals and ceramics, the commercial importance of semiconductors is now com-
parable to that of metals and ceramics. Advances in semiconductor technology are
driving the rapid growth of business sectors involved with computing, communi-
cations, consumer electronics, and software, and are enabling emerging fields
such as biotechnology. Today’s transistor performance and the incredible ad-
vances of integrated circuits in silicon technology are the result of more than 50
years of dedicated research in electronic materials. The understanding achieved
from this focused research has enabled high-volume manufacturing of circuits
with ever-increasing complexity and performance.
In addition to driving computing and communications, the steady decrease in
cost-per-function has created literally hundreds of applications for silicon inte-
grated circuits. Semiconductors are ubiquitous. Microprocessors are used al-
most everywhere today—from household appliances, to banking and smart cards,
to automotive and aircraft control systems, automatic fuel injection engines, and
cockpit instrumentation—and will be in even more applications tomorrow. The
same sustained rate of progress that permitted the widespread application of
semiconductors has created a global semiconductor industry with 1997 revenues
of about $150 billion, supported by a materials and equipment infrastructure of
about $60 billion. Semiconductor technology is also the heart of the $1 trillion
global electronics industry and vital in many other areas of the approximately $33
trillion global economy.
The increasing functionality of integrated circuits, which comes as a by-
product of scaling to smaller feature sizes, has been achieved by comparable
increases in their complexity and that of the attendant manufacturing process.
Today’s leading-edge microprocessors are manufactured with minimum feature
sizes of 250 nm and require six levels of metallization to connect the transistors
and circuit components. A beneficial by-product of the steady decrease in feature
size is higher speed devices and circuits. Based on technology projections that
form the basis of the National Technology Roadmap for Semiconductors,3 the
semiconductor industry expects to manufacture integrated circuits with feature
sizes of 180 nm in 1999 and 150 nm by 2001. If the scaling trend continues as
indicated by Moore’s Law, which the industry has followed since its inception,
integrated circuits with minimum feature sizes of 50 nm will be manufactured in
high volumes within 15 years (see Box 1.2). Continuing to advance this technol-
ogy requires that the industry invest in expensive new manufacturing facilities
and an ever-increasing scientific understanding and control of semiconductor
3Semiconductor Industry Association, National Technology Roadmap for Semiconductors,

SEMATECH, Austin, Tex. (1997).

BOX 1.2 A Brief History of Ion Implantation
In the early 1940s, the basic machines that were later adapted for ion implan-
tation in the semiconductor business were used at Oak Ridge National Laboratory
for uranium isotope separation. This was a critical part of the Manhattan Project.
Ion beams were first used as part of semiconductor-device processing at Bell Lab-
oratories in 1952. Bell filed a comprehensive patent in 1954 covering the use of
ion implantation for doping semiconductors, but it was not until 1966 that implanta-
tion was actually used to manufacture commercial semiconductor devices.
Hughes Research Laboratory used the technique to form junctions in the man-
ufacturing of diodes. In 1970 Texas Instruments began using ion implantation in
integrated circuit manufacturing to set threshold voltages. Concurrent with these
developments in processing, several companies attempted to enter the implant-
tool manufacturing business with only moderate success, most successful among
them being Accelerators Incorporated. In 1971, however, a new company, Extri-
on, was formed to build commercial implanters specifically designed for integrated
circuit manufacturing. Extrion soon became the primary supplier of implant tools.
This led to the development of a whole new industry in America.
Today, ion implantation is used in several steps of the integrated circuit manu-
facturing process to control the concentration and depth distribution of dopants.
Ion implantation tool manufacturing, an almost exclusively U.S. industry, has grown
to a more than $1 billion per year business. Three U.S. companies (Applied Mate-
rials, Eaton, and Varian) supply virtually all the commercial ion-implant systems
worldwide.
materials and manufacturing processes. Conversely, our rate of understanding

has been greatly enhanced by the technology created by the rapid advances in
semiconductor-related technologies.
Many daunting scientific and engineering problems must be overcome in
order to continue at the Moore’s Law rate of progress for the next 15 or even 10
years. For instance, the number of wires needed to connect the transistors grows
as a power of the number transistors. As transistor dimensions are shrunk,
computer chip manufacturers pack an ever-increasing number of them into their
devices. The complexity of wiring the transistors in these devices may eventually
reach the limits of known materials. Moreover, the cost of manufacturing in-
creasingly layered and complex wiring structures may limit the performance of
these systems. Even if solutions to the interconnect problem can be identified,
continued scaling of silicon technology will ultimately encounter fundamental
limits. For example, metal-oxide semiconductor transistors can be built today
with gate lengths of 30 nm (only about 150 atoms long) that display high-quality
device characteristics. Manufacturing complex circuits that rely on devices with
these feature sizes will require several hundred processing steps with atomic-
level control. However, the performance of complex integrated circuits with tens
of millions of transistors may be degraded because of nonuniform operating

characteristics. In time, continued decreases in device dimensions may result in

the information being carried by an ever-decreasing number of charge carriers;
ultimately, simple statistical fluctuations will limit the uniformity of device char-
acteristics as the number of charges used to convey information decreases.
To delay this limitation as long as possible, research is under way on new
materials with a high dielectric constant for memory applications or to limit
leakage from tunneling currents. As understanding of synthesis and processing
increase, ferroelectric materials are being introduced for nonvolatile memory
applications. Even with these advances, as feature sizes continue to decrease,
integrated circuits based on field-effect transistors will eventually encounter fun-
damental limits, such as interconnect delays caused by the ever-increasing num-
ber of interconnects, heat generation, or quantum limits of transistors that are too
small to confine the electrons in the channels. Today’s approach to the design
and manufacture of integrated circuits will no longer be extendible to smaller
feature sizes and higher densities. The fundamental limits of the current technol-
ogy and our addiction to exponentially increasing computational power offer
exciting scientific and engineering challenges in the search for the materials and
device structures of the future.
Compound Semiconductor Technology

Compound semiconductors, which consist of more than one element, offer
intrinsically higher speed and lower noise compared with silicon. These advan-
tages have been exploited to develop very high frequency electronic devices and
circuits for microwave and wireless communication applications.
The worldwide electronics market for compound semiconductors is estimated
to be growing at about 40 percent per year and is expected to be about $1 billion in
2000. In addition to the high-speed microwave applications for which they have
long been the materials of choice, discrete components are widely used in the low-
noise receivers of telephone handsets. Compound semiconductors such as GaAs,
AlGaAs, InGaAs, SiGe, GaN, and GaAlN are key to the development of next-
generation wireless telephones, which will use higher frequency microwaves to
transmit more information and allow more channels. GaN transistors, for example,
have a high breakdown voltage and great robustness, although extensive research
and development is required before the material can be understood and fabricated
in a well-controlled fashion. Advancing the limits of semiconductor materials
technology is essential for increasing the speed of transistors and advancing our
ability to modulate light-emitting diodes and semiconductor lasers for high-speed
optical information transmission. Because compound semiconductors are com-
posed of more than one element, they offer a vastly increased range of materials
from which to create structures with desired electronic properties.
The technology of modern compound semiconductor device fabrication is
predicated on the ability to produce extended planar layers of uniform composi-

tion and thickness. Band-structure engineering through complex heterostructures

formed from combinations of compound semiconductors greatly increases the
performance, potential applications, and research opportunities. Heterostructure
devices such as heterojunction bipolar transistors, field-effect transistors, semi-
conductor lasers, or light-emitting diodes require the presence of epitaxial layers
with different compositions and well-controlled thicknesses in the same device.
This promise can be realized with manufacturing techniques such as molecu-
lar beam epitaxy or metal-organic chemical vapor deposition, developed in the
1960s by materials physicists. These techniques allow atomic layer control in the
growth of one material on another in single atomic layers to produce materials not
found in nature. The use of novel forms of microscopy for fabrication and
testing, and the development of comprehensive modeling techniques that take
into account all of the materials physics and carrier dynamics of the structures,
will determine our ability to design and build such structures on the atomic scale
with feature sizes comparable to the quantum de Broglie wavelength of the
electrons.
The ability to span the broad spectral region from ultraviolet to long-wave-
length infrared was enhanced by the invention of strained-layer systems. Very
high crystal quality layers can be grown for systems with different equilibrium
atomic spacing, provided the thickness of the layer is less than the critical layer
thickness at which detrimental dislocations nucleate and grow. Superlattices of
such systems are called “strained-layer superlattices,” whereas single layers sand-
wiched between two layers with identical lattice constant are called either
“strained-quantum well” or “pseudomorphic structures.” The recognition that
alloys with different equilibrium lattice constants, such as GaIn1-xAsx on GaAs,
could be grown epitaxially to create strained layers opened up major opportuni-
ties for “band-gap engineering.” These so-called pseudomorphic layers removed
the constraint that epitaxial materials must have equilibrium atomic spacings that
match the atomic lattice spacings of the substrate. Recently, dislocation-free
growth of a different lattice constant material has been obtained on a thin layer of
compliant substrate that has been wafer bonded at an angle with respect to the
bulk substrate lattice. Such strained thin layers offer an additional degree of
control over the electronic band structure of the resulting artificially structured
material.
The ability to create nearly ideal two-dimensional electron gases (2DEGs)
through the growth of artificially structured materials with charge carriers con-
fined to potential wells, and modulation doping, in which the dopant impurities
that donate charge carriers are located far away from the potential wells that
confine the charge carriers, allowed the development of very high performance,
high electron-mobility transistors (HEMTs). Today’s highest performance tran-
sistors, in terms of speed-power product and noise, are pseudomorphic HEMTs.
The ability to fabricate complex structures with atomic-level control permits
research into fundamentally new structures for technology applications. One

example of a concept that is beginning to receive attention is that of quantum-

state logic, in which a device can be switched between multiple states, in contrast
to a field-effect transistor that is either “on” or “off.”
The creation of heterostructures and quantum wells also led to the develop-
ment of new tools to study the fundamental physical phenomena associated with
these artificially structured materials, greatly increasing our understanding of
their electronic band structure and optical properties. One of the recent examples
is the use of ballistic electron energy microscopy to measure the energy band
offsets in buried heterostructures (see Box 1.3).
The Science Underlying Semiconductor Microelectronics Technology

As noted earlier, for the past 30 years silicon technology has been dominated
by Moore’s Law: the density of transistors on a silicon integrated circuit doubles
about every 18 months. This increased functionality-per-unit cost is the basis of
the information revolution. The same technology that allows us to shrink the size
of devices has allowed us to learn new physics. The synergy of technological
development and new physics has been remarkably successful in the past few
years, and it is difficult to anticipate the many new directions that synergy will
take in the next decade or two.
The technology that fuels Moore’s Law rests on the ability to make high-
quality silicon field-effect transistors. In these transistors a metal gate confines
electrons near the interface between silicon and a SiO2 gate oxide. As feature
sizes decrease, quantum mechanical effects become observable. Combining the
small feature size available with electron-beam lithography with very high qual-
ity artificially structured materials that can be grown in compound semiconduc-
tors led to the discovery of entirely new physical effects, such as the fractional
quantum Hall effect (FQHE) discovered in two-dimensional electron systems.
The elegant physics underlying the FQHE is discussed in Chapter 3.
To continue the increasing levels of integration beyond the limits mentioned
above, new approaches and architectures are required. One of the alternative
approaches that has received recent attention is quantum-dot (see Box 1.4) cellu-
lar automata (QCA). QCA is an approach that takes advantage of the quantum
tunneling between dots to perform the operations that transistors perform. In
today’s digital integrated circuit architectures, transistors serve as current switches
to charge and discharge capacitors to the required logic voltage levels. In QCA,
logic states are encoded by the positions of individual electrons rather than by
voltages. Such structures are scalable to molecular levels, and the performance
of the device improves as the size decreases; artificially structured QCA cells
studied to date operate only at low temperatures, but molecular-sized QCA cells
would function at room temperature.
Electron-beam lithography was developed to make very small semiconductor
devices. The short wavelength of electrons allows one to pattern structures with

BOX 1.3 Ballistic Electron Emission Microscopy
Ballistic electron emission microscopy (BEEM) is a variant of scanning-tunnel-

ing microscopy (STM) which probes, with nanometer lateral resolution, the subsur-
face electronic properties of materials. The technique was first developed in 1988
to investigate lateral variations of Schottky barriers formed at metal/semiconductor
interfaces and has since been applied to a wide variety of materials systems. The
study of semiconductor heterostructures and quantum structures buried beneath
the Schottky barrier has shown particular promise because BEEM is able to ac-
cess length scales smaller than those available to more traditional techniques.
In BEEM, an STM tip locally injects hot carriers through a thin metal layer and
over the Schottky barrier without making direct contact. Carriers that are further
transmitted through the heterostructure are collected by a third terminal usually
located at the semiconductor substrate. As the tip is scanned or its bias is
changed, changes in the collected BEEM current give spectroscopic information
about the heterostructure, such as heights of band offsets or positions of quantized
electronic states.
Figure 1.3.1 shows schematically a BEEM measurement of ~50 nm-diameter
GaSb self-assembled quantum dots located ~7.5 nm below an Au/GaAs interface.
Because the dots are close to the surface, their profiles can be seen in the STM
topography, so that the tip can be located on and off the dot for comparison. Fig-
FIGURE 1.3.1 BEEM measurement of self-assembled quantum dots. [Reprinted

from L.D. Bell and V. Narayanamurti, Current Opinion in Solid State and Materi-
als Science 3, 38 (1998).]

ure 1.3.2 shows concurrently scanned STM and BEEM images of a single dot.
The BEEM image clearly shows a reduction in BEEM current through the dot,
which shows the presence of a localized conduction band offset at the dot.
FIGURE 1.3.2 STM and BEEM images of a single dot. [Reprinted with permis-
sion from M.E. Rubin, H.R. Blank, M.A. Chin, H. Kroemer, and V. Narayanamurti,
“Local conduction band offset of GaSb self-assembled quantum dots on GaAs,”
Applied Physics Letters 70, 1590 (1997). Copyright © 1997 American Institute of
Physics.]
dimensions that are smaller than 100 nm. Such structures have been used as gates
on submicron GaAs/AlGaAs devices (see Box 1.5), eliminating the 2DEG under
them. In this way, confinement both in the plane and perpendicular to the plane of
the 2DEG can be achieved. The simplest structure of this kind is a narrow constric-
tion in the 2DEG that exhibits a resistance quantized in units of h/e2.
Electron-beam lithography can be used to make nanometer-sized metal wires
and rings. This opened the field of mesoscopic physics: the study of systems that
are larger than atoms but small enough that they are not bulk materials. In such
mesoscopic systems, the wavelength of the carriers is comparable to the device
dimensions and to the mean free path for phase breaking, and statistical averaging
does not eliminate quantum mechanical phenomena. One dramatic phenomenon
of this kind is universal conductance fluctuations.
Most mesoscopic effects for systems in one- or two-dimensional confine-
ment are subtle. However, when electrons are confined in all three dimensions
the results can be dramatic. Structures in which electrons confined to metals and
semiconductors with tunnel junctions connecting the confined regions to the
leads (essentially “artificial atoms”) enhance the electron-electron correlations,

BOX 1.4 Transport in Quantum Dots
Quantum dots are semiconducting or metallic regions so small that the elec-
trons are confined in all three dimensions. Like an atom, a quantum dot contains
a finite number of charges and has discrete energy levels. The study of electron
transport through these minuscule conducting regions has revealed a variety of
fascinating phenomena including observable effects caused by individual elec-
trons. Current versus voltage measurements for a quantum dot show discrete
staircases where each successive plateau represents the addition of one electron
to the quantum dot (see Figure 1.4.1).
10
Conductance (e 2 /πh)
0 –2 –1.8 –1.6 –1.4 –1.2 –1
Gate Voltage (V)
15
;;;;;;;
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W = 250 nm
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;;;;;;;
GATE
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;;;;;;;
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;;;;;;;
L = 1 µm
10 @@@@@@@
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;;;;;;;
Resistance (kΩ)
0
–2 –1.8 –1.6 –1.4 –1.2 –1 –0.8 –0.6
Gate Voltage (V)
FIGURE 1.4.1 Current versus voltage measurements for a quantum dot illustrat-
ing the discrete electronic states. Each successive plateau represents the addi-
tion of one electron to the quantum dot. (Courtesy of Massachusetts Institute of
Technology.)

Transmission through the dot can be measured by application of a bias volt-

age and measurement of the current (Figure 1.4.1, top). If, in addition, one steadi-
ly changes the potential of the dot by the application of a bias voltage to a gate
electrode, a succession of resonance peaks are observed (Figure 1.4.1, bottom).
The peaks occur when the energy levels in the quantum dot coincide with the
Fermi level of the electrons in the leads.
Although the transmission probability (which has a shape independent of the
number of electrons initially on the dot) is understood, these measurements did not
provide information about the coherence of the tunneling electrons. Recent mea-
surements of the phase of the electrons demonstrated that the tunneling was co-
herent. In the experiments, a semiconducting path around an insulating region
penetrated by magnetic flux lines was constructed. This approach exploited the
Aharonov-Bohm effect, in which an electron acquires a phase shift as it goes
around a magnetic flux line. Interference was observed between the parts of the
electron wave function that traveled on opposite sides of the flux line. Using a four-
terminal configuration, the change in phase versus potential is measured as an
electron enters the quantum dot and interacts with a quasi-bound state and leaves.
The phase shift on both transmission and reflection were measured, yielding the
unexpected result that the phase shifts are independent of the number of electrons
initially on the quantum dot, a result that is not yet understood.
resulting in the quantization of both charge and energy. The energy levels of
these artificial atoms can be measured by the voltage required to add an extra
electron. These artificial atoms are large enough to display behavior that is not
observed in natural atoms; for example, the superconducting energy gap in
mesoscopic Al structures is quantized.
From the perspective of potential applications, single-electron transistors
(SETs) (see Box 1.6) can be realized in systems with three-dimensional confine-
ment provided by structures with two tunnel junctions and a gate. SETs turn on
and off again every time an electron is added. This device not only functions as
a transistor, but also provides insight into the physics of mesoscopic structures.
Using the sharp peaks associated with the addition of an electron, the equilibrium
ground-state energy of the droplet of electrons, as well as some low-lying excited
states of the droplet, can be measured. Furthermore, application of a magnetic
field reveals phase transitions between different states of the system. The mag-
netic field alters the balance between the confining potential, which favors a high
electron density, and the Coulomb interaction, which favors a low electron
density.
Based on recent successes in nanostructures, we can speculate about the
kinds of nanostructures likely to yield new physics and technology. Three differ-
ent physical effects in nanostructures that can be exploited for nanoelectronics
are illustrated in Figure 1.2. In resonant tunneling, the probability for charge
carriers to tunnel through barriers is greatly enhanced when the energy levels on

BOX 1.5 Double Electron Layer Tunneling Transistor (DELTT)
The double electron layer tunneling transistor (DELTT) is a recently developed

quantum transistor that, unlike previous quantum transistors, does not require tight
control over lateral dimensions and is thus easy to reproducibly fabricate in large
numbers. It is based on the gate control of two-dimensional-two-dimensional (2D-
2D) tunneling between the two electron layers in a double quantum well (QW)
heterostructure, first investigated in 1990. Because the DELTT exhibits negative
differential resistance, it is multifunctional, allowing the same circuit functions to be
performed by fewer devices. It is also expected to be exceptionally fast, although
such high speeds have yet to be demonstrated.
The source and drain terminals of the DELTT are formed by electrically con-
tacting both QWs, and then locally depleting electrons (by gating or etching) from
the QW one does not wish to contact (see Figure 1.5.1). A third gate terminal
controls the tunneling between the two QWs. Close-proximity backgates—neces-
sary for both good I-V peak-to-valley ratios and for small size and high speed—are
achieved by an epoxy-bonding flip-chip technique that yields a total device thick-
ness of less than one micron.
quantized top QW top control top depletion

2D electron contact gate gate
layers (source)
top QW < 1 mm
tunneling
bottom QW
bottom QW
contact
back depletion gate (drain)
FIGURE 1.5.1 Schematic illustration of the DELTT. The energy band diagram of
the double quantum well heterostructure is shown at left. [Reprinted with per-
mission from J.A. Simmons, M.A. Blount, J.S. Moon, S.K. Lyo, W.E. Baca, J.R.
Wendt, J.L. Reno, and M.J. Hafich, “Planar quantum transistor based on 2D-2D
tunneling in double quantum well heterostructures,” Journal of Applied Physics
84, 5626 (Nov. 15, 1998). Copyright © 1998 American Institute of Physics.]

Current in the DELTT flows only if both energy and momentum can be con-
served in a tunneling event. Because both layers are two-dimensional, this is
equivalent to the QW subbands being aligned. This can be achieved by applying
a source-drain bias, a control gate bias, or both. Figure 1.5.2 shows source-drain
I-V characteristics at several control-gate voltages for an AlGaAs/GaAs DELTT.
Both the height and position of the resonant current peak are clearly controlled by
the gate. Similarly good behavior has been obtained at 77 K, and bistable memo-
ries and digital logic gates have been demonstrated. Although obstacles remain,
the DELTT shows excellent promise as a practical, room-temperature quantum
transistor.
TC
T = 0.3 K
FIGURE 1.5.2 Source-drain current versus source-drain voltage for several val-
ues of top control gate voltage (VTC). Both the height and position of the reso-
nant tunneling current peak is controllable by the gate. [Reprinted with permis-
sion from J.A. Simmons, M.A. Blount, J.S. Moon, S.K. Lyo, W.E. Baca, J.R.
Wendt, J.L. Reno, and M.J. Hafich, “Planar quantum transistor based on 2D-2D
tunneling in double quantum well heterostructures,” Journal of Applied Physics
84, 5626 (Nov. 15, 1998). Copyright © 1998 American Institute of Physics.]

BOX 1.6 Kondo Effect in an Artificial Atom
The analogy of a quantum dot to an artificial atom has been extended with the
demonstration that a quantum dot interacts with nearby metallic leads in much the
same way that a single magnetic impurity interacts with a surrounding metal—in
the phenomenon known as the Kondo effect. Kondo behavior was found recently
in a single-electron transistor, which consists of a semiconductor quantum dot
sandwiched between two metallic leads. This miniature device turns on and off as
individual electrons controlled by a nearby gate flow on and off the dot.
The theory of the Kondo effect was developed in the early 1960s to explain a
long-standing puzzle about the resistance of some metals: Why does the resis-
tance start to increase as the metal is cooled below a certain temperature? Ac-
cording to the picture that has emerged, the increased resistance comes from
magnetic impurities whose local magnetic moments couple antiferromagnetically
to those of the conduction electrons. The coupling becomes stronger and increas-
ingly impedes the flow of current as the temperature is decreased.
The concept of the Kondo effect is intriguing because it involves the pairing of
a localized electron with an electron in an extended state in the metal. Its manifes-
tation in a quantum dot is no less compelling. Although interactions between elec-
trons in quantum dots are known to be important, the Kondo phenomenon is a true
many-body effect requiring a coherent state resulting from the coupling of the lo-
calized electrons in the dot and a continuum of electron states outside the dot.
Experimenters have tried to see a manifestation of the Kondo effect in quantum
dots ever since its presence was predicted in the late 1980s, but succeeded only
recently. Kondo behavior for a single spin had been observed in resonant tunnel-
ing through a charge trap created unintentionally in a point contact. A collaborative
experiment involving the Massachusetts Institute of Technology (MIT) and the
Weizmann Institute in Israel has attracted additional interest because it shows the
Kondo effect in a way that will allow one to explore the phenomenon in a system
with many tunable parameters.
Kondo-like effects in quantum dots are observable only under a very narrow set
of conditions. To see the effects of coupling between the dot and the leads, one
needs to make the rate for tunneling of electrons between the dot and the leads as
high as possible. The higher this rate, the higher the temperature at which the
Kondo effect survives. However, if one makes the rate too high, the electrons on
the dot become completely delocalized. With a smaller dot, the electrons are more
localized to begin with, and a higher rate is possible.
To make a semiconductor quantum dot, one starts with a two-dimensional elec-
tron gas of electrons confined in a plane at the boundary between two semicon-
ducting materials. Additional semiconductor layers go on top of this boundary
region. At the top of the structure, one lays down electrical gates; the electrical
potentials created by these gates confine the electrons in the plane below the
gates to a very small region. Typically the quantum dots lie 100 nm below the
surface. The MIT-Weizmann team made a much smaller artificial atom by forming
the two-dimensional electron gas closer to the surface.
The conductance of a single electron transistor displays a peak when the sum
of the voltage (Vg) on one of the gates and of the voltage (Vds) between the two
leads on either side of the dot, each multiplied by the appropriate capacitance, is
large enough to add an electron to the dot. A gray-scale plot of the conductance

(see Figure 1.6.1) therefore consists of a series of bright diagonal bands, marking
the positions of the peaks, whose slopes are determined by the relative capaci-
tances. The highest peaks occur where the bands intersect on the Vds = 0 axis.
These maxima cluster in pairs along the Vds = 0 axis, with the intra-pair peak
separation smaller than the inter-pair separation. (One pair is shown in the figure.)
The two peaks correspond to the addition of a pair of electrons to the same spatial
state; one electron enters the state with spin up and the other with spin down. The
next electron must go into the next spatial state. Thus, in the region between the
paired peaks the artificial atom has an odd number of electrons.
The peak structure described so far is that expected for any artificial atom. One
tip-off in the data to the presence of the Kondo effect is the non-zero conductance
between the paired peaks, the bright, narrow vertical line along the Vds = 0 axis. In
this region the quantum dot has an unpaired electron, which is free to form a
singlet with the electrons in the leads. This singlet state couples electrons from the
FIGURE 1.6.1 Evidence for the Kondo effect in a single electron transistor.
(Courtesy of Massachusetts Institute of Technology and the Weizmann Institute.)

BOX 1.6 Continued
left lead to the unpaired electron on the dot and thence to the right lead, giving
conductance in a region where none is ordinarily expected. As predicted by theory,
this interpeak conductance increases as the temperature is decreased.
If the enhanced conductance that appeared between the two peaks were due
to the Kondo effect, it would require a symmetric interaction of the unpaired elec-
tron on the quantum dot with electrons in both leads. But if one applies a voltage
Vds across those two leads, separating the Fermi energy levels of the two reser-
voirs, that interaction is no longer symmetric, and the conductance must fall. An-
other signature of the Kondo effect is the disappearance of the enhanced conduc-
tance as the voltage between the leads is increased, leading to the narrowness of
the vertical line in the figure.
Finally, a magnetic field splits the unpaired electrons, causing the conductance
peaks to split as well, by an amount equal to 2 gµBB. This signature is also observed.
the two sides of the barrier are identical. Large changes in the tunneling current
are realized with small changes in the bias voltage across such structures. In
structures that confine electrons to regions with dimensions comparable to the
electron wavelength, quantum interference effects can be used to switch elec-
tronic currents. A conceptual approach to a transistor based on quantum interfer-
ence is shown in Figure 1.3a.
Quantum confinement structures can be created that serve as electron wave-
guides, conceptually similar to the waveguides encountered in optical structures.
Nanostructure switches based on guided-wave coupling can be created in quan-
tum confinement structures, illustrated in Figure 1.2b. In these switches, illus-
trated in Figure 1.3b, electrons in input channel 1 (IN1) can either exit through
output channel 1 (OUT1) or be switched to output channel 2 (OUT2) depending
on the gate bias voltage.
Resonant
Tunneling Quantum Confinement Coulomb Blockade
2D 1D
a) b) c)
FIGURE 1.2 Illustration of physical effects realizable in nanostructures: (a) resonant
tunneling; (b) quantum confinement; and (c) Coulomb blockade. (Courtesy of Stanford
University.)

GATE
Quantum
Interference
IN OUT
a)
GATE
Guided-Wave IN1 OUT1

Coupling IN2 OUT2
b)
GATE
Single Electron
Tunneling
IN OUT
c)
FIGURE 1.3 Schematic illustrations of nanoswitching concepts based on the physical
effects illustrated in Figure 1.2. (Courtesy of Stanford University.)
In the Coulomb blockade structure illustrated in Figure 1.2c, adding an elec-

tron to a quantum dot creates a Coulomb field that repels the addition of another
electron. A SET can be realized by placing the quantum dot between the input
and output channels as illustrated schematically in Figure 1.3c. The transistor is
switched between on and off by changing the voltage on the gate.
A number of novel circuits based on capacitively coupled arrays of artificial
atoms have been proposed based on SETs; however, because the original SETs
operated only at very low temperatures, the effort in this area was initially lim-
ited. The operating temperature scales with the energy required to add an elec-
tron to the artificial atom, which increases with decreasing size of the mesoscopic
structure. Recently, nanometer-size SETs and single-electron memories (SEMs)
have been demonstrated that have quantum dots sufficiently small to operate near
room temperature (see Box 1.7), stimulating increased interest in these meso-
scopic structures.

BOX 1.7 Single-Electron Transistors and Memories

Single-electron transistors (SETs) rely on quantum dots of small semiconduct-
ing or metallic regions in which electrons are confined in all three dimensions. In
a conventional field effect transistor, electrons (or holes) travel through a semicon-
ducting region, known as a channel. The channel connects two electrically con-
ducting contacts, known as the source and drain. A gate electrode located above
the channel is used to control the flow of charge in the channel. In complementary
logic, the channel is normally in a nonconducting state. Application of a voltage to
the gate electrode increases the conductivity of the channel, allowing charge to
flow across it; the transistor turns from off to on.
SETs can be made by replacing the channel between the source and drain in
conventional devices with quantum dots surrounded by an insulator. The key is
that the quantum dots are so small that, when an electron is on the island, Cou-
lomb repulsion prevents other electrons from crowding on. Changing the gate
voltage on the quantum dot aligns the energy level of the dot and the electrode,
allowing the electron to tunnel to the electrode. Because the separation of the
energy levels in the quantum dot increases with decreasing size of the dot, very
small structures, analogous to artificial atoms with dimensions on the order on 1 to
4 nm, are required for room-temperature operation of a SET.
Single-electron memories (SEMs) are made using a variation on the SET. The
crucial difference is that, in a SEM, the quantum dots sit between the channel and the
gate electrode rather than replacing the channel as they did in the SET. A SEM
structure based on silicon technology is shown in Figure 1.7.1. The source and drain
are sufficiently separated from the quantum dots to prevent spontaneous electron
tunneling. In the uncharged, or 0 state, there are no electrons on the quantum dot and
a given geometry-dependent gate voltage allows current to flow between the source
and drain. In the 1 state, an electron is injected into the quantum dot. When an
electron is on the quantum dot, a different voltage is required to turn on the transistor
because of the Coulomb field caused by the presence of the electron. Using quantum
dots formed from polycrystalline silicon and standard integrated-circuit processing
technology, researchers at Hitachi have recently fabricated 128-Mbit single-electron
dynamic random access memories (DRAM) that operate at room temperature.
Single-Charge Trap
Narrow channel blocked
Polysilicon gate
Polysilicon
quantum dot
stores single electron
Silicon channel
blocked
(25 nm X 35 nm)
Insulating layer
Buried oxide
Silicon substrate
FIGURE 1.7.1 Single-electron memory structure based using a silicon quantum

dot. (Courtesy of the University of Wisconsin.)

Challenges, Priorities, and Frontiers of Electronic

Materials and Phenomena
Based on the progress in scanning microscopies, we can speculate that the
successor to electron-beam patterning for fabrication of nanostructures could be
atom-by-atom assembly. In recent years, scanning-tunneling microscopes have
been used to arrange atoms on surfaces and to measure changes in the energies of
the surface electrons by tunneling spectroscopies. Scanning probes have been
used to construct single-atom switches in which the movement of an atom from
one position to another opens or closes a circuit created by assembling rows of
atoms on a surface.
The inexorable pressure to reduce the dimensions of semiconductor devices
has introduced to condensed-matter physicists and materials scientists the con-
cept of self-organizing structures in the nanometer-size regime. Self-assembly
promises a broader frontier of nanostructures. A self-assembled array of quan-
tum dots can be grown either by strained-layer nucleation of islands between
quantum wells during growth or by assembly of nanometer-sized dots grown by
solution chemistry into a macrocrystal. Both approaches are discussed in detail
in Chapter 4. Such nanocrystals are a different approach to forming artificial
atoms analogous to the artificial atoms discussed above. A major research area
will be learning how to control self-assembled materials to create ordered one-,
two-, and three-dimensional structures. These self-organized structures will be
technologically useful to the degree that their size and nucleation density can be
controlled.
The committee concentrates, in this section, on the electronic properties of
quantum structures, but photonic lattices are beginning to emerge and are dis-
cussed in more detail in the following section. In photonic lattices, photons are
confined in arrays of structures with dimensions comparable to the wavelength of
light in the medium. Combining such lattices of quantum wells with feature sizes
comparable to the wavelength of electrons will lead to coupled electron-photon
systems with new and interesting electronic and optical properties.
Numerous outstanding scientific and technological problems have been iden-
tified in the research in electronic materials. Beginning with silicon integrated-
circuit technology, major materials-related technical questions include, What
interconnect technology will be used beyond copper and low k (i.e., beyond
normal metals and dielectrics) for silicon integrated circuits? and How do we
manufacture SETs and SEMs at reasonable operating temperature and cost?
Recognizing that one cannot continue to scale silicon integrated circuits to
smaller feature sizes indefinitely raises the question, What is beyond silicon?
Additional questions that need to be investigated to address this question are the
following: How can self-assembled materials be controlled to create the desired
one-, two-, and three-dimensional structures? How does one create hybrid struc-
tures that exploit the best properties of, e.g., organics or plastics and semiconduc-

tors, magnetic materials and semiconductors, or superconductors and semicon-

ductors? How do we understand and exploit quantum state logic?
To continue to advance our fundamental knowledge, and to use this knowl-
edge to continue to advance technology based on electronic materials, the com-
mittee offers the following recommendations:
• Perform the long-range research required to allow the semiconductor in-

dustry to follow Moore’s Law and maintain its historical rate of productivity
improvement.
• Accelerate research into materials, structures, and technologies that will
go “beyond silicon,” i.e., to discover what technology will be used after today’s
silicon integrated-circuit technology reaches its limits.
• Expand the research efforts in self-assembled materials to create struc-
tures that promise needed technologies.
• Continue to develop the processing and characterization tools required to
create and evaluate ever more-complex, ever-smaller, artificially structured materials.
OPTICAL MATERIALS AND PHENOMENA
Materials and Physics That Drive Today’s Technology
Optical Communications
As mentioned in the introduction, fueled by the explosion of Internet use and
the globalization of voice and data communications, lightwave communication
systems capacity and installation are growing exponentially with a growth rate of
about a factor of 10 every 6 years. The current global market for lightwave
systems is about $8 billion per year and is expected to grow to about $15 billion
per year by 2000. Optical telecommunication was introduced into the market in
1980; today, not only is optical fiber the medium of choice for long-distance
voice and data communications, but it is also rapidly growing to be a leading
player in the local area network (LAN) market. Optical fiber is predicted to have
revenues of about $20 billion in the year 2000 and dominate the analog cable
television and fixed wireless loop markets.
The first undersea optical cable was installed in 1988, with a capacity of
about 8,000 voice circuits per cable, at a cost of about $400 per circuit per year.
More than 300,000 km of undersea lightwave cable had been installed by the end
of 1996. Cable installed in 1996 cost less than $30 per year per voice channel and
had a capacity of 120,000 voice channels per cable (5 Gb/s per fiber).
The first major terrestrial lightwave system installed in the United States
linked Washington and New York with a capacity of 90 Mb/s per fiber in 1983.
A similar system linked New York and Boston in 1984. More than 100,000 km
of fiber had been installed in terrestrial systems, one-third of it in the United

States, by the end of 1996. The latest systems incorporate wavelength division
multiplexing (WDM) that uses many separate wavelength channels per fiber,
dispersion-shifted fiber, and optical amplifiers. Currently in deployment are 120-
Gb/s-per-fiber systems using 48 channels with 2.5 Gb/s per channel. In the next
2 years 400-Gb/s, 80-channel systems will be introduced into the market.
These advances in technology were made possible by advances in our under-
standing of materials and growth techniques that reduced the transmission losses
of silica-germania optical fiber from 400 dB/km in 1965 to about 0.15 dB/km by
the early 1990s. Such losses allow a signal to travel 800 km (about the distance
between Washington and Boston) before the signal intensity decreases to about
1/100 of its original value. These advances were accompanied by recent major
advances in InP-based electrically modulated single-wavelength semiconductor
diode lasers operating in the 1.3-µm and 1.5-µm wavelength regions, where the
lowest loss in silica fiber occurs; in fast avalanche photodiode detectors; in
erbium-doped fiber amplifiers and other fiber devices (see Box 1.8); and in high-
power semiconductor diode lasers used to pump the fiber devices.
Current digital optical telecommunications networks typically use the NRZ
(non-return-to-zero) format to transmit data in the linear amplitude regime. Fu-
ture systems could use nonlinear effects in fiber with high-power lasers to exploit
the properties of soliton transmission.
Solitons are wave packets that propagate without changing shape. They are
solutions to the electromagnetic wave propagation equation in fiber waveguides
that arise from the nonlinear effects of self-phase modulation and dispersion in
the group velocity. Solitons are dispersion-free and exhibit a pulse shape that
retains its waveform over long distances because the two nonlinear effects are
exactly counterbalanced. They were first proposed as a means of data transmis-
sion in optical fiber in the 1970s and observed in the research laboratory in 1980.
They offer extremely high bit-rate transmission (>100 GHz) at a single wave-
length. Extensive research on the use of other nonlinear effects in both fibers and
semiconductors and in artificially poled piezoelectric materials is under way to
enable future ultrahigh-speed all-optical processing devices.
Local area networks (LANs), optical data links, and optical signal processing
are emerging growth areas enabled by new technologies such as vertical-cavity
surface-emitting lasers, smart pixels and microelectromechanical systems. All of
these technologies were implemented as devices within the past decade. The
emergence of low-loss graded index multimode plastic optical fibers in the past 5
years could lead to a low-cost medium to deliver high bandwidth communica-
tions over short links from a single-mode glass fiber backbone to the desktop.
The advantage of extremely low-cost connectors and low-cost transceivers could
outweigh the high cost of fluorinated polymer materials compared with the cost
of glass fiber based LANs. The predicted annual market for optical data links is
$1 billion by the year 2000 and $3.3 billion by 2005, with approximately half in
computers and half in LANs.

BOX 1.8 Fiber Devices
The revolution in optical communications over the last decade began with the
invention of the erbium (Er)-doped optical-fiber amplifier in the late 1980s. With
the invention and implementation of a number of key optical-fiber devices, evolu-
tion of an all-optical network architecture has begun. Fiber gratings were first
made in 1975. The technological revolution in fiber devices was enabled by the
discovery in 1993 that when exposed to ultraviolet (UV) light, an index of refraction
change as large as 0.01 occurs in the cores of silica fiber doped with hydrogen-
loaded germania. This UV-induced irreversible chemical change permits stable
fiber Bragg gratings to be easily written into the cores of standard optical fiber.
These Bragg gratings serve as key building blocks for a large range of both active
and passive fiber devices such as filters, amplifiers, fiber lasers, dispersion com-
pensators, pump laser reflectors, demultiplexers, and equalizers.
The optical power in communications systems increased sharply with the intro-
duction of the Er-doped fiber amplifier. This amplifier is basically a single-pass
laser consisting of several meters of a spliced silica fiber doped with 1,000 ppm
Er3+ in the core with an input coupler for the pump light. Optical amplification can
be achieved through stimulated emission from the excited states of Er atoms in the
glass if a population inversion is created with pump light from a semiconductor
diode laser.
The optical properties of rare-earth impurities in a glass matrix were first stud-
ied in the 1960s. Rare-earths are ideally suited for use as an amplification and
lasing medium; they have strong optical transitions in the infrared and their proper-
ties are nearly independent of the host material. Er, pumped with 1488-nm or
980-nm light, is ideal for an amplifier in the 1.55-µm communications window.
Optical amplification has many advantages over electronic regeneration: am-
plification occurs over a relatively wide (80-nm) gain curve, ideal for dense wave-
length division multiplexing systems; amplification is transparent—i.e., indepen-
dent of modulation format and bit rate—and in principle the gain is bidirectional. It
also allows watts of optical power, which is important for higher data rates of wave-
length division multiplexing, increased passive split architectures where one source
is split into many channels, and extended repeater spacings. Systems with optical
amplification are far simpler to upgrade to higher bit-rate systems after initial instal-
lation because all optical repeaters are independent of bit rate. Er-fiber amplifiers
were first deployed in undersea communications systems in the mid-1990s.
Because silica fiber has more wavelength dispersion in the 1.55-µm region
than at its minimum in dispersion at 1.31 µm, additional dispersion compensating
fibers were installed at intervals in the system. New fiber designs have shifted the
dispersion minimum to 1.55 µm. New installations use this fiber to minimize the
effects of dispersion at high data rates. In the 1.31-µm optical communications
window used by most of the installed terrestrial base, amplifiers using praseo-
dymium (Pr) ions in fluoride glass hosts (because Pr in silica does not emit at this
wavelength) and Raman-shifted silica fiber amplifiers have been recently demon-
strated in the research lab.
Fiber lasers using rare-earth ion dopants and fiber Bragg gratings as cavity
mirrors were demonstrated in the early 1990s in both silica and fluoride fiber hosts.
A cascaded Raman-shifted laser was demonstrated in 1990 in standard silica-
germania fiber. Raman-shifted lasers eliminate the need for specialty fiber doped

with rare-earths. Figure 1.8.1 shows a block diagram of a Raman-shifted laser

operating at 1.3 µm. The laser consists of five stages of amplification of succes-
sively Raman-shifted light. Each stage is a cavity defined by its own tuned set of
fiber Bragg grating mirrors. The Raman shift of the light in each stage is the
inelastic scattering of the high-intensity light in the laser cavity from the phonons of
the silica core. Higher conversion efficiencies and output power were recently
obtained by sending the pump light into an optimally designed cladding that cou-
ples efficiently to the single mode waveguide core.
FIGURE 1.8.1 Block diagram of a Raman amplifier at 1.3 µm. (Courtesy of Bell
Laboratories, Lucent Technologies.)
Future demand for broadband communications is expected to drive deploy-

ment of fiber-to-the-home communications access systems that will bring GHz
bandwidths from the central office to each home. Over the next 20 years the
predicted expenditure on deployment of wideband access in the United States is
$150 billion. Predicted expenditures on access infrastructure globally is a factor
of 3 to 5 more. The limiter for both the technology and deployment of access is
low-cost, reliable components, which poses major challenges for materials and
device physics. For example, lasers that can operate at elevated temperatures
without active cooling are necessary, as are passive optical distribution systems
and low-cost upstream communication devices such as optical modulators.
Multiple wavelength optical transmission systems for long-distance networks
(DWDM, or dense wavelength division multiplexing), which use sophisticated
integrated optoelectronic devices and waveguide circuits such as multiwave-
length lasers, optical routers, and all optical cross-connects will be rapidly de-
ployed. These technologies are currently in their infancy compared to their
silicon microelectronics counterparts.

Optical Data Storage

The data storage market, fueled by the insatiable appetite of consumers for
generating, collecting, and storing information, is growing exponentially. The
total number of stored bits is expected to exceed 1020 by the year 2000 with the
total data storage market about $100 billion. Of that, the market for optical
storage is projected to be about $12 billion. In addition, the enormous consumer
entertainment electronics market of digital audio and video storage will add
another $20 billion in compact disk (CD) and digital video disk (DVD) technol-
ogy sales and $40 billion in media sales.
The essential idea of optical storage is to store bits by forming pits or spots
on a reflective surface. A spot is read by shining a focused laser beam onto the
disk and measuring the intensity of the reflected light. Optical disk technologies
can be classified by the number of times each portion of the surface can be
written. Read-only disks, such as the ubiquitous audio CDs and computer com-
pact-disk read-only memories (CD-ROMs) introduced in the early 1980s, are
manufactured with data already recorded as pits stamped from a master onto the
polycarbonate disk surface, which is subsequently aluminized and covered with a
protective transparent layer. Write-once disks (also called WORM, for write
once, read many) were introduced in the late 1980s. They are manufactured in an
erased condition, and each sector can be written once by burning pits into the
surface, such as with a laser in the disk drive. Read-write disks, also called
rewritable disks, were introduced in the mid-1990s. They record data via revers-
ible effects such as light absorption inducing a phase change between amorphous
and polycrystalline states (phase-change, PC) or by flipping the direction of a
macroscopic magnetic polarization in an optical medium in conjunction with an
applied magnetic field (magnetooptic, MO). In PC drives data are read by moni-
toring the reflectivity change between an amorphous and crystalline spot, while
in MO drives data are read by detecting the polarization rotation of a laser beam
as it traverses the thickness of the medium.
A key enabler for today’s optical recording technology was the invention of
the compound semiconductor laser diode in the mid-1960s. Also necessary was
the subsequent development of these tiny diode lasers into low-cost, robust,
reliable, relatively high-power devices. Today’s diode lasers are about the size of
a grain of salt, compared to table-top-size gas-ion lasers that require expensive
parts, water cooling, and high-voltage, high-current operation. Today’s optical
drives use near-infrared GaAlAs diodes that operate at 780 nm and 830 nm.
Next-generation DVD technology will migrate to AlInGaP lasers operating near
530 nm (yellow) around 1999. Other enablers were PC media based on binary
and ternary chalcogenides and MO media based on thin films of magnetic FeTb
and CoPt alloys. These alloys, invented by materials physicists in the 1960s and
1970s, are still undergoing intense materials development.
Currently a typical optical drive has a slower positioning time, by a factor of

3, than a magnetic disk drive, a data transfer rate 4 to 10 times slower, and a cost
per gigabyte about 5 times higher. However, the platter of an optical drive is
typically removable and costs about a factor of 10 less than a typical magnetic
disk of equivalent capacity. Optical drives occupy niche markets of data back-up
and distribution rather than the far larger market of main drives in computers.
This latter market is dominated by magnetic drives (discussed below). Future
improvements in optical storage technology could potentially allow higher den-
sity optical storage with access speeds similar to those of magnetic drives, and
thus become a displacement technology for magnetic storage. Development is
under way in four areas for discontinuous improvements in the speed or data
density of optical drives.
One development to improve storage density involves focusing a laser beam
into the desired storage layer of a three-dimensional sandwich produced by stack-
ing semitransparent layers. Data storage density is thereby increased by as much
as a factor of 10.
Also under development are shorter wavelength lasers, permitting smaller
spot sizes. Extensive materials research is required to make low-cost high-
reliability blue-green lasers commercially available (see Box 1.9).
The third emerging development is near-field optical recording. Flying a
special design optical head very close to the storage medium allows write and
read spots smaller than the wavelength of laser light. This direct outgrowth of
condensed-matter and materials physics and optical physics was initiated in 1928
when British scientist E.H. Synge proposed the physics of near-field optics for
microwaves. The first near-field visible optical microscope was not constructed
until the late 1980s, after the invention of the scanning-tunneling microscope
(STM) in 1981. The STM created the technology required for scanning a small
tip in a controlled manner a specified distance away from a surface with atomic-
scale resolution. Near-field technology has the potential for data storage density
one to two orders of magnitude higher than conventional optical and magnetic
storage projections to the year 2000. Another potential advantage of this technol-
ogy is the ability to use very low mass optical heads mounted directly onto sliders
that have been developed for magnetic storage to reduce seek times.
The fourth development on the horizon is holographic data storage. In holo-
graphic storage a page of binary data is stored as pixels of a monochrome image. It
is possible to record thousands of holograms in a spot of a storage medium with
resolution on the order of the wavelength of light. Because of the three-dimen-
sional capability, holographic storage promises a projected density two to three
orders of magnitude larger than conventional optical storage. In addition, it has
extremely high data rates because an entire image is transferred simultaneously.
Development of low-cost, reliable, blue-green lasers and solid-state spatial light
modulators, along with low-cost, robust, and reliable storage media for three-di-
mensional holograms, are needed to enable commercialization of the technology.

BOX 1.9 GaN Lasers
A major breakthrough in condensed-matter and materials physics in the last

decade was the development of blue-green semiconducting laser diodes in the
direct wide band gap GaN/AlN/InN quantum well materials system. Serious ma-
terials problems hampered research efforts concerned with the growth of quan-
tum wells of these materials in the 1960s and 1970s, however: there was no bulk
substrate crystal for lattice matching; high impurity concentrations during growth
permitted growth of only very high concentration n-type material; and the rela-
tively deep levels of p-type donors made it difficult to achieve p-type material
required for current injection devices. By the mid-1970s most major U.S. indus-
trial research efforts in this area were terminated because of the apparent intrac-
tability of these problems. Meanwhile, research in the much less robust II-VI
(Zn,Cd,Mn/S,Se) materials revealed major difficulties caused by the migration of
dislocation-induced dark-defect regions into the active laser area causing cata-
strophic damage.
Two groups in Japan, lead by Akasaki and Nakamura, continued to try to im-
prove materials properties in the far more robust GaN system. A major break-
through was reported in 1989 by the Akasaki group, who found p-type material
after exposing as-grown GaN to an electron beam in an electron microscope.
Soon thereafter Nakamura discovered that GaN grown by standard metallo-
organic chemical vapor deposition was passivated by a high density of H impuri-
ties. With these breakthroughs in understanding, Nakamura was able to produce
n-type material. By 1994 Nichia Chemical announced blue, and soon thereafter
green, light-emitting diodes (LEDs) with extended color range. These early diodes
had external quantum efficiencies higher than 5 percent, five times higher than the
competing yellow-green lasers in the AlInGaP materials system. The high efficien-
cies of commercial LEDs in the AlGaAs and InGaN materials have opened up new
markets in vehicle and brake running lights, and in highway status and traffic con-
trol signs. This market is now in excess of $1 billion per year. The addition of blue
and green LEDs rounds out the visible spectrum and opens up new markets in
long-life traffic lights and high efficiency, high brightness, white lighting systems.
In 1996 these LEDs were already incorporated into commercial full-color displays.
Figure 1.9.1 shows an outdoor full-color display incorporating blue and green In-
GaN LEDs and red GaAlAs LEDs by Arami Electric Co., Ltd. Several groups have
subsequently demonstrated a blue-green laser in the GaN/AlInGaAs system, and
a worldwide race is now under way to achieve a reliable continuous wave laser at
room temperature.
Display, Printing, and Copying Technologies

Exciting recent developments in synthesis of semiconducting organic mate-
rials have enabled researchers to demonstrate a variety of optoelectronic devices
based on electronically active organics. These include light-emitting diodes,
thin-film transistors, photovoltaics, and nonlinear optical elements. The great
potential for these devices resides primarily in the ability to process organics
using cost-effective methods such as spin casting and screen printing, not in
performance considerations. The potential to produce large-area devices and

FIGURE 1.9.1 A black-and-white depiction of a full-color outdoor display incorpo-

rating blue and green InGaN LEDs and red GaAlAs LEDs. [MRS Bulletin 22, 30
(February 1997).]
patterns easily compatible with plastic substrates is the vision driving scientific
investigation of semiconducting organics.
Application of organic materials in electrophotographic photoreceptors is
already commercially successful. In that case, large-area molecularly doped
polymer films with high-charge photogeneration yield have demonstrated ex-
tremely high contrast between photoactivated and dark conductivity. This prop-
erty, combined with the ability to rigorously exclude deep-charge transport traps,
has made organic materials superior for photocopying applications.

The new classes of semiconducting organic materials fall into two catego-
ries: discrete evaporable molecular systems and conjugated polymers. The
former tend to be compositionally pure and easily suitable for layering; the latter
are more thermally stable and are usually amenable to solution processing. The
most mature application of these materials is light-emitting diodes; and commer-
cial low-resolution pixelated monochrome display products based on the
evaporable organics are currently available (see Figure 1.4). It is likely that
analogous products based on conjugated polymers will be available in 1999.
Material stability, device efficiency, and low operation voltage remain important
areas of research and engineering. Further progress in synthesis of systems
resistant to oxidation and electrochemical degradation, synthesis of stable elec-
tron transport materials for the polymeric devices, preparation of materials where
aggregation quenching of luminescence is negligible, and development of contact
modification treatments that improve injection efficiency remains a challenge for
organic chemists. Meanwhile, understanding injection and transport, which de-
termine current voltage characteristics, is crucial. Identification and passivation
of luminescence-quenching sites and study of the effects of high fields present in
light-emitting diodes remain important areas for basic research. A number of
FIGURE 1.4 Flexible light-emitting diode display based on evaporated organic materi-
als. (Courtesy of University of California at Santa Barbara.)

systems issues associated with electrical drive scheme, color fidelity, and pattern-
ing must also be resolved if organic emitters are to have wide application in
display technology.
The requirements for other promising applications of light-emitting organics
such as printing and lighting are substantially the same. A flurry of activity
directed at making electrically pumped organic lasers, however, has raised a
number of additional issues. The current injection requirements are significantly
larger than what is presently achievable, and improved transport will be required.
Also, design of resonator geometries suitable for retaining these large injection
currents, while avoiding absorption loss associated with metallic contacts, will be
required. A significant body of clever work involving distributed feedback,
photonic gap, and microdroplet resonators has begun to address this problem.
Hot carrier effects in the organics may also become quite important at the applied
electric fields necessary to drive lasers, and “interband” emission analogous to
that in inorganic semiconductors has been reported recently under conditions
near dielectric breakdown. The high density of excited states required for stimu-
lated emission gain has also spurred interesting new research on exciton-exciton
interactions and cooperative emission phenomena. These rely on optical excita-
tion of the organic films. It may turn out that the best way to make suitable solid-
state organic lasers is a hybrid design using passive organic gain media that are
optically pumped by electrically pumped inorganic semiconductor lasers such as
those based on InGaN. For these applications, traditional laser dyes doped into
inert polymers may be satisfactory.
Many of the scientific issues noted above are common to the application of
organic semiconductors to transistor applications and photovoltaics. These tran-
sistor applications are likely to be further in the future because performance
remains somewhat inferior to alternative technologies. Organic thin-film transis-
tors that perform within an order of magnitude of amorphous silicon have been
fabricated and may be promising as pixel-switching transistors in active-matrix
liquid-crystal displays. Charge injection and transport are critical to these appli-
cations. Interface chemistry and physics at contacts remain poorly understood;
control of these is essential to stable low-voltage operation. Exciting and prom-
ising results using dipole layers to reduce injection barriers have been reported.
Dipole layers function much as graded gap contacts do in traditional semiconduc-
tors. Charge transport has been studied extensively, and deep traps are com-
monly observed that both reduce mobility for transistor applications and raise
injection voltages resulting from space charge limitations on the current. Re-
search to identify and reduce trap sites is also important to make these applica-
tions viable.
A final general class of promising applications involving active organics in
electronics (see Box 1.10) relies on the conductivity of doped conjugated poly-
mers. Doped trans-polyacetylene, although unstable in ambient conditions, has
exhibited conductivities higher than metals. More stable systems, such as doped

polypyrrole, that are more easily processed and are more compatible with plastic
than traditional systems like indium tin oxide, show promise for application as
transparent contacts for displays.
We anticipate a variety of scientific opportunities, for which the ultimate
technological implications are as yet unclear, to emerge from studying electronic
polymers in the next decade. Some of these opportunities may come as a result of
photochemically modifying single domains or arrays of domains with a near-
field optical microscope, synthesizing materials with giant optical nonlinearities,
linking organic materials to inorganic quantum dot structures, examining the
phase diagrams of mixed polymeric systems, and designing functional polymers
that interface to biological systems. Most likely, even more exciting but unantici-
pated phenomena will arise from this young and vital area of research.
Although the vision for future consumer electronics as described in Box 1.10
is somewhat hyperbolic, the past decade has marked the synthesis of new active
organic materials and advances in the science underlying their electronic, optical,
and mechanical properties. Technologies based on these materials have the
promise that comes with the processability of organic materials—namely, the
potential to use inexpensive manufacturing methods like spray painting, dip coat-
BOX 1.10 A Future Vision for Organic Consumer Electronics
As you walk into the train station, you notice the large multicolor advertisement
for the evening paper glowing on the electroluminescent schedule board. The
large-area light-emitting diodes are made from organic conducting electrodes and
luminescent polymers that have been spray painted onto the board. You want
your usual sections of the local paper and then a few from different papers, so you
slide your plastic profile card into the newspaper machine. The card is a few
thousand transistors made from organic materials that have been printed by an ink
jet printer modified to deposit organic charge transporters and electrodes. It con-
tains your medical records, frequent flier numbers, custom newspaper prefer-
ences, and a host of other information. It also serves as a cash card. The machine
asks you to put in your display. You unroll your pocket display and insert it into the
machine. Several organic lasers write your customized newspaper into a thin
patch of organic material about the diameter of a dime in the upper right corner of
your portable display that functions as an erasable compact disk. On the train, you
plug your display into the seat back. The reader is a moving organic laser whose
reflection from the writing on the disk is recorded by a photovoltaic cell, which is
also made from organic materials, and the display is a high-resolution luminescent
color display made from organic light-emitting diodes. The active switching matrix
for the display pixels is made from hybrid materials, inorganic charge transporters
that have been solubilized to be processable using organic chemistry. The display
was printed on a flexible polymer in a reel-to-reel manufacturing process. A tiny
dot of silicon circuitry containing a microprocessor to interpret the information read
from the disk and containing display drive circuitry was attached. You marvel that
the display cost less than your monthly rail pass.

ing, and reel-to-reel processing. The organic materials can be designed at a

molecular level to incorporate different functional entities that bring the desired
optical, electrical, and mechanical properties and can then be modified to make
them suitable for economical processing schemes. Active work to develop hy-
brid organic/inorganic structures, copolymers with regular blocks of several dif-
ferent types, and layered materials will likely spur development of new devices
and new ways of integrating them into systems. Further research and develop-
ment promises to allow us to make materials that self-organize into complex
supramolecular arrays. Three-dimensional structures made in this way may be
useful in fabricating photonic gap structures for telecommunications, color re-
flective displays, artificial photosynthetic cells, synthetic membranes, and im-
proved electrophotographic materials.
Applying the physical science that underlyies these prospects will offer many
challenges. The practical limits to charge photogeneration, injection, and trans-
port are still poorly understood, especially at a microscopic level that would be
prescriptive for synthetic chemists. The basic physics of charge and energy
transfer is well established; but predictive understanding, given the complexity of
morphologically disordered and compositionally impure systems such as poly-
mers, is both an experimental and theoretical challenge. This is especially true at
interfaces between materials, which are becoming increasingly important as de-
vice dimensions shrink. Overcoming challenges associated with making efficient
electrical contact to organic materials is central to developing efficient light-
emitting diodes, transistors, and electrically pumped lasers. Similarly, the basic
science of material stability is critical in making relatively delicate organic mate-
rials commercially viable. An enormous amount of empirical progress has been
made toward this end, and we expect commercial products based on organic
electroluminescence to be widely available in 2000. It is likely that a deeper
understanding of the chemistry of degradation will lead to even more robust and
widely applicable materials.
The Physics of Optical Nanostructures

and Artificially Structured Materials
As electronic devices are made smaller and faster, it will become increas-
ingly difficult to transmit electrical signals over wire interconnects at low power
consumption for chip-to-chip or, at very high speeds, on-chip communications.
One possible development will be the use of miniature optical interconnects to
solve the timing, power, and switching-speed limitations of electrical intercon-
nects. This will require the development of low-power optical nanodevices that
are compatible with silicon technology. Other possible applications for arrays of
tiny light-emitting diodes are displays and optical correlators for producing paral-
lel computation of images. In the last decade major advances in optical micro-
cavity lasers, light-emitting diodes, and detectors resulted from increased under-

standing of the physics of quantum microcavities and advances in III-V and II-VI
compound semiconductor growth and processing techniques. Simultaneously,
these new materials fabrication and processing techniques have led to beautiful
insights into the science of quantum optical structures, which will in turn enable
more advances in technology.
By changing the dimensionality of a material by growth or processing, one
can greatly alter the density of electronic states, as shown in Figure 1.5. A bulk
three-dimensional distribution of electrons in a metal or semiconductor has a
density of available electronic states that rises as the square root of the energy.
The nature and the energies of these electronic states are greatly affected by
“quantum confinement.” Enclosing a thin layer (with thickness comparable to
the electron’s de Broglie wavelength, about 20 nm in GaAs) of lower band-gap
material between two slabs of higher band-gap material, yields a two-dimen-
sional quantum well with sharp steps in the electronic density of states (Figure
1.6a). Confining the electrons into a one-dimensional quantum wire produces a
series of sharp peaks at the onset of each new quantum mode in the wire (Figure
1.6b). Confining the electrons into a zero-dimensional “quantum dot,” a box
comparable in size to the wavelength of the electron in all directions, produces a
series of even sharper spikes that correspond to a series of confined quantum
levels for the electrons in the box (Figure 1.6c). Therefore lowering the dimen-
sionality of a structure on the atomic scale of a few nanometers will cause very
large changes in the physics of electronic transport. The advances in simulations
of electronic and optical processes in semiconductors, along with programmable
molecular-beam epitaxy (MBE) techniques for fabrication of multiple quantum
wells with atomic-scale accuracy—(“quantum engineering” of structures), have
led to the invention of the quantum cascade laser, which operates between con-
fined levels of electrons in a series of tailored quantum wells (see Box 1.11),
giant “pseudomolecules” with large optical nonlinearities, and resonant tunneling
devices.
The optical properties of a semiconductor are greatly affected by reducing
the dimensionality of its structure. For example, an exciton, an optical excitation
of the system near the band edge, comprises a bound state between a conduction
band electron and a valence band hole with wave functions similar to those of
Rydberg atoms. Either an electron or a hole, or both, can be bound in a lower
dimensional material by being confined in one, two, or three dimensions. This
can also greatly affect the excitonic levels and thus the optical properties near the
band gap. The dimensionality of the system is reduced if the size of a dimension
(for example, the thickness of a slab) is comparable to the diameter of the exciton,
which in GaAs is about 5 nm. In materials with strong coupling to light, the
optical and electronic plasma modes of the material interact to form coupled
exciton-polariton modes that are also greatly affected by the dimensionality of
the system. Theoretically, manipulating the density of states of the optical exci-
tations of a system can produce lasers with zero current threshold, in contrast to


THREE TWO ONE ZERO
DIMENSION
CURRENT
ZERO RESONANT VALLEY
VOLTAGE VOLTAGE VOLTAGE
20 NANOMETERS
DENSITY OF STATES
ENERGY
ENERGY ENERGY ENERGY ENERGY ZERO VOLTAGE RESONANT VOLTAGE VALLEY VOLTAGE
FIGURE 1.5 Illustration of the effect of quantum confinement on the density of elec-
tronic states. [Reprinted from Scientific American 8(1), 26 (1997) with permission from
John Deecken (artist).]
FIGURE 1.6 Two-, one-, and zero-dimensional small optical devices. [Reprinted from
Scientific American 8(1), 27-29 (1997) with permission from (a) S.N.G. Chu, Lucent
Technologies; (b) Lucent Technologies; (c) James S. Harris, Stanford University.]

BOX 1.11 Quantum Cascade Lasers
In conventional semiconductor lasers used for applications such as fiber-optic

communications and compact disk players, light is generated by the annihilation of
a negative and a positive charge (an electron in the semiconductor’s conduction
band and a hole in the valence band) in the active region. As such, the laser
wavelength is determined by the energy difference between the conduction and
valence bands (the so-called energy band-gap) and its differential efficiency, in the
limit of zero optical losses, cannot exceed unity, corresponding to one laser photon
created per electron-hole pair annihilated. These constraints are overcome in a
radically new semiconductor laser, called a quantum cascade (QC) laser, invented
at Bell Laboratories in 1994. In a QC laser, light is not generated by electrons and
holes recombining across the band-gap but by electrons alone as they make a
transition between two excited states of ultrathin quantum wells. The QC laser is
the first semiconductor unipolar laser. These energy levels arise from size quan-
tization when their thickness becomes comparable to or less than the electron de
Broglie wavelength. The wavelength is therefore not fixed by a material property
(the band-gap), but can be tailored over a very wide range by changing the thick-
ness of the layers using the same combination of materials. QC lasers are an
excellent example of materials by design. The energy levels and wave functions,
the optical matrix elements and the electron-phonon scattering times are designed
to achieve population inversion and the desired wavelength along with other laser
characteristics. The active regions of a QC laser are alternated with electron injec-
tors from which electrons tunnel into the upper excited state of the laser transition
(Figure 1.11.1 and see Figure 1.6). Electrons tumble down an energy staircase,
emitting a photon in each active region. Thus in an N-stage device (where N is
typically 25) N photons are created by a single electron traversing the structure.
This leads to much higher optical powers than in a conventional diode laser oper-
ating at the same wavelength. The Bell Laboratories group has been able to
demonstrate QC lasers based on quantum wells made of AlInAs/GaInAs material
grown by molecular beam epitaxy with wavelengths spanning a large portion (3 to
13 µm) of the mid-infrared spectrum. This spectral range includes the two atmo-
spheric windows (3 to 5 µm and 8 to 13 µm). In operating temperature and optical
power these devices outperform all other semiconductor lasers emitting at these
wavelengths and are the first to operate at room temperature and with powers of
several hundred milliwatts in pulsed and continuous wave operation. Single-mode
operation with wide wavelength tuning has also been demonstrated. QC lasers
are important in the detection by absorption spectroscopy of trace gases for pollu-
tion monitoring applications. Other potential commercial uses include industrial
process control, combustion diagnostics, and medical applications such as breath
analyzers for the early detection of ulcers, diabetes, and various forms of cancers.
Military applications include countermeasures and battlefield detection of toxic
gases and biological toxins via point sensors and lidar techniques.

FIGURE 1.11.1 The active regions of a QC laser are alternated with electron
injectors from which electrons tunnel into the upper excited state of the laser
transition. (Courtesy of Bell Laboratories, Lucent Technologies.)
conventional lasers in which gain is only achieved after sufficient excitation such
that the excitons have overlapped in space and have ionized into an electron-hole
plasma. Because excitons are bound states of two fermions, they should there-
fore obey Bose statistics and can themselves exhibit Bose condensation into a
macroscopic quantum ground state. The phase diagram of the excitonic matter in
semiconductors and its interaction with photons, the observation of lasing be-
tween sharp excitonic levels or lasing from Bose-condensed excitons is still
controversial, however, and is a field of much current interest.
Over the last decade four approaches for forming small optical devices have
been used:
1. MBE has been used for growing programmed series of two-dimensional

quantum wells (Figure 1.6a).
2. Cleaved-edge overgrowth with MBE has also been used to make one-
dimensional quantum wires (Figure 1.6b). Quantum wells are grown by MBE,
the sample is cleaved in vacuum perpendicular to the original growth direction,
and new quantum wells are grown to make T-intersections of two quantum wells,
forming wires of lower binding energy. Alternatively, growth in the intersection
of wells forms one-dimensional wires.
3. Two successive cleaved-edge overgrowths were used to make a series of

double-T zero-dimensional quantum dots (Figure 1.6c); or, another approach, the
clever use of strain in pseudomorphic overgrowth was used to produce strained
dot arrays (Figure 1.3.1).
4. Solution chemistry, described in Chapter 5, was used to produce a mono-
disperse colloidal suspension of semiconductor quantum dots.
Selective area overgrowth has also been successfully used to tailor the quan-
tum well thickness and composition laterally to make integrated semiconductor
optical devices; examples include electro-optical modulators that consist of a
ridge waveguide semiconductor laser and an optical modulator adjacent to each
other on a single chip. The fabrication of novel optical nanodevices is in its
infancy; many advances in design and manufacturing (such as self-assembly) are
required to allow mass applications.
Enclosing a material between highly reflecting mirrors produces an optical
microcavity, which can be tailored to control the angular distribution of the
output light from the structure as well as the spectrum and spontaneous emission
from any emitters inside. This is the principle behind vertical-cavity surface-
emitting lasers, or VCSELS, which are made by enclosing an active gain medium
between two highly reflective dielectric stacks of mirrors grown vertically on a
substrate. Microcavities with very sharp resonances (very high Q) have been
achieved by making whispering gallery mode resonators out of semiconductors
or droplets of dye solution or polymer in which the index change between the
material and air produces a high-Q waveguide around the outside diameter of the
structure (Figure 1.7). In fact, optical nanocavities have been produced that have
Q as high as several thousand. Because of the enormous field enhancement in the
cavity with such Q, nonlinear effects should be observable with only a few
incident photons. The intense emission of light observed, and yet to be conclu-
sively understood, from porous silicon is to some extent both a confinement and
microcavity effect. Another exciting new field involves tailoring optical materi-
als to achieve periodic opposite polarities of the ferroelectric polarization on a
length scale tailored to maximize the intensity of optical nonlinearities by effi-
cient phase matching of coherent four-wave mixing.
Extending the concept of optical microcavities into three dimensions leads to
the prediction of photonic band-gap materials, structures with periodic variations
of dielectric constant on a length scale comparable to the wavelength of light.
The idea is to design materials such that they can affect the properties of photons
in a manner similar to the way semiconducting crystals affect electrons. In a
semiconductor, the atomic lattice presents a periodic potential to an electron
propagating through the electronic crystal. The geometry of the lattice and the
strength of the potential are such that, owing to Bragg-like diffraction from the
atoms, a gap in energy for which an electron is forbidden to propagate in any
direction appears. In a photonic crystal, the periodic potential is caused by a
lattice of periodic dielectric media instead of atoms. If the dielectric contrast is

FIGURE 1.7 Very high-Q microcavity. (Courtesy of Bell Laboratories, Lucent Technol-
ogies.)
sufficient, Bragg scattering of light off the lattice can also produce a forbidden
band that extends over a certain energy range in which light cannot propagate in
any direction. However, a defect in the periodicity will introduce localized states
in the photonic band-gap in much the same way that localized states exist for
electrons within the semiconducting gap. The nature and shape of the localized
states will depend on the dimensionality of the defect: a two-dimensional slab or
a one-dimensional line will define mirrors and waveguides in the dielectric array,
and a zero-dimensional defect will define a microcavity. The design and manipu-
lation of these defects in the photonic band-gap material promises far more
control of photons.
As the technology for fabricating photonic lattices in the near infrared (IR)
and visible spectral regions advances, they will offer a radically different means
for controlling light. For example, Figure 1.8 shows a theoretical model of how
light propagates in a periodic square lattice of dielectric rods with a waveguide
produced by the intersection of two missing rows of rods. Remarkably, propaga-
tion is predicted to occur with no losses even though the bend in the waveguide is
on a length scale comparable to the wavelength of light! In ordinary dielectric
waveguides today, the bending losses caused by leakage from evanescent fields
requires very smooth bends with bending radii of 10 cm—thus the waveguides
are large, making manufacture and packaging of integrated optical structures

FIGURE 1.8 How light propagates in a periodic square lattice. (Courtesy of Massachu-
setts Institute of Technology.)

difficult. Low-cost fabrication of photonic band-gap waveguides for communi-

cations wavelengths of 1.3 and 1.5 µm, or wavelengths in the near IR and visible
regions important for display, copying, and data-storage technologies, would
revolutionize the field of integrated optical devices in much the same way as the
integrated circuit has revolutionized electronics.
Challenges, Priorities, and Frontiers of Optical Materials and Phenomena

The frontiers in the field of optical materials and phenomena are novel
manufactured materials with tailored optical properties made by self-assembly,
poling, lithography, MBE and other techniques not yet invented, organics and
other complex materials, nanostructures and micromachined components, biol-
ogy, and ultrafast phenomena.
Some of the outstanding scientific questions about optical materials involve
understanding the physics of lasing and the coupling of exciton-polariton-phonons
in nanostructures and quantum cavities, fundamental understanding of the phys-
ics of electro-optical processes in organics, and understanding the physics of
ultrafast nonequilibrium processes in semiconductors, metals, and biological
molecules and tissues.
Some outstanding technology needs are low-cost all-optical communications
network and consumer access components such as new fiber materials and de-
vices; all-optical buffer memory, add-drop filters, amplifiers, semiconductor blue
lasers, fast light switches, fast spatial light modulators; materials with tailorable
optical properties such as better nonlinear optical materials, resists, and photonic-
band gap materials in the near IR communications wavelength region; and low-
cost assembly and manufacturing techniques for optical components such as self-
assembly, stamping, and printing.
SCIENCE AND TECHNOLOGY OF MAGNETISM

Beginning with the Ancient Mariner’s compass and continuing with such
applications as automobile starter motors, refrigerator magnets, and computer
hard disk drives, the importance of magnetic materials (Figure 1.9) in a wide
range of technological uses steadily grows. Such materials display a host of
fascinating properties of scientific interest. Many of these properties have proved
to be useful in technological applications. The interplay of science and applica-
tions has made magnetism an extremely exciting segment of condensed-matter
and materials physics. The last decade has seen an acceleration in the advances
of both the technology and science of magnetism—advances that have set the
stage for even more profound discovery and technological developments in the
near future.
The field of magnetism enjoys an unusually strong technology pull, second
in condensed-matter and materials physics only to that of semiconductors, par-

ticularly silicon. Various forms of magnetic storage technology dominate this

pull. Bulk materials have long had applications in technologies such as motors,
generators, and transformers. In addition, the emerging field of magnetoelec-
tronics, with its potential impact on microelectronics technology, is stimulating a
fresh wave of enthusiasm along with a broadened research agenda.
This section begins with a review of a few exciting recent developments and
future directions of selected important technologies based on magnetic materials
and phenomena. Against this backdrop, selected scientific accomplishments of
the past decade and opportunities for the future will be presented. The section
concludes by summarizing some of the major outstanding scientific questions
and suggesting priority directions for future research.
Technology Pull
The industry of magnetic recording, in all its forms, constitutes an enterprise
FIGURE 1.9 Magnetic response of a ferromagnetic particle. The initially unmagnetized

magnetic particle exhibits a hysteresis loop in its magnetization (M) as an external mag-
netic field (H) is increased from zero to a maximum value, reversed through zero to a
minimum value, and subsequently returned to zero. Characteristic features of hysteresis
curves include the saturation magnetization, Ms (the maximum magnetization of the sam-
ple); the remnant magnetization, Mr (the magnetization that persists in the sample when
the external field is zero); and the coercive field, Hc (the external field necessary to return
the magnetization to zero). “Soft” magnetic materials have low Hc, high permeability
(~dM/dH), and a small area enclosed by the hysteresis loop. “Hard” magnetic materials
have high Hc, high Mr, and a large area enclosed by the hysteresis loop.

with annual revenues in excess of $100 billion. This consists primarily of mag-
netic disk, magnetic tapes, and optical disks for digital data storage together with
various forms of magnetic recording for audio and video. This industry is expe-
riencing an overall compound annual growth rate in revenue of about 10 percent
per year. This growth rate is expected to continue for at least another decade,
with magnetic storage playing the dominant role. The United States “owns”
about 40 percent of the magnetic storage business, the largest single component
of which is hard disk drives (see Box 1.12). This component alone is a $30
billion a year business.
The accelerating interplay of the science and applications of magnetism is
well illustrated by the phenomenon of magnetoresistance. Lord Kelvin first
observed this effect in 1856. Beginning in the early 1980s, a decade of research
and development (at IBM) with this basic laboratory phenomenon perfected a
product of major commercial importance. The first magnetoresistive sensor used
in the recording head of a hard disk drive has an intricate structure in which data
is sensed by a 20 nm thick permalloy (a NiFe alloy) layer. The useful change in
resistance of this film as it passes in close proximity to a small magnetized region
of a magnetic disk is about 2 percent. The time from discovery of the phenomena
to a high-volume product was 135 years.
Recent research activities led to the discovery of a superior form of magneto-
resistance, called giant magnetoresistance (GMR). GMR requires the interaction
between at least two very thin ferromagnetic films and can register a resistance
change at room temperature of about 10 percent in the same magnetic field range
as permalloy. Moreover, as an interfacial phenomenon, its performance in so-
called spin-valve recording sensors improves with decreasing film thickness,
which also increases the storage density. In contrast to the case of magnetoresis-
tance, only 10 years have passed since the original discovery of GMR before an
initial product was produced. In the exponentially growing global hard-drive
industry, GMR sensors will be needed to sustain this rate of improvement into the
third millennium.
A range of magnetic tape storage systems with applications from audio and
video to data storage constitute another third of the magnetic storage business.
Storage densities in this arena are experiencing a single-digit compound annual
growth rate with continuing cost reduction. Here, too, magnetoresistive heads
play an important role in the continued scaling to higher densities. Magnetic
particle tapes are still the industry standard, but thin film tapes have been intro-
duced and will undoubtedly dominate some time in the future.
In a completely different arena, bulk magnetic materials constitute a $4
billion global market, with the United States holding approximately 20 percent of
the market share. This market is projected to grow to more than $6 billion by the
year 2000. “Hard” bulk magnetic materials are essential constituents in a wide
variety of electric motor and generator technologies. For such applications, the
strength of the permanent magnetism, or so-called “maximum BH-product,” is

BOX 1.12 Magnetic Storage in Hard Disks
The basic configuration of a hard-disk drive is illustrated in Figure 1.12.1. Key

aspects of this technology include the read/write head, media, head-disk interface,
tracking of the head with respect to the disk, and signal processing to distinguish
the ones and zeros as the disk spins beneath the head.
The evolution of the areal storage density in leading-edge products was illus-
trated in the introduction. This exponential growth in storage density has led to an
associated growth in the number of hard-disk drive bytes shipped per year, as
shown in Figure 1.12.2.
FIGURE 1.12.1 Magnetic recording disk drive assembly with a magnetoresistive

head. Three disks and one of the movable arms supporting a read/write head are
visible. The arrow zooms in on the magnetic sensor of a recording head. The
NiFe film measures 20 nm in thickness by 1 or 2 µm in width. The permanent
magnetism of the hard bias induces a reference state of the magnetization inside
the NiFe film. The magnetic field emanating from small magnetized regions,
representing the stored data, in the rotating disk changes the resistance in the
NiFe films thus reading out the data as voltage changes across the contacts,
which also supply a constant current through the NiFe film. (Courtesy of IBM
Research.)

10000
HDD Capacity Shipped, Petabytes
2830
1545
1000
639
CGR = 95% 335
161
100
80.7
32.9
14.9
10
8.18
4.71
3.73
1.56
1
1990 1992 1994 1996 1998 2000 2002
Year
FIGURE 1.12.2 The number of hard disk drive bytes shipped in products per
year. The compound annual growth rate of 95 percent is projected to continue
for the foreseeable future. (Courtesy of IBM Research.)
Exponential improvement in storage density has been achieved through con-

tinued advances and scaling of all aspects of the technology. As an example,
consider advances in magnetic head technology. Through the first half of the
decade thin film inductive heads dominated the industry and became ever more
difficult to scale. The first magnetoresistive heads were introduced in 1992 and
played a pivotal role in increasing the compound annual growth rate of the areal
storage density from 30 percent to 60 percent (with a 40 percent annual reduction
in cost per bit!). Giant magnetoresistive heads introduced at the end of 1997 will
help ensure the continuation of this trend.
the defining materials characteristic. Research and development leading to in-

creased BH-products (Figure 1.10) has steadily decreased the costs, sizes, and
weights of motors in diverse devices like auto starters, cordless shavers, hand-
held drills, vacuum cleaners, washing machines, dryers, machine tools, motor-
ized toys, and disk drives in laptop computers. Motor vehicles alone account for
70 percent of permanent-magnet usage in starters, electric windows, speakers,
and cassette and CD players. A luxury car may contain 80 motors.
The most recent permanent-magnet development spurt occurred in the mid-

1980s and dramatically illustrates the unpredictable effects of the interplay be-
tween politics, economics, research, and development. Samarium-cobalt was the
leading hard magnetic material in the late 1970s in spite of the high cost of
samarium. The cost of samarium-cobalt magnets ballooned fivefold when the
world’s principal source of cobalt disappeared during the 1978 national upheaval
in Zaire. Intense focused research established that samarium and cobalt could be
replaced by neodymium and iron, respectively. Not known in advance was that
the attainment of permanent magnetization in the new compositions hinges on
complicated processing sequences including, in one case, creation of amorphous
material by melt-spinning followed by crystallization through severe mechanical
treatment and subsequent annealing. Equally unexpected was that the product
would be stronger, both magnetically and mechanically, and less expensive. The
rapidly growing NdFeB segment of the bulk magnetic materials market is pro-
jected to reach $4 billion by the year 2005.
“Soft” bulk materials play key technological roles in radio frequency (rf) and
power distribution applications. At frequencies higher than 100 kHz, ferrites
remain the materials of choice. They are widely used in all manner of rf and
microwave elements such as antennas, filters, circulators, and insulators. Histori-
cally, advances in ferrite performance (higher permeability, higher frequency
100
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Steels
0.1
1880 1900 1920 1940 1960 1980
Year
FIGURE 1.10 Chronological trend of (BH)max where the data represent initial demon-
stration in the laboratory. [Reviews of Modern Physics 63, 819 (1991).]

response, and lower losses) have been driven by niche military applications, with
commercialization following rapidly. At lower frequencies, soft magnetic mate-
rials are used extensively in transformers for the power-distribution industry.
Here, incremental improvements can have an enormous technological and eco-
nomic impact. Particularly important is magnetic metglass, an amorphous mate-
rial in ribbon form prepared by ultra-fast quenching. The absence of magneto-
crystalline anisotropy has the consequence that the magnetization vector can be
easily rotated. Therefore, a metglass has high magnetic permeability and low
losses. When used in the core of a power transformer, metglass is more expen-
sive than crystalline materials and increases capital costs; however, this increased
capital cost is often rapidly amortized by continuing savings from decreased
transformer loss in electric power transmission. Worldwide savings of several
billion dollars have been realized by the introduction of magnetic metglass.
Magnetostriction is another area of magnetism of considerable, and growing,
interest for both military and commercial applications. Most of the materials
development work in this area has been focused on rare-earth transition metal
alloys. Strains of up to 1 percent, along with considerable force actuation, have
been demonstrated in practical applied fields. Applications range from sonar
pulse generation to high-reliability replacement of hydraulic systems in aircraft
and even tanks.
A final area is magnetoelectronics (exclusive of magnetic storage), which
includes a variety of devices and associated assemblies. The largest component
of this industry today is sensors used for commercial, scientific, and military
applications. Such sensors range from Hall effect sensors, to superconducting
quantum interference devices (SQUIDs), flux gate magnetometers, search-coil
magnetometers, magnetoresistance (MR) and GMR sensors, to magnetic force
microscopes. Magnetoelectronics is characterized by a number of small but
stable niche markets. The worldwide market for SQUID instrumentation, for
example, is about $20 million per year; the market for magnetic force micro-
scopes is similar.
The potential sleeping giant in the field of magnetoelectronics is a growing
collection of novel devices and circuits that possibly can be integrated onto a
high-performance chip to perform some complex function. More realistically,
key elements may be integrated with high-performance semiconductor technol-
ogy to produce new generations of microchips with function, density, and/or
performance beyond that achievable with semiconductor technology alone. Non-
destructive read out memory chips in which bits are stored in small electrically
addressable magnets have been demonstrated at capacities of up to 256 kb (Fig-
ure 1.11). The nonvolatile radiation-hard nature of this memory together with
potential for scaling to much higher density and performance, especially as new
magnetic elements are developed, show considerable promise.

FIGURE 1.11 Micrograph of prototype 256-kb nonvolatile magnetic random access

memory chip. (Courtesy of Honeywell.)
The Physics of Magnetism

It is evident from the above discussion that there is a strong technology pull
for research in magnetism. The last 10 years have seen numerous exciting dis-
coveries, a number of which have already had a direct impact on technology.
Others are providing us with a better understanding of the world around us and/or
are helping lay the groundwork for future technology. It is amazing that, al-
though much is known about magnetism and while effects drive a $100 billion
per year industry, our basic understanding of magnetism, even in a material such
as iron, is incomplete. As an example, Figure 1.12 shows the results of a simula-

tion of a two-dimensional array of magnetic moments approximating a 10 nm ×

500 nm × 1000 nm sheet of permalloy. One might anticipate that for a system of
this size, the moments would all work in unison, switching together under the
influence of an applied field; however, as shown in Figure 1.12, such is not the
case. The behavior of this rather elementary system exhibits a great deal of
structure and complexity. There is neither experimental nor theoretical consen-
sus on the detailed behavior of such a system. Nor is it understood how small
such a system must be to ensure true, single-domain behavior in which all of the
moments always remain parallel to each other.
The fundamental limit on stability of magnetic domains is an important area
of basic investigation in magnetism. The advancing march of magnetic technol-
ogy makes investigation of these limits inevitable, but probing these limits raises
some of the most challenging questions for condensed-matter physics and mate-
rials science, such as, What is the smallest size magnetic element stable against
external perturbations such as temperature fluctuations? and, Given that quantum
mechanics sets bounds on the lifetime of any magnetic state, how do such bounds
ultimately establish limits on the size of the smallest possible magnetic entities
useful for technological applications?
Molecular magnets such as the ferric wheel shown in Box 1.13 are the
subject of a wide variety of physical analyses aimed at shedding light on these
and other challenging questions about magnetism in small structures. Traditional
FIGURE 1.12 Micromagnetic simulation of the switching behavior of a 10 nm × 500 nm

× 1000 nm permalloy dot. The arrows indicate the direction of the magnetization (m) at
the point in the hysteresis cycle indicated on the curve in the lower left. (Courtesy of
IBM Research.)

BOX 1.13 Nanomagnets
Fundamental questions about nanomagnets could not be addressed were it

not for the remarkable advances made by materials scientists and chemists in the
synthesis of exquisitely controlled nanometer-scale magnetic structures. Many
“traditional” synthesis techniques have been applied successfully in this area: sub-
100 nm scale permalloy particles can be made with lithographic techniques, and
growth assisted by scanning-tunneling microscopes has proven that it is possible
to fabricate pure iron particles with a variety of sizes and aspect ratios. The most
exciting new techniques involve various “self-assembly” strategies that are emerg-
ing as extensions of chemical synthesis techniques. The relatively low-tech tech-
niques of colloid growth have been adapted to make cobalt particles 8 nm in diam-
eter with close to atomic control. Actual atom-by-atom control in the magnetic
domain is now achieved by metallo-organic molecular synthesis; magnetic mole-
cules containing exactly 10 iron atoms (the “ferric wheel,” see Figure 1.13.1), or
exactly 12 manganese ions, for example, are now routinely available.
FIGURE 1.13.1 Structure of the Fe10 “ferric wheel” cluster, where the large solid
circles represent the iron atoms and the empty circles are, in order of decreasing
size, chlorine, oxygen, and carbon. The 10 Fe3+ ions, each with a magnetic
moment corresponding to the same angular momentum or spin, are bound to-
gether into a perfectly regular ring. High magnetic field experiments have shown
that the Fe3+ ions exhibit antiferromagnetic behavior; neighboring spins prefer to
be antiparallel. The spin structure of the molecule passes through a rich se-
quence of phase transitions resembling those in bulk layered antiferromagnets.
These experiments open the prospect of precisely controlling the structure, inter-
actions, and dynamics of nanomagnets. [Reprinted with permission from D.
Gatteschi, A. Caneschi, L. Pardi, and R. Sessoli, “Large clusters of metal ions:
The transition from molecular to bulk magnets,” Science 265, 1056 (1994). Copy-
right © 1994 American Association for the Advancement of Science.]

characterization gives the basic magnetic parameters of the particle: ionic mo-
ment (i.e., the local state of spin), exchange interaction (the coupling strength
between the spins), and anisotropy (the height of the energy barrier in the double-
well potential separating the “up” state from the “down” state). Such character-
izations demonstrate that the ferric wheel behaves very much as an atomic-scale
analog of a layered antiferromagnet. Less traditional characterizations are re-
quired to understand the ultimate stability of such molecular magnets, which is
determined by quantum tunneling. One particularly interesting example is the
observation of what might be called “quantized hysteresis” in the Mn(12) mol-
ecule: at low temperatures, this structure shows a propensity to switch from up to
down at a sequence of regularly spaced magnetic fields. Some evidence suggests
that these magnetic fields coincide with resonances between quantum levels of
the up and down wells, resulting in enhanced tunneling. Although some details
of the tunneling mechanism remain to be understood, this is a particularly simple
example of the stability (up versus down) of the moment of a molecular magnet
being ultimately limited by a purely quantum effect.
Of more profound significance than the observation of quantum tunneling
would be the observation of “quantum coherence” in these nanomagnets. The
phenomenon is closely analogous to the microscopic quantum coherence (MQC)
effect sought in small SQUIDs for years—the creation of a quantum state in a
controlled superposition of up and down states. The regular advance of the phase
of this superposition would result in the sinusoidal oscillation of the magnetic
domain between the up and down states. Observation of such coherence oscilla-
tions would foreshadow a significant change in the role that quantum mechanics
might play in the dynamics of magnetic domains. Although we might view
magnetic tunneling as a nuisance, destroying the stability of a bit stored in the
magnetic domain, coherence, if controllable, could be the resource needed to
realize the basic element of storage and processing in quantum computing. Signs
of magnetic quantum coherence have in fact been observed in a naturally occur-
ring magnetic nanoparticle.
In the past 10 years rapid progress has been made in the characterization and
understanding of magnetic multilayers, exchange coupling, and spin-dependent
transport through magnetic materials and interfaces. Results from an experiment
representative of this exciting, ground-breaking work is shown in Figure 1.13.
This experiment measured the oscillatory exchange coupling between iron layers
separated by a chromium spacer of varying thickness. The chromium wedge was
grown epitaxially on the nearly perfect surface of an iron whisker crystal whose
magnetization is split into two opposite domains along the [001] direction. A thin
iron film was deposited on top of the chromium, and its magnetization was
measured using scanning electron microscopy with polarization analysis
(SEMPA). The SEMPA image, drawn on the wedge schematic, clearly shows
that the exchange coupling reverses direction with almost every single monolayer
change in chromium thickness. The oscillatory coupling period, which arises

from nesting features in the Fermi surface of chromium, is actually slightly

incommensurate with the chromium lattice, producing the phase slips observed at
chromium layers 24 and 44.
The applications focus provided by GMR has helped to stimulate and invigo-
rate the search for new magnetic heterostructures and nanostructures and new
magnetoresistive materials. GMR materials consist mainly of nanometer thick-
nesses of interleaved metallic layers that are alternately ferromagnetic and non-
ferromagnetic. (Analogous nano-dispersed two-phase composites can also exhibit
GMR properties.) Key to strong in-plane GMR are spin-dependent scattering at
layer interfaces and an electron mean free path (approximately 10 nm) greater
than sublayer thickness. The relative resistance change can be greater for current
flow perpendicular to the layer planes. Resistance changes as large as 100 per-
cent relative to the low-resistance state have recently been reported.
Work on magnetic multilayers is also stimulating new thinking concerning
novel devices that can be made by integrating magnetic materials with standard
semiconductor technology. An example of this is shown in Figure 1.14 where a
GMR (Co/Cu) multilayer serves as the base of an n-silicon metal base transistor.
Biased in the common base configuration, this device exhibited a 215 percent
change in collector current in a magnetic field of 500 G at 77 K with typical GMR
characteristics. The in-plane GMR of the multilayer was only 3 percent. Al-
though by no means a practical transistor, this structure allows the study of spin-
dependent scattering of hot electrons in magnetic multilayers. More practical
spin transistors may be forthcoming, particularly if ways to achieve 100 percent
spin-polarized injection can be devised.
FIGURE 1.13 Oscillatory exchange coupling in Fe/Cr/Fe. [Physical Review Letters 67,
140 (1991).]

Spin-polarized tunneling experiments in magnetic thin-film planar junctions

are helping to elucidate novel magnetic properties as well as demonstrate features
of considerable device potential. The first successes in spin-polarized tunneling
between two ferromagnets through an insulating tunnel barrier occurred only
very recently, even though spin-polarized tunneling was predicted more than 20
years ago. A simplified structure of this type of junction is shown in Figure 1.15.
The magnetization of the ferromagnetic base electrode is pinned in the direction
indicated. The magnetization of the ferromagnetic counter electrode is shown as
aligned with that of the base electrode but can be reversed by application of a
modest magnetic field. A proper magnetic design yields a hysteretic response
curve symmetric about H = 0. Resistance changes of greater than 30 percent have
been demonstrated. Such junctions are of considerable interest as potential stor-
age elements in one approach to magnetic RAMs. Slightly different configura-
tions give devices with nonhysteretic characteristics but with similar magnetore-
sistance. These devices are attractive candidates for sensor applications and may
provide a follow-on to GMR sensors for hard-disk drives.
The enormous surge in the synthesis and study of high-Tc perovskite materi-
als spawned a concerted effort to explore the magnetic properties of similar
materials. Some of these materials exhibit what has been termed colossal magne-
toresistance (CMR). The magnetoresistance of doped manganite structures such
as La1-xSrxMnO3 changes by a factor of 2 or 3, although not at temperatures and
magnetic fields suitable for practical device applications. These systems share
much in common with high-Tc cuprate superconductors, from which dozens of
new crystal structures have emerged. Replacing copper with manganese, for
example, could generate a platform of new crystal chemical systems, some of
which will undoubtedly exhibit promising CMR properties.
Ie e_ Pt
Co
Cu
Co
Ie
e_ Si Emitter
- _
Vbc e Si Collector
+
Ic
A e_
FIGURE 1.14 Schematic cross section of a prototype spin-valve transistor. [Physical
Review Letters 74, 5260 (1995).]

a) Structure
b) Magnetoresistance
0
H
FIGURE 1.15 Magnetic tunnel junction structure. (Courtesy of IBM Research.)
Steady advances in improving the characteristics for technological applica-

tions has been realized in the more traditional bulk materials. For example, in the
case of high-permeability soft materials, we have learned how to compensate for
the deleterious magnetic anisotropy from one magnetic element by introducing a
second element having an anisotropy of the opposite sign. Another way to cancel
anisotropic effects, and thereby increase permeability, is to rapidly quench a
magnetic ribbon, as with magnetic metglass, thus making its structure amor-
phous. The preferred axes of the atomic moments are now random and therefore
the atomic contributions to anisotropy energy tend to cancel, making it easy to
remagnetize. In the case of permanent magnets, the magnetic anisotropy, and
therefore the coercivity of a ferromagnet, decrease steeply as its temperature
approaches the Curie critical point, where these parameters necessarily vanish.
We have learned how to increase the Curie temperature, and thereby the coerciv-
ity, of permanent magnet materials of the RexFey type by introducing interstitial
N or C or, to lesser degrees, Ti, V, W, Mo, or Si. The complexity as well as the
importance of processing details in the synthesis of high-performance magnetic
materials is well demonstrated in the case of NdFeB discussed previously.
Measurement techniques are vital in the research of magnetic materials and
phenomena. Experimental advances that have contributed to breakthroughs in
the last decade include scanning-tunneling microscopy (STM), magnetic force
microscopy (MFM), magneto-optic Kerr imaging, and scanning electron micros-
copy with polarization analysis (SEMPA). STM has been critical to understand-
ing how subtle differences in physical structure can make profound differences in
magnetic structure or properties. Characterization techniques based at major
facilities are equally important. For CMR, as for high-Tc research, neutron dif-

fraction is needed to obtain the position of the oxygen atoms within the unit cell
as a function of temperature, field, pressure, and doping. Electron microscopy is
needed to understand growth inclusions that form two-dimensional stacking
faults. Synchrotron sources enable advanced spectroscopies to identify the +3
and +4 valence states of Mn and their ratio. Diffuse x-ray scattering and quasi-
elastic neutron scattering are used to investigate the presence and dynamics of
polaronic distortions. A number of other techniques based on such effects as
spin-polarized photoemission, magnetic circular dichroism, and second harmonic
generation are becoming increasingly prevalent, while many others are in the
initial stages of demonstration.
Major Outstanding Materials and Physics Questions

and Issues in Magnetism
Many outstanding scientific questions remain in the field of magnetism. An-
swers to a number of these questions will have an important technological impact
and are necessary to continue the momentum and growth of the magnetics industry.
With a few notable exceptions, we lack detailed understanding of the mag-
netic properties of nanostructured magnetic elements and arrays of such ele-
ments. Examples include the following:
• The nature of domain structure and its influence on switching behavior;

• The dynamics and switching times in such elements or systems;
• The influence of temperature, both in the context of stability against
thermally induced switching and in the context of structural change at elevated
temperature;
• The nature of the interaction of spin-polarized currents with such ele-
ments, both reversible and irreversible; and
• The role and the impact of quantum coherence and macroscopic quantum
tunneling in the smallest of such structures consisting of a cluster of atomic spins.
We need to understand the impact of the issues above and related issues
regarding technologies such as magnetic recording and the synthesis of new
materials with improved properties such as higher BH-products. Because of the
resurgence of the science and applications of magnetism, it is important that we
reestablish the teaching of magnetism as a priority in our universities as a whole
rather than at only a few institutions that presently teach it.
Much remains to be learned concerning the nature of spin-polarized trans-
port. Questions need to be answered about the role of structure and the relation-
ship of surface and interface structure to magneto-transport, the scattering mecha-
nisms at interfaces in GMR, and the physics of the temporal and spatial decay of
nonequilibrium magnetism. Also required is a detailed understanding of the
mechanism of spin injection, either directly or through tunneling barriers from

magnetic metals into metals and semiconductors. Answers to these types of

questions are needed to engineer better GMR, CMR, and magnetic tunnel junc-
tion (MTJ) materials and devices. In a particularly useful spin transistor with true
on and off states separated by many orders of magnitude in conductance will
require very nearly 100 percent spin-polarized current injection from one region
of the device into another.
Advanced synthesis and processing techniques need to be developed to pro-
duce novel material with a high potential for scientific and technological impact.
Layered structures, nanostructured three-, two-, and one-dimensional materials,
and materials with higher BH-products are all attractive areas for further explora-
tion. As in other areas of condensed-matter and materials physics, a systematic
approach—technically and organizationally—is needed to explore the vast phase
space of magnetic materials. As applications develop, methods to bridge the gap
between fabrication techniques that serve to produce initial demonstrations and
more controlled and reliable techniques that can be migrated to development and
manufacturing will be needed.
Several difficult challenges remain in the measurement area. We need to
understand how to magnetically probe individual electron and nuclear spins di-
rectly. Questions to be addressed include, What is the ultimate spatial resolution
of magnetic measurement techniques? And, Can we fabricate a spin-polarized
STM? Advances in measurement technology related to such questions will have
a profound impact on our ability to understand the nature of magnetism in
nanostructures.
Finally, in the technology arena, continued focus on scaling the density for
magnetic storage is needed. This will involve a strong, systematic, ongoing
program in both media and detectors that will draw heavily on several of the
condensed-matter and materials physics areas mentioned above. In addition,
there is enormous opportunity in the arena of magnetoelectronics for new mag-
netic effects and devices that may set the stage for magnetism to play a key role
in future microelectronic chip technology. A key element will be integration of
complex magnetic materials with mainstream semiconductor technology.
FUTURE DIRECTIONS AND RESEARCH PRIORITIES

Numerous outstanding scientific and technological research needs have been
identified in electronic, photonic, and magnetic materials and phenomena. If
those needs are met, it is anticipated that these technology areas will continue to
follow their historical exponential growth in capability per unit cost for the next
few years. Silicon integrated circuits are expected to continue to follow Moore’s
Law at least until the limits of optical lithography are reached; transmission
bandwidth of optical fibers is expected to grow exponentially with advances in
optical technology and the development of soliton propagation; and storage den-
sity in magnetic media is expected to continue to grow exponentially with the

maturation of GMR and development of CMR and MTJs in the not too distant
future. Although these changes will have major impact on computing and com-
munications over the next few years, it is clear that extensive research will be
required to produce new concepts, as will new approaches to reduce research
concepts to practice, if these industries are to maintain their historical growth rate
over the long term.
Continued research is needed to advance the fundamental understanding of
materials and phenomena in all areas. For example, despite the extensive techno-
logical application and impact of magnetic materials and, despite more than a
century of research in magnetic materials and phenomena, we lack a first-prin-
ciples understanding of magnetism. By comparison, the technology underlying
optical communication is very young. The past few years has seen enormous
scientific and technological advances in optical structures, devices, and systems.
New concepts such as photonic lattices, which are expected to have significant
technological impact, are emerging. We have every reason to believe that this
field will continue to advance rapidly with commensurate impact on communica-
tions and computing.
As device and feature sizes continue to shrink in integrated circuits, scaling
will encounter fundamental physical limits. The feature sizes at which these
limits will be encountered and their implications are not understood. Extensive
research is needed to develop interconnect technologies that go beyond normal
metal and dielectrics in the relatively near term. Longer term, technologies are
needed to replace today’s silicon field-effect transistors. One approach that bears
investigation is quantum state switching and logic as devices and structures move
further into the quantum mechanical regime.
A major future direction is nanostructures and artificially structured materi-
als, which was a general theme in all three areas. In all cases, artificially struc-
tured materials with properties not available in nature revealed unexpected new
scientific phenomena and led to important technological applications. As sizes
continue to decrease, new synthesis and processing technologies will be required.
A particularly promising area is that of self-assembled materials. We need to
expand the research into self-assembled materials to address such questions as
how to control self-assembled materials to create the desired one-, two-, and
three-dimensional structures.
As our scientific understanding increases and synthesis and processing tech-
nologies of organic materials systems mature, these materials are expected to
increase in importance for optoelectronic and, perhaps electronic, applications.
Many of the recent technological advances are the result of strong interdiscipli-
nary efforts as research results from complementary fields are harvested at the
interface between the fields. This is expected to be the case for organic materials;
increased interdisciplinary efforts—for example, between condensed-matter and
materials physics, chemistry, and biology—offer the promise of equally impres-
sive advances in biotechnology.

In conclusion, the committee identifies a few major outstanding scientific

and technological questions and research and development priorities.
Major Outstanding Scientific and Technological Questions

• What technology will replace normal metals and dielectrics for intercon-
nect as speed continues to increase?
• What is beyond today’s FET-based silicon technology?
• Can we create an all-optical communications/computing network?
• Can we understand magnetism on the meso/nano scales needed to con-
tinue to advance technology?
• Can we fabricate devices with 100 percent spin-polarized current injec-
tion?
Priorities
• Develop advanced synthesis and processing techniques, including those
for nanostructures and self-assembled one-, two-, and three-dimensional struc-
tures.
• Pursue quantum state logic.
• Exploit physics and materials science for low-cost manufacturing.
• Pursue the physics and chemistry of organic and other complex materials
for optical, electrical, and magnetic applications.
• Develop techniques to magnetically detect individual electron and nuclear
spins with atomic-scale resolution.
• Increase partnerships and cross-education/communications between in-
dustry, university, and government laboratories.

New Materials and Structures
Our ability to make new materials and structures—both in bulk and in re-
duced dimensions or length scales—is inextricably linked to the advancement of
our understanding of fundamental phenomena in condensed-matter and materials
physics. This chapter describes some of the past decade’s advances in inorganic
materials and structures. Some of the advances and promising new areas in
organic materials are discussed in Chapter 5. As described in Box 2.1, an aston-
ishing array of new materials with unexpected properties has come over the
horizon. Improvements in synthesis and processing have led to dramatic im-
provements in the properties of established materials and our ability to exploit
these properties. As a result, we can now fabricate new combinations of materi-
als, features of reduced dimensions, and other characteristics that differ in signifi-
cant ways from previous possibilities. Some of these developments have pro-
vided fertile ground for condensed-matter and materials physicists to explore
novel fundamental phenomena; others show promise for finding applications
quickly; some have the potential to change our lives.
New materials underlie the science and technology described throughout this
report. Beyond condensed-matter and materials physics, they enable both sci-
ence and future technologies. In some cases, entirely new and unexpected phe-
nomena appear in a class of new materials. Layered cuprate high-temperature
superconductors are a new class of materials that has kept experimentalists and
theorists alike searching to understand the physical basis of high-temperature
superconductivity. New materials sometimes allow entirely new device concepts
to be realized or lead to a dramatic change in their scale, such as single-molecule
wires made of carbon nanotubes; and new forms of already known materials can
93

possess different properties. Semiconductor nanoclusters, which emit light whose

wavelength depends on cluster size, offer the possibility of tailoring material
properties to suit a particular need. Even mature techniques, such as those for
bulk crystal growth, demand continuous improvements in process control to
produce the size or quality of material required for either technological applica-
tions or fundamental studies.
Better understanding of the mechanisms at play in materials that have been
known for decades can lead to new approaches that alleviate detrimental prop-
erties. An excellent example is the introduction of metallic oxide electrodes in
ferroelectric devices, which reduces aging effects dramatically. Better under-
standing of the details of materials preparation can give rise to improvements in
processing. Improved insight into the kinetics of epitaxial growth can dramati-
BOX 2.1 Additions to the Zoo: New Materials and Structures

of the Past Fifteen Years
There have been far too many new developments in the past 15 years or so to
document them all in detail, but all these developments have been made possible
by advances in two intertwined areas: complexity and processing. Many of the
new materials and structures are dramatically more complex, compositionally or
structurally, than have been studied previously. In general, this trend has required
advances in processing to allow control of the increased complexity. In other
cases, the final product may not be much more complex than other well-known
materials or structures, but the processing itself may need to be altered to achieve
more control over the growth process in order to obtain the new material.
Advances giving rise to new materials and structures fall into three categories.
Some involve the synthesis of an entirely new compound or material. The ad-
vance may have been revolutionary, meaning that the properties of the new mate-
rial (or in some cases its existence) could not have been predicted. In other cases,
advances in processing have allowed fabrication of new or modified materials or
structures whose properties were suspected before the material was actually
made. This may allow a well-known compound to be remade in a new form with
different properties. Third, well-known materials are sometimes found to exhibit
new (in some cases unexpected) properties that appear when the ability to pro-
cess them is improved. The new property may be found in a known material
simply by looking at it in a new light, which shines on it as a result of insight gained
from another materials system.
The materials advances listed in Table 2.1.1 were driven by different motiva-
tions. Many addressed a technological need, such as the need to transfer or store
information. Others were driven by scientific curiosity. Although the driver can be
clearly identified in each case, the two sets are not mutually exclusive. Many
discoveries that result from pure scientific curiosity ultimately find their way into
products. For example, low-temperature superconductors are now used in mag-
nets for magnetic resonance imaging. Other discoveries, though originally moti-
vated by a technological need, give rise to very beautiful and fundamental insights.

NEW MATERIALS AND STRUCTURES 95
For example, the fractional quantum Hall effect was first observed in high-mobility
semiconductor structures now used in high-frequency applications.
TABLE 2.1.1 Some New Inorganic Materials of the Past Fifteen Years
Advance Driver Nature of Advance
New compounds/materials
High-temperature superconductors Science Revolutionary
Organic superconductors Science Revolutionary
Rare-earth optical amplifier Technology Evolutionary
Intermetallic materials Technology Evolutionary
High-field magnets Technology Evolutionary
Organic electronic materials Technology Evolutionary
Magnetooptical recording materials Technology Evolutionary
Bulk amorphous metals Technology Evolutionary
New structures of known materials

Quasicrystals Science Revolutionary
Buckyballs and related structures Science Revolutionary
Nanoclusters Science Evolutionary
Metallic hydrogen Science Evolutionary
Bose-Einstein condensates Science Evolutionary
Giant magnetoresistance materials Technology Revolutionary
Porous silicon Technology Evolutionary
Diamond films Technology Evolutionary
Quantum dots Technology Evolutionary
Foams/gels Technology Evolutionary
New properties of known materials

Gallium nitride Technology Revolutionary
Silicon-germanium Technology Evolutionary
cally lower the growth temperature in semiconductor processing. Understand-

ing and exploiting fundamental growth mechanisms can lead to previously
unattainable structures as in the use of strain to induce the self-assembly of
quantum dots.
Many advances in condensed-matter and materials physics are the direct
result of the availability of materials and structures of a quality not previously
attainable. These materials and structures in turn exist because of improvements
in the technology used to make, study, measure, and see them. The impetus for
improvements in the materials is often a technological need, not the search for
new knowledge. The new knowledge generated, however, in some cases itself
becomes the enabler of revolutionary technology. This interplay is explored in
Box 2.2.

BOX 2.2 The Science—Technology Circle
Tremendous advances in compound semiconductor devices were enabled by

dramatic improvements in the growth of thin films that began in about 1970 with
the invention of molecular beam epitaxy (MBE, see Figure 2.2.1). The direct ante-
cedents of MBE were developments in vacuum technology beginning in the 1960s
and continuing into the 1970s, driven by accelerator development and space phys-
ics. As the attainable vacuum improved, it became possible to keep a surface
atomically clean for long enough to study it. Surface probes such as Auger spec-
troscopy and electron diffraction techniques allowed the clean surfaces to be
studied.
MBE enabled the controlled, layer-by-layer growth of compound semiconduc-
tors. The composition of the film could be changed abruptly. Extremely high
mobility was achieved in GaAs-GaAlAs heterostructures through “modulation
doping.” Research into these structures was pursued because of their utility in
high electron-mobility transistors (HEMTs, see Figure 2.2.2) which are used today
in high-speed electronics.
Study of these layers at low temperatures in extremely high magnetic fields led
to the discovery of the quantum Hall effect, which takes place in a two-dimensional
electron “gas” produced in a transistor-like device. Under these conditions, elec-
tron correlations dominate, leading to precise quantization of the Hall conductance.
As the quality of the layers was improved further, the mobility also improved, and
the fractionally quantized Hall effect (FQHE) was discovered, in which the quan-
tum number describing the system is a fraction rather than an integer (see Figure
2.2.3). The FQHE has subsequently been used for unprecedentedly accurate
measurements of the fundamental quantity h/e2 (Planck’s constant divided by the
square of the charge of the electron).
FIGURE 2.2.1 Molecular beam epitaxy was invented at Bell Laboratories in

about 1970 as an outgrowth of advances in vacuum technology and surface
science techniques. (Courtesy of Bell Laboratories, Lucent Technologies.)

FIGURE 2.2.2 A high electron-mobility transistor (HEMT) such as those used in

cellular telephones. The round bonding pads are 100 µm in diameter, roughly the
size of a human hair. The gate of the transistor, just 0.05 µm across, appears as
the two narrow lines in the center of the scanning electron micrograph. (Courtesy
of Sandia National Laboratories.)
FIGURE 2.2.3 A pictorial representation of the many-particle state that underlies

the fractional quantum Hall effect. The height of the landscape represents the
amplitude of the quantum wave of one electron as it travels among its com-
panions (shown as balls). The arrows indicate the vortices induced by the mag-
netic field, which attach themselves to the electrons to form composite particles.
(Courtesy of Bell Laboratories, Lucent Technologies.)

The remainder of this chapter examines a few of the past decade’s most im-
pressive advances in materials and structures. The selections emphasize a number
of themes that have emerged in materials research. Some of the discoveries have
been completely unexpected. Others were predicted, although the experimentalists
did not always know of these predictions when they did their work. Our thinking
about new materials has changed fundamentally; we now consider dramatically
more complex possibilities in our search for new materials than we did a decade
ago. In some classes of materials that have been studied for many decades, we have
achieved a much deeper understanding of physical and chemical mechanisms that
govern their properties. This understanding in turn has led to improvements in the
properties of the materials, either through elimination of problems inherent in
existing materials by improved processing or by the introduction of new materials.
Even in a material as thoroughly studied as carbon, a myriad of new forms has been
discovered, exhibiting a wide range of properties. Shrinking the dimensions of
well-known materials such as semiconductors has led to properties dramatically
different from those of the bulk. New concepts in thin-film growth have led to
improved film properties by changing the growth and processing windows. Fi-
nally, there has been a change in the attitude toward strain in heteroepitaxial sys-
tems that allows strain to be used to tailor the morphology as well as the electrical
properties of the layers. The culmination of this effort is in the use of strain to
induce self-assembly of quantum dots.
COMPLEX OXIDES
Surely one of the most surprising developments since the publication of the
Brinkman report1 has been the discovery of high-temperature superconductivity
in complex oxide materials, beginning in 1986 with the observation by Bednorz
and Müller of superconductivity near 30 K in La2-xBaxCuO4. This discovery was
rewarded with the 1987 Nobel Prize in Physics (see Table O.1). The field ex-
ploded with the discovery of superconductivity at temperatures in excess of the
boiling point of liquid nitrogen (77 K). The family of known high-temperature
superconducting materials now numbers near 100, with the highest supercon-
ducting transition temperature (Tc) above 130 K. High-temperature superconduc-
tivity has significantly altered the direction of condensed-matter and materials
physics in several ways. The excitement generated by this totally unexpected
discovery attracted researchers from throughout the field of condensed-matter
and materials physics and beyond to the study of these fascinating materials.
More recently, the principles that have been successful in the study of these
materials have proven valuable in the study of other areas of condensed-matter
and materials physics, most notably other sorts of oxides.

High-temperature superconductors are much more complex than many of the

materials that have occupied the attention of condensed-matter and materials
physicists for many decades (see Figure 2.1). This complexity, however, is a
two-edged sword, giving rise to a richness in the possible structures and proper-
ties of the materials, but also making the materials extremely challenging to
produce, control, and understand.
The crystal structures of these materials are dramatically more complicated
and have lower symmetry than those of low-temperature superconductors or
semiconductors. The physical properties are similarly anisotropic. This makes
the control of crystallographic orientation extremely critical. The unit cell is
large. A large unit cell and low symmetry offer many opportunities for the
formation of defects during materials preparation, either in individual atomic
sites or in long-range crystallographic perfection.
The superconducting coherence length is of the order of the interatomic
spacing in some crystallographic directions. This makes the materials exquisitely
sensitive to defects—from atomic-scale defects, such as vacancies, interstitials,
and substitutional atoms, to grain boundaries and other larger-scale imperfec-
tions. Separating the intrinsic properties of such materials from artifacts caused
by defects is critical to gaining full understanding of the high-Tc phenomenon. It
places extreme emphasis on materials preparation and serves as an example of
the true collaboration that must exist between those who seek to understand and
control the growth of the materials and those who probe their underlying physics,
as illustrated in Box 2.3. Conversely, the carefully controlled introduction of
FIGURE 2.1 Historical development of inorganic superconductors, with Nobel prizes

indicated by stars. Increasing superconducting transition temperature correlates with in-
creased chemical complexity and more constituent elements, as shown by the numbers 1
to 5. (BCS stands for the Bardeen-Cooper-Schrieffer theory of classical superconductors.)
[MRS Bulletin 19, 26 (1994).]

BOX 2.3 Vortex Matter: A Novel Window on Materials Physics
In the past 5 years, a new area of condensed-matter investigation has

emerged, based on the remarkable behavior of vortices in superconductors. For
decades, type-II superconductors in a magnetic field have been understood as
arrays of quantized tubes of magnetic flux, each surrounded by a circulating “vor-
tex” of supercurrent that defines its interaction with its neighbors and the outside
world. In traditional superconductors, thermal energy is limited to about 20 K by
the superconducting transition temperature, and the vortex tubes form an elastic
solid. High-temperature superconductors offer a new possibility: thermal energies
up to about 100 K may melt the vortex solid, creating a novel liquid state with
dramatically different properties that arise from the relative motion of vortices. As
early as 1988, motion of vortices below Tc was found to create undesired dissipa-
tion in high-Tc cuprates. The thermodynamic nature of the melting phase transi-
tion and of the resulting vortex liquid has been vigorously debated. Theorists soon
realized that vortex phases and phase transitions embody many fundamental fea-
tures of condensed-matter physics, including reduced dimensionality, entangle-
ment of flexible line objects, and the role of disorder on elastic media. Studies of
vortex matter provide new insight into these basic materials physics issues in other
condensed-matter environments. The diversity of equilibrium vortex phases is
illustrated in the phase diagram of Figure 2.3.1.
Although theoretical analysis of vortex liquids and solids abounded, experi-
mentalists were frustrated by the quality of the available high-temperature super-
conducting materials. Real materials contain defects like impurity clusters, dislo-
cations, twin boundaries, and rough surfaces. In superconductors, these defects
generate pinning sites that immobilize vortices and remove them from participation
in equilibrium behavior. The experimental observation of vortex phase transitions
had to await more perfect materials with dramatically reduced defects and vortex
pinning.
In 1992, the first indications of vortex lattice melting were observed in electrical
transport experiments. These measurements accurately located the melting line
in the H-T plane and gave tantalizing but indirect evidence that the transition was
first-order in clean materials. Further transport experiments suggested that first-
order melting was destroyed by controlled pinning disorder and suggested the
existence of a critical point in the melting line. These and other experimental
observations created new interest and activity in the field.
Experimentalists then sought the next level of fundamental information—thermo-
dynamic characterization of the order and entropy changes on vortex melting—with
magnetization and specific heat experiments. Such experiments require an even
higher level of sample perfection to ensure thermodynamic equilibrium in the solid
phase, where pinning effectiveness is significantly enhanced by shear elasticity.
Sample size was a second serious problem: the most perfect crystals are also the
smallest, making it extremely difficult to resolve the tiny magnetic and thermal signa-
tures of melting from the much larger background. Nevertheless, sample prepara-
tion techniques continued to improve with better understanding of the roles of com-
position, growth rates, and annealing procedures. Improved materials enabled
several landmark thermodynamic experiments, which have now settled the question
of the thermodynamic order of the transition and raised new questions about critical
points, vortex entanglement, and the dimensionality of the liquid.

FIGURE 2.3.1 A suggested phase diagram of vortex matter in the magnetic field-
temperature plane. Several vortex liquid and solid phases are illustrated, includ-
ing a liquid of entangled vortex lines, a perfect hexagonal lattice, a polymer glass
of entangled lines, and solid phases disordered by point pinning defects (vortex
glass) or by line pinning defects (Bose glass). The melting transition is first-order
from a lattice and proposed to be second-order or continuous from a glass. A
critical point may occur on the melting line, where the first-order character disap-
pears. The normal and vortex liquid states are separated by a fluctuation domi-
nated by crossover rather than by a true phase transition. (Courtesy of Argonne
National Laboratory.)
Vortex matter has emerged as a vital field, with its own developing issues and
international community of researchers. It extends traditional studies of atomic
matter in several ways. For example, vortex density is linear in the applied mag-
netic field, so it can easily be changed by an order of magnitude with the twist of a
dial. Experimental access to such a large density range is unheard of in atomic
matter. The interactions among vortices are well-known Lorentz forces, which can
be treated analytically or in simulation with no uncontrolled approximations. Ad-
vanced materials development has produced clean crystals with few pinning de-
fects, revealing intrinsic thermodynamic behavior and its evolution under controlled
disorder induced by electron or heavy ion irradiation. Finally, vortices can be set in
motion by the Lorentz force from an externally applied transport current, enabling
studies of driven phases, steady-state motion, and the new area of dynamic phase
transitions. This remarkably rich microcosm of condensed-matter physics owes its
existence to two materials developments: the landmark discovery of high-temper-
ature superconductors, which introduced large thermal energies into the vortex
phase diagram, and dramatic improvements in materials perfection, which enabled
experimental studies of the delicate thermodynamics of collective vortex behavior.

defects of a particular type into the material by, for example, ion irradiation or
judicious atomic substitution allows the properties to be adjusted.
The superconducting oxides with Tc above 77 K all contain at least four
elements, two of which are copper and oxygen. Oxygen moves readily in these
materials, during both sample preparation and subsequent processing. Changing
the oxygen content by just a few percent can determine whether a material is a
superconductor or an insulator. It can also govern the symmetry and crystal
structure of the material, resulting in phase transformations during specimen
preparation that, to date, have been unavoidable. Precise control of the stoichi-
ometry of the metal constituents is also required to optimize the superconducting
properties, although the consequences of deviations from ideal stoichiometry are
not nearly as critical for the metals as for oxygen.
Current interest in the high-temperature superconducting materials centers
around two general areas: superconducting electronics and the carrying of large
currents. The electronics applications can be further subdivided into logic and
high-frequency applications. Electronics applications require thin films, generally
in combination with films of other materials. The fabrication of reproducible
tunnel junctions with useful properties for logic applications has been very chal-
lenging because of the incompatibility of high-temperature superconducting mate-
rials with most nonoxide barrier materials and the extremely short coherence length
of the superconductor. Quite a few metallic oxides with compatible crystal struc-
tures have been identified and studied as a result of considerable research into
suitable barrier materials. A promising area of application is in components for
communications, particularly in the gigahertz frequency domain. The major issues
are the surface resistance of the material and electrical nonlinearities at high fre-
quencies. Though there has been considerable progress in improving surface resis-
tance in the past few years, detailed understanding of the relationships between this
and other relevant properties and the structure of the materials is still emerging.
Technological applications demand large-area films that can be deposited
fast enough to be economically viable. There has been dramatic progress, with
high-quality films of YBa2Cu3O7-x (see Figure 2.2) now available on substrates
several hundred square centimeters in area.
Current-carrying applications require bulk material or thick films. Grain
boundaries, especially those with significant misorientation between grains, are
extremely detrimental to high critical currents because of both the extreme anisot-
ropy of the materials properties and the properties of the grain boundaries them-
selves. The most successful approach for bulk materials with properties of poten-
tial technological interest has been the use of drawn, multifilament wires, especially
in the bismuth system. The drawing induces alignment of the grains in the fila-
ments and increases the critical-current density. More recently, biaxial orientation
has been achieved in thick YBa2Cu3O7-x films deposited on metal substrates, either
coated with an aligned buffer layer fabricated by ion beam-assisted deposition or
with strong crystallographic alignment induced in the substrate by rolling.

FIGURE 2.2 The orthorhombic crystal structure of superconducting YBa2Cu3O7-x. The

superconducting transition temperature of this material is above 90 K. Note the presence
of four elements in the compound and the low symmetry of the structure. These charac-
teristics make materials synthesis challenging and give rise to dramatic anisotropy in the
physical properties of the material. (Courtesy of Princeton University.)
It has proven very fruitful to apply the principles discovered and techniques
developed for high-temperature superconductivity to other classes of complex
oxides. In some cases, this research has been driven by the need for materials
with specific electronic or magnetic properties that are chemically and structur-
ally compatible with high-temperature superconductors. These materials are
typically needed as buffer or barrier layers. Compatible materials with other
properties could be needed in the future if high-temperature superconducting
devices are to be successfully integrated with devices having other functionality,
such as memory and optical devices. Perhaps the most impressive demonstration
of the application of lessons from high-temperature superconductivity has been
the recent interest in colossal magnetoresistance in LaMnO3-derived materials
(see Box 2.4).

BOX 2.4 Colossal Magnetoresistance:

A Rediscovered Property of Old Materials
The discovery of high-temperature superconductivity changed our thinking

about complexity in materials composition and structure. It emphasized that truly
different properties could be obtained when new dimensions of complexity are
considered. A particularly good example of the change in paradigm that high-
temperature superconductivity has caused is the observation and study of colossal
magnetoresistance (CMR). CMR was first observed in a perovskite material, lan-
thanum manganate (LaMnO3) in which some of the lanthanum is substituted by
an alkaline-earth element: calcium, strontium, or barium (see Figure 2.4.1). The
manganates have been known for many decades and had previously been studied
for their promising catalytic properties. Presumably, more recent advances in
magnetic storage technology sensitized researchers to rediscover the CMR ef-
fect and to pursue it with the vigor and determination sparked by the potential
applications.
As innumerable materials with perovskite-based crystal structures received
new attention in the aftermath of the high-temperature superconductivity discov-
ery, the alkaline-earth-substituted manganates were found to have magnetoresis-
tance effects up to three orders of magnitude larger than the previously known
FIGURE 2.4.1 Resistivity (ρ), magnetoresistance ratio (∆R/RH), and magnetiza-

tion (M) as a function of temperature curves for an epitaxial La-Ca-Mn-O film.
[Reprinted with permission from S. Jin, M. McCormack, T.H. Tiefel, R.M. Fleming,
J.M. Phillips, and R. Ramish, Applied Physics Letters 64, 3045 (1994). Copyright
© 1994 American Institute of Physics.]

giant magnetoresistance metal multilayers. This observation was not predicted,

and an understanding of the phenomenon is even now just being developed. The
current consensus is that the relevant magnetic behavior of these compounds
results from the motion of electrons between adjacent manganese ions via the
intervening oxygen ion. This “double-exchange” interaction favors parallel (ferro-
magnetic) spins of neighboring Mn3+ and Mn4+ ions produced by the alkaline-
earth substitution. This interaction competes with the antiferromagnetic coupling
of manganese ions in the absence of the mobile electrons.
Ultimately, the symmetry of the spin ordering on neighboring manganese sites
determines the electrical resistivity: parallel spins lead to low resistivity while anti-
parallel spins give high resistivity. Thus the variation of resistivity with temperature
can be understood in terms of the transition between a semiconducting paramag-
netic state above the Curie temperature, Tc , and a metallic ferromagnetic state
below Tc . Above Tc , a magnetic field enhances spin alignment and reduces
resistance, but it has little effect below Tc . Therefore the largest bulk magneto-
resistance effect is observed in the temperature region near Tc .
Magnetoresistive effects, Tc , and the mobility of electrons between manganese
ions are thus closely connected. This is one of the key ingredients of manganite
physics, and it has been tested recently in experiments in which the manganese-
manganese overlap has been systematically varied through controlled bond-angle
variations induced by substitutions of ions with various sizes. Because the rich-
ness of physical phenomena derives from the interplay among these electronic
properties, local lattice strains, and other parameters of comparable magnitude,
control and modification of materials properties are of paramount importance to
exploration and exploitation of the manganites.
Although the bulk properties of manganites are of great interest in their own
right, the recent discovery of spin-dependent electron transport across grain
boundaries holds further promises. These phenomena occur in fields low enough
for possible sensor applications in magnetic storage. Active research has now
started on the development of small-area thin-film devices that rely on the spin-
dependent resistance across interfaces, and this work will benefit from the many
advances in materials engineering developed in contact with high-temperature
superconductors.
Progress in these materials demonstrates once again the complex interplay
among the detailed chemistry, materials structure, and electronic and magnetic
properties, which provides a fruitful research field for fundamental studies and
hope for future technology.
Although ferroelectric materials have been a topic of considerable research

for a long time, developments in high-temperature superconductivity within the
past decade have aroused new interest and insight, leading to improved electrode
materials and better control over the structure and properties of the ferroelectrics
themselves. An outgrowth is the current interest in high dielectric constant
materials, generally complex oxides, for use in high-density semiconductor
memories.

Research on complex oxides in general and high-temperature superconduc-

tors in particular has spawned new growth and processing techniques as a result
of the unusual properties of these materials. This research has given rise to
materials of ever-improving quality, which allow physicists to probe the funda-
mental mechanisms at work and technologists to explore more fully their promise
for applications. The area is vital and will be a source of exciting physics and
materials research for the foreseeable future.
ELECTROCERAMICS
Electroceramic materials have been studied and used for many decades be-
cause of their interesting and in some cases novel properties, such as ferroelec-
tricity, piezoelectricity, pyroelectricity, and electro-optic activity. Current interest
in the ferroelectrics centers on their potential in nonvolatile memories and high
dielectric constant capacitors. Micromachines, such as accelerometers, displace-
ment transducers, actuators, and so on, require piezoelectric materials. Room-
temperature infrared detectors make use of pyroelectric properties. Electro-optic
properties enable color filter devices, displays, image storage systems, and the
optical switches required in integrated optical systems.
Electroceramics can serve as “smart” materials, functioning as both sensors
and actuators (see Box 2.5). All smart materials have at least two phase transi-
tions (e.g., crystallographic and electronic), and their synthesis and processing
must be carefully controlled to regulate their excursions through phase space.
The complexity of these phenomena and the materials that display them has made
this an exciting area. There has been dramatic progress in the control of electro-
ceramic materials properties, in understanding the relationships between proper-
ties of interest and the underlying microstructural mechanisms that control them,
and in integrating various materials to give improved properties or even new
behavior.
Progress has been especially impressive in the ferroelectric materials. Ex-
tensive research has focused on understanding the mechanisms responsible for
the degradation of ferroelectric and high-permittivity perovskite thin films with
time, temperature, and external field stress. The three most important degrada-
tion phenomena are ferroelectric fatigue, ferroelectric aging, and resistance
degradation.
Ferroelectric fatigue, the loss of switchable polarization with repeated polar-
ization reversals, is caused by pinning of domain walls, which inhibits switching
of the domains. Elimination of fatigue is critical for nonvolatile memory applica-
tions. Recent results have shown that charge trapping at internal domain bound-
aries is the primary fatigue mechanism. Fatigue also induces changes in the
oxidation states of isolated impurity point defects, which are much more stable
than optically generated ones in unfatigued samples.
Fatigue can be largely eliminated in some ferroelectric systems [e.g., lead

BOX 2.5 Electroceramics in Composite Smart

Materials and Biomimetic Systems
As the sensitivity and selectivity of a sensor increases, its structure generally

becomes more complex. This often involves moving from single-phase materials
to composites in which the connectivity, symmetry, or scale of the composite is
designed to give a desirable field concentration or composite symmetry. Each
constituent material has an associated phase transition. For example, polymeric
materials with phase transitions in which the elastic properties change dramatically
may be combined with ferroelectric materials in which the dielectric properties have
an associated instability. The different types of instability allow fabrication of struc-
tures especially good for sensing and actuating. Different connectivity patterns
optimize the tensor coefficients that contribute to the figure of merit for the applica-
tion. Figure 2.5.1 shows the figure of merit for composite piezoelectric materials
with different connectivities. The largest figure of merit by far is for the “moonie”
structure, which consists of either a piezoelectric ceramic disk or a multilayer stack,
sandwiched between two specially designed metal end caps. This design pro-
vides a sizable displacement, as well as a large generative force.
The evolution of these sensors and actuators moves the composites progres-
sively closer to the configurations adopted by biological systems that perform the
same function. The 1-3 composite hydrophones, for example, mimic the geometry
and sensing function of the lateral line of the North Atlantic cod, a series of fibrous
sensors spaced along the length of the fish. Similarly, the air space in the moonie
transducer is a resonant cavity that corresponds to the fish swim bladder. By
vibrating the bladder wall, a fish emits a low-frequency grunt that propagates well
through the ocean. The same cavity also makes the moonie and the fish more
sensitive. As more complex sensing and actuating functions are designed, inspi-
ration can be gained by studying the analogous biological “composite” systems.
60,000
50,000
Figure of Merit (10 -15 MKS)
40,000
30,000
20,000
10,000
0
PZ
T 0-3 1-3 3-1 3-3 3-2 on
ie
Mo
FIGURE 2.5.1 Hydrophone figure of merit for composite piezoelectric materials.

The connectivity is indicated schematically above each bar. (Courtesy of Penn-
sylvania State University.)

zirconate titanate (PZT)] by using electrodes of metallic oxides, such as

(La,Sr)CoO3 (LSCO) and (RuO2). The interaction between the ferroelectric
material and its electrode plays a critical role in determining fatigue performance,
perhaps because of the accumulation of oxygen vacancies near the electrodes
during cycling. This suggests that electrodes with a large tolerance for oxygen
deficiency, such as some of the metallic oxides, should offer better fatigue char-
acteristics than those that serve as ineffective sinks for oxygen vacancies. The
improvement in fatigue characteristics offered by this approach is shown in
Figure 2.3.
Layered perovskite materials such as SrBi2Ta2O9 have recently received
attention because of their lack of polarization fatigue even with simple metal
electrodes. The emerging picture attributes this to less oxygen vacancy accumu-
lation at the electrodes caused by either a smaller vacancy population or reduced
FIGURE 2.3 Developments in new electrode materials for ferroelectric capacitors have
reduced the fatigue in these devices by more than 6 orders of magnitude. The upper
image shows a “conventional” capacitor structure of the ferroelectric material
Pb((Nb,Zr)Ti)O3 (PNZT) with unbuffered platinum electrodes, along with the fatigue of
the remanent polarization. The polarization decays to half its initial value after 105
cycles. The lower image shows a capacitor structure with the platinum electrodes buff-
ered by La0.5Sr0.5CoO3. This capacitor shows no fatigue even after 1012 cycles. (Cour-
tesy of the University of Maryland.)

mobility. Smaller polarization in these materials should also result in weaker

pinning and thus higher unpinning rates.
In addition to their ferroelectric and dielectric properties, many of the same
materials also exhibit piezoelectric properties. PZT is the most widely used. On
cooling from high temperature, the crystal structure of PZT undergoes a displacive
phase transformation, and the point symmetry changes from cubic to tetragonal.
To make use of piezoelectric ceramics, compositions near a second phase transi-
tion are chosen. At the Curie point, PZT converts from a paraelectric state with
the ideal cubic perovskite structure to a ferroelectric phase located near a mor-
photropic phase boundary between the tetragonal and rhombohedral states. Very
large piezoelectric coupling between electric and mechanical variables is ob-
tained near this phase boundary. Much of the current research in this field
involves looking for other morphotropic phase boundaries to further enhance the
electromechanical-coupling factors. Ferroelectric thin films have been success-
fully used in a variety of microelectromechanical systems applications, including
accelerometers, microvalves, pressure sensors, and infrared detectors. Micro-
actuators and microsensors are designed to make use of the strong piezoelectric
response of ferroelectrics such as PZT and to ease the fabrication and incorpora-
tion of on-chip electronics. The development of fabrication methods such as
surface micromachining, low-stress silicon nitride deposition, and solution depo-
sition of ferroelectric thin films has been essential.
Control of the growth of ferroelectric films has been a prerequisite for the
progress that has been made. Film crystallinity has improved dramatically, and
techniques such as ion bombardment have allowed the growth temperature to be
lowered, improved the selection of the desired perovskite phase over the pyro-
chlore phase, improved the degree of preferred alignment in the films, and re-
sulted in denser, smoother films. The use of oxide electrodes and templates for
growth has helped eliminate unwanted orientations and dramatically improved
the electrical properties. Control of the film microstructure has led to improved
leakage current.
Nanoscale force microscopy has begun to allow examination of the switch-
ing of individual grains in a polycrystalline matrix with resolution of about 10
nm, as shown in Figure 2.4. The ability to follow localized processes will be
important in unraveling the physical phenomena that govern these complex
materials.
NEW FORMS OF CARBON

The first documented conjecture of the existence of hollow-cage molecules
of carbon appeared in 1966. Four years later, the existence of C60 (buckminster-
fullerene) was predicted theoretically, with more rigorous treatments appearing
in subsequent years. Nevertheless, the molecule itself was not observed until
1985, when it appeared serendipitously during a series of graphite laser vaporiza-

FIGURE 2.4 Scanning-force microscopy of topographic (a) and piezoresponse (b-f) im-
ages of a PZT film grown on a LSCO/TiN/Si substrate. The central grain was switched
completely from the polarization direction down (dark) to up (white). The switch back of
the central grain into the polarization down direction starts mainly at the grain boundaries
with the surrounding grains. [MRS Bulletin 23, 39 (1998).]

tion experiments designed to simulate the chemistry in a red giant carbon star.
Finally, in 1990, a method was developed to produce macroscopic quantities to
allow the intense investigation of this and related compounds that have been a
focus of research in the present decade. As suggested in Figure 2.5, C60 turns out
to be just one of a veritable menagerie of three-dimensional closed carbon mol-
ecules: spheres, tubes, particles, and combinations thereof, with one or multiple
layers. The discovery of fullerenes by Curl, Kroto, and Smalley was recognized
with the 1996 Nobel Prize in chemistry (see Table O.1).
The remarkable geometry of these molecules is enabled by slight deviations
from the hexagonal bonding configuration found in graphite resulting from the
desire to eliminate energetic dangling bonds at the edges of graphite sheets. The
addition of twelve pentagons to the hexagonal array transforms the open graphite
structure into any of the observed closed molecules that have only positive curva-
ture. Heptagonal rings give rise to a saddle-shaped surface when buried among
hexagons.
Carbon nanotubes, which were originally grown as a by-product in the
fullerene-generating chamber, are quasi-one-dimensional structures with a simple
and well-understood atomic structure. A chemist might think of a carbon nano-
tube as a monoelemental polymer. The nanotube is an ideal model for quasi-one-
graphite
diamond
C60
(10, 10) tube
C70
FIGURE 2.5 Some representative forms of carbon. (Courtesy of Rice University.)

dimensional structures because its known atomic structure makes computer simu-
lations more reliable. Nanotubes can be as much as several microns long, and
tube diameters range from one to a few tens of nanometers. A metal serves as a
catalyst for nanotube formation, preventing the growing tubular structure from
wrapping around and closing into a smaller fullerene cage. Nanotube growth is
believed to take place at the open ends of the tubes. During growth, the open
tubule end required to fabricate long, single-wall nanotubes can be maintained by
a high electric field, by the entropy opposing orderly cap termination, or by the
presence of a metal catalyst. The tube ends tend to close quickly when the growth
conditions become inappropriate, for example, when the temperature drops or
when the carbon atom flux is too low. As long as the tube end is open, carbon
atoms can be deposited on the tube-end peripheries, and they can grow. When
pentagons are formed for some reason, the tubes will be capped. If the axial
growth rate is dominant over the radial one, the tubule will become a single-shell
tube. A comparable growth rate in both the axial and radial directions will form
spheroidal particles.
Characterization of carbon nanotubes has been slow compared to fullerene
research activity, partly because of the inability to synthesize macroscopic quan-
tities of the tubules and to refine them. Many nanotubes are in the form of a
multiple-shell structure of nested cylindrical tubes separated by about 0.34 nm,
which is the same as the d0002 lattice spacing of graphite. Cylindrical crystals are
often seen in biological protein crystals but rarely in inorganic materials. Recent
measurements on single-wall carbon nanotubes have shown that they do indeed
act as genuine quantum wires, confirming theoretical predictions, as shown in
Figure 2.6.
Electronic and mechanical properties of nanotubes deviate from those of a
bulk graphite crystal. Depending on tubule diameter and helicity, both of which
affect the band gap, the behavior can range from metallic to semiconducting.
Because it makes for a more symmetrical structure, less helicity leads to better
conductivity. This leads to true molecules that are also true metals, something
chemistry has never had before. Because of the quasi-one-dimensionality of
these nanotubes, conduction is quantized.
One unexpected phenomenon in nanotubes is the ability to fill them with a
material. Nonhexagonal carbon rings in the hexagonal network are responsible
for tubule morphologies and presumably local strain. After deposition of a small
amount of lead on tubule surfaces and heating, some of the metal clusters move to
heptagon sites. Nanotubes can be opened by mild oxidation at the reactive site at
the closed end. On heating, some of the lead is transported into the central hollow
in the tubule. The intercalated material is crystalline and not pure lead but lead
carbonate or oxide. This finding suggests that the tubule tips react selectively in
air at elevated temperature, but the rest of the tubules do not react. Strain induced
by including pentagons in the tubule tips may be responsible for the selective
reaction. Carbon onions have also been stuffed with metals and metal carbides.

a 3 µm
Vgate Vbias
50 nm
b C
B
A
0.5
1
0
-4 0 4
0.0
A B C
-0.5
-4 -2 0 2 4
Bias voltage (mV)
0.1
0.0
-200 0 200
Gate voltage (mV)
FIGURE 2.6 (a) Atomic-force microscope tapping-mode image of a carbon nanotube on

top of a Si/SiO2 substrate with two 15-nm-thick platinum electrodes and a corresponding
circuit diagram. This single-wall nanotube has a diameter of ~1 nm. Its total length is 3
mm, with a section of 140 nm between the contacts to which a bias voltage (Vbias) is
applied. A gate voltage (Vgate) applied to the third electrode in the upper left corner of the
image is used to vary the electrostatic potential of the tube. (b, top) Current-voltage
curves of the nanotube at a gate voltage of 88.2 mV (trace A), 104.1 mV (trace B), and
120.0 mV (trace C). The inset shows more I-Vbias curves with Vgate ranging from 50 mV
(bottom curve) to 136 mV (top curve), with vertical offsets for clarity. The variation with
Vgate of the gap around Vbias = 0 implies Coulomb charging of the tube. The stepwise
increase of the current at higher voltages may result from an increasing number of excited
states entering in the bias window. (b, bottom) Current versus gate voltage at Vbias = 30 mV.
The two traces shown were performed under the same conditions. [Reprinted with per-
mission from S.J. Tans, A.R.M. Verschueren, and Cees Dekker, “Individual single-wall
carbon nanotubes as quantum wires,” Nature 386, 474 (1997). Copyright ©1997 Nature.]

A large family of structures can be generated in the high-temperature re-

gimes of the arc experiments used to produce fullerenes and nanotubes. In
addition to nanotubes, the arc yields a large quantity of polyhedral graphitic
particles with well-defined faceting and a wide-ranging size distribution (8 to 60
nm). If electrodes incorporating a metallic salt or oxide are used, a small percent-
age of encapsulated metallic particles within closed graphitic shells is produced.
The quasi-spherical onionlike structure (buckyonion) is the exclusive result of
the irradiation process. The same effect may be obtained from diverse starting
carbon materials (polyhedral graphitic particles, buckytubes, and even disordered
forms of carbon). The onions grow by a kind of internal epitaxy as the layers
reorganize, progressing from the surface to the central shell. The model structure
for the final product is the concentric arrangement of spherical fullerenes, formed
by 60n2 carbon shells. Small buckyonions (2 to 4 shells) are very stable under
intense electron bombardment, suggesting that they may be the most stable forms
of carbon cluster.
By virtue of their unique structures, fullerenes exhibit novel chemical trans-
formations. These molecules are spherical or nearly so. Molecules with high
point-group symmetry, which are not bound strongly in the solid state, tend to
crystallize into structures with long-range periodicity of the molecular centers of
mass, but the molecular orientations are random or even dynamically disordered.
Because C60 has high electron affinity, it forms anion salts with alkali and alka-
line-earth metals as well as with strong organic molecules. K3C60 and other alkali
fulleride salts exhibit superconductivity with Tc above 30 K, as discussed in
Box 2.6.
The organic molecule tetrakis dimethylaminoethylene (TDAE) is known to
be an effective electron donor. A C60-TDAE salt has been formed that exhibits a
ferromagnetic state below 16 K. This material, which has a low-symmetry mono-
clinic structure because of the highly nonspherical nature of TDAE, holds the
record for the highest Curie temperature of any purely organic molecular solid.
NANOCLUSTERS
Ever since the early 1980s, when scientists began discovering the various
potentially advantageous properties of ultrasmall grains of material—nano-
clusters—there has been tremendous activity as researchers strive to create and
control new types of particles. Much of the recent research has been directed at
finding ways to make small clusters of uniform size with common optical, electri-
cal, and mechanical properties. These efforts have already begun to have com-
mercial payoffs, as in the case of ceramics and chemical catalysts that have
increased efficiency because of their high surface-to-volume ratio.
In any material, substantial variation of fundamental electrical and optical
properties with decreasing size will occur when the electronic energy-level spac-
ing exceeds the temperature. The variation is especially pronounced for semi-

BOX 2.6 Superconductivity in Alkali and

Alkaline-Earth-Doped C60
Because fullerenes act as electron acceptors, they can form different types of
salt. Those of the alkali and alkaline-earths have particularly interesting electronic
properties. Photoemission studies probing the occupied electronic states, as well
as inverse photoemission measurements probing the unoccupied electronic states,
have allowed direct monitoring of the nature of electron doping into the C60 levels.
The valence band of solid C60 is derived from a fivefold degenerate hu orbital. The
stability of this orbital makes it difficult to remove electrons from C60. On the other
hand, C60 is a good acceptor because of the threefold degenerate t1u and t1g
levels. Exposing C60 to alkali vapor results in electron filling of the t1u level. Be-
cause the Fermi energy is pinned to the top of the filled level, with increased filling,
the spectral manifold is shifted to lower energy. The threefold degeneracy of the
level means that half-filling corresponds to three electrons. K3C60 is a metal that
becomes superconducting at temperatures lower than 19 K. Further filling leads to
the compound A6C60 (where A is an alkali element). Because this material has a
fully filled t1u lowest unoccupied molecular orbital, it is insulating. The structures of
C60, K3C60, and Cs6C60 are shown on the right in Figure 2.6.1. The structures are
cubic but are represented in tetragonal form. The alkali metal atoms sit in the
tetragonal and octahedral voids of the fcc-C60 structure. With alkaline-earth met-
als, the t1g orbital derived band is also partially filled. Thus Ca5C60, Sr6C60, and
Ba6C60 are also superconducting.
x=6
BCC
x=3
FCC
x=0
FCC
FIGURE 2.6.1 Normal (PES) and inverse (IPES) photoemission density of states
of C60 as a function of exposure to potassium vapor. The gradual filling of the
C60 t1u lowest unoccupied molecular orbital is clearly seen. The spectral mani-
fold shifts to lower energy with increasing exposure because of Fermi level pin-
ning. On the right, body-centered tetragonal representations show the structures
of Cs6C60 (x = 6), K3C60 (x = 3), and C60 (x = 0). [Left: Journal of the Physics and
Chemistry of Solids 53, 1433 (1992); Right: MRS Bulletin 19, 28 (November
1994).]

conductors, in which size dependence emerges at relatively large size compared

with metals, insulators, or molecular crystals. This arises because the bands of a
solid are centered about atomic energy levels, with the width of the band related
to the strength of the nearest-neighbor interactions. In the case of van der Waals
or molecular crystals, which have weak nearest-neighbor interactions, the bands
in the solid are very narrow, giving little size dependence of optical or electrical
properties in the nanocrystal regime. As the cluster grows, the center of a band
develops first and the edges last. Thus, in metals, for which the Fermi level lies
in the center of a band, the relevant energy-level spacing is small, and at tempera-
tures above a few Kelvin, even small clusters (10 to 100 atoms) have electrical
and optical properties that resemble those of a continuum. Because the Fermi
level lies between two bands in semiconductors, the band edges dominate the
low-energy optical and electrical behavior. Optical excitations across the gap
thus depend strongly on size even for clusters as large as 10,000 atoms (see
Figure 2.7). Electrical transport also depends heavily on size, mainly because of
the large variation in energy required to add or remove charges on a nanocrystal.
As a consequence, many useful size-dependent phenomena are observed in clus-
ters characterized by an interior that is structurally identical to the corresponding
bulk solid and a surface layer that contains a substantial fraction of the total
number of atoms in the cluster.
° diameter
21 A
°
23 A
Optical Density
°
27 A
°
30 A
°
40 A
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6
Energy (eV)
FIGURE 2.7 Quantum confinement causes the optical spectra of CdSe nanocrystals to
sharpen and move to higher energy as the size of the particle shrinks. [MRS Bulletin 20,
23 (1995).]

The surface of a semiconductor exerts a critical influence on optical and

electrical properties. Passivation is critical to the control of these properties, and
clusters are no exception. As in the bulk, the ideal termination removes the
surface reconstruction, leaves no strain, and simply produces an atomically abrupt
jump in the chemical potential for electrons or holes at the interface. A great deal
of current research into semiconductor clusters is focused on the properties of
quantum dots with the bulk bonding geometry and with surface states eliminated
by immersion in a material of larger gap.
There have been two approaches to the fabrication and investigation of quan-
tum dots. The top-down approach involves the gradual reduction of the extent
and dimensionality of solid matter. The quantum dots thus produced are between
1 µm and 10 nm in size. They are well passivated and immobilized on a substrate
where they may be investigated optically and electrically. The bottom-up ap-
proach views quantum dots as extremely large molecules or colloids. Nano-
crystals vary in diameter from 1 nm to about 20 nm. Their surfaces are derivatized
with organic molecules, which prevent them from aggregating and render them
soluble. Whether these organic molecules provide electronic passivation as well
is an open question. These samples may be manipulated chemically in a wide
variety of ways, yielding entirely new sample configurations (see Figure 2.8).
Much of the work on semiconductor nanocrystals started with the realization
that it is possible to precipitate a semiconductor out of an organic liquid. A set of
precursors are injected into a very hot liquid. Upon injection the temperature
immediately rises above the nucleation limit so that nucleation occurs, and then
the temperature quickly drops. The concentration drops quickly because dilution
occurs, resulting in crystallites in a fluid. The crystallites become encapsulated in
a layer of organic material so that they do not collide and fuse. The crystallites
are each single-crystalline, and they have a preponderance of low-energy, low-
index facets with very few high-index surfaces. One issue that quickly emerges
in the study of nanocrystals is that approximately half the atoms or more are on
the surface of the crystal, making control of the surface even more important than
in bulk materials or conventional films.
Although the high-pressure behavior of semiconductor nanocrystals is ulti-
mately the same as that of the bulk, the details differ rather dramatically. For
example, CdSe nanocrystals 4.2 nm in diameter require almost three times greater
pressure than does bulk material to transform from the wurtzite to the rock salt
crystal structure. When the nanocrystal does transform, it remains a single crys-
tal, indicating that only a single nucleation event has occurred per crystallite. The
smaller the crystallite, the higher the transformation pressure. This difference has
been explained by noting that the transformation involving the least atomic mo-
tion requires transforming from a wurtzite crystallite with only low-index sur-
faces to a rock salt structure with numerous high-energy faces. This consider-
ation increases in importance with decreasing crystallite size, as more and more
atoms in the crystallite occupy its surface.

a 0.5 nm b1 b2 c
5 nm
b3 b4
50 nm
d1 d2 e
500 nm 50 nm 100 nm
FIGURE 2.8 Gallery of quantum dot structures: (a) Positions of cadmium and sulfur
atoms in the molecular cluster Cd32S55, as determined by single-crystal x-ray diffraction.
This cluster is a small fragment of the bulk CdS zincblende lattice. The organic ligands
on the surface are omitted for clarity. (b1) and (b2) Transmission electron micrographs of
CdSe nanocrystals with hexagonal structure, as viewed down different crystallographic
axes. These nanocrystals were prepared colloidally and exhibit well-defined facets. The
surfaces are passivated with organic surfactants. (b3) and (b4) Transmission electron
micrographs of CdS/HgS/CdS quantum dot quantum wells. The faceted shapes show that
epitaxial growth for passivation is possible in colloidally grown nanocrystals. (c) Trans-
mission electron micrograph of a CdSe quantum dot superlattice. (d1) Scanning electron
micrograph of two coupled GaAs quantum dots about 500 nm in diameter. The strength
of the coupling can be adjusted by adjusting the gate voltage. (d2) Transmission electron
micrograph of coupled CdSe nanocrystal quantum dots 4 nm in diameter. These crystal-
lites are joined by an organic molecule. The coupling can be tuned by changing the linker
length. (e) Transmission electron micrograph of InAs quantum dots in a GaAs matrix,
prepared by molecular beam epitaxy. [Reprinted with permission from A.P. Alivisatos,
“Semiconductor clusters, nanocrystals, and quantum dots,” Science 271, 934 (1996).
Copyright © 1996 American Association for the Advancement of Science.]
The main reason for the high level of interest in semiconductors of reduced
dimensionality results from their large quantum-size effects. The band gap in
cadmium selenide can be tuned between 4.5 and 2.5 electron volts (eV) as the
size is varied from the molecular regime to the macroscopic crystal, and the
radiative lifetime for the lowest allowed optical excitation ranges from tens of
picoseconds to several nanoseconds. The energy above the band gap required to
add an excess charge decreases by 0.5 eV. The melting temperature increases
from 400 to 1600°C, and the pressure required to induce transformation from a

four- to a six-coordinate phase decreases from 9 to 2 GPa. There are many

questions in the literature about what would happen to an indirect-gap material,
such as silicon, as the nanocrystallite size decreases. As silicon crystallites be-
come smaller and smaller, they become more emissive because of the quantum-
size effect. However, the fundamental matrix element does not change; it is only
a density-of-states effect. Silicon will never become a direct-gap material in the
relevant size range. On the other hand, a direct-gap semiconductor like cadmium
selenide already has an allowed electronic transition, and as it shrinks, it is more
allowed. Direct-gap semiconductors will retain their advantages over indirect-
gap materials proportionally. As they are made smaller and smaller, they will
continue to radiate more efficiently than indirect-gap semiconductors. One recent
development with potentially far-reaching impact is the development of ultra-
small, highly efficient semiconductor lasers, known as quantum dot lasers. Be-
cause of quantum confinement, controlling the size of the nanocluster leads to
control of the color of light emitted (see Figure 2.9). Quantum dots are so small
that they tightly confine normally mobile electrons, so the charges spend less
energy on their wanderings. Thus more energy is released when the electron and
ABS
Absorbance (arbitrary units)
Intensity (arbitrary units)
PL
400 500 600 700
Wavelength (nm)
FIGURE 2.9 Solid lines show optical absorption (ABS) and photoluminescence (PL)
spectra at 10 K for close-packed solids of CdSe quantum dots 3.85 nm (curve a) and 6.2
nm (curve b) in diameter. Dotted lines are photoluminescence of the same dots but in
dilute form dispersed in a frozen solution. [Reprinted with permission from C.B. Murray,
C.R. Kagan, and M.G. Bawendi, “Self-organization of CdSe nanocrystallites into three-
dimensional quantum-dot superlattices,” Science 270, 1336 (1995). Copyright © 1995
American Association for the Advancement of Science.]

hole combine, resulting in a shorter wavelength. The smaller the dot, the greater
the frequency shift. Making a true quantum dot laser has proven difficult. It is
not straightforward to make the dots the same size, and the result has been that the
devices emit a range of light frequencies. Very recent work in this area has
yielded dots of more uniform size, with characteristics more indicative of true
laser activity.
THIN FILMS, SURFACES, AND INTERFACES

The revolution in the control of the growth and properties of thin films,
surfaces, and interfaces traces its origin to advances in vacuum technology in the
1960s and 1970s and to the development of surface-sensitive probes such as
surface spectroscopies and electron diffraction techniques. Although the field is
no longer new, there have been impressive gains in the past decade, both in the
enabling technologies for thin-film growth and in the insights that growth and
surface studies have provided. The result has been more control over and under-
standing of the growth process, and hence the properties of the resulting film.
Defects can be placed as desired or eliminated altogether. More complex materi-
als can be grown with acceptable quality as a result of the increased control.
The base vacuum available in molecular beam epitaxy systems has improved
by more than an order of magnitude to ~10−12 torr. Such improvement allows the
surface contamination prior to growth to be lowered and also results in less
contamination in the growing film. Alternatively, the growth rate can be lowered
while preserving low levels of contamination, improving control over the process.
Various growth techniques have been developed or refined, as discussed else-
where in this report. Of particular relevance are pulsed-laser deposition, which
has proven particularly useful for the deposition of complex materials such as
high-temperature superconductors; ion beam-assisted deposition, which induces
crystallographic alignment in a growing film independent of the crystallography
(or lack thereof) of the substrate; and various refinements of traditional techniques
such as molecular beam epitaxy, chemical vapor deposition, and sputtering.
The ability to image surfaces and films in real space, as discussed in Chapter
6, has revolutionized studies of film growth. Most of the earliest studies using the
new scanning probe microscopies corroborated surface structures previously ar-
rived at through tortuous interpretation of surface spectroscopic and diffraction
data. It quickly became apparent, however, that the ability to observe surfaces
and films in real space with atomic resolution could enable far more understand-
ing of surfaces than could be derived through more indirect techniques. Nucle-
ation sites, evolution of surface morphology, etc., can now be observed directly,
as discussed in Box 2.7. Another advance in the area of monitoring that has had
a significant impact on thin film studies is the ability to monitor film growth in
real time. Perhaps the most impressive demonstration of the power of this tech-
nique is the in situ studies of chemical vapor deposition growth performed at

BOX 2.7 Early Stages of Film Growth
The study of film growth has been increasingly characterized by the application
of surface science methods to understanding growth at the atomic level. Both
technology and the desire for fundamental knowledge at the atomic level are driv-
ing the search for atomic-level control of the fabrication processes for novel mate-
rials and new devices.
Growth of thin films from atoms deposited from the gas phase is intrinsically a
nonequilibrium phenomenon, governed by a competition between kinetics and
thermodynamics. Precise control of the growth and thus of the properties of thin
films becomes possible only through an understanding of this competition. Exper-
iment and theory have both made impressive strides in exploring the kinetic mech-
anisms of film growth, including adatom diffusion on terraces, along steps, and
around island corners; nucleation and dynamics of the stable nucleus; atom at-
tachment to and detachment from terraces and islands; and interlayer mass trans-
port. The synergism between experiment and theory has tremendously improved
our understanding of the kinetic aspects of growth.
The diffusion of an adatom on a flat surface or terrace is by far the most impor-
tant kinetic process in film growth. Despite the vital importance of surface diffu-
sion, accurate determination of the surface diffusion coefficient in a broad range of
environments has been a major challenge. Scanning-tunneling microscopy (STM)
has improved the situation considerably. STM can image a vastly broader range
of surfaces than can field ion microscopy, which has traditionally been used for
such studies. Atom-tracking STM has been especially valuable because it allows
an atom or cluster to be followed as it migrates. Information from such experi-
ments can then be fed into theories to provide deeper understanding of the mech-
anisms at play in adatom diffusion.
The availability of new probes of the initial stages of nucleation and growth has
meant that even well-studied systems have continued to yield new insights. Much
recent attention has focused on the possible pathway for nucleation of a silicon ad-
dimer, the stable nucleus for a wide range of growth conditions for homoepitaxy on
Si(100) (see Figure 2.7.1). A silicon adatom may have multiple diffusion pathways
on the surface before finding a partner, as all calculations have suggested. Recent
experiments have focused on determining the relative stability of different dimer
orientations and have been able to distinguish slight differences. Studies have
also focused on the preferred locations of dimers, where there are still significant
differences between experiment and theory. Experiments have revealed some
surprisingly large anisotropies in larger islands as they grow.
As islands grow, specific island shapes or morphologies develop. One class is
compact, whereas another is fractal-like, with rough island edges or highly aniso-
tropic shapes. Recent studies of two-dimensional island formation in metal-on-
metal epitaxy have identified several aspects of atom diffusion along island edges
that are important in controlling the formation of fractal islands. Fractal island
growth is very dependent on bonding geometry, having been reported only on
face-centered cubic (111) or hexagonal close-packed (0001) substrates, both of
which have approximately triangular lattice geometry. Growth on face-centered
cubic (100) surfaces with square lattice geometry has so far resulted only in com-
pact islands. This observation has required modification of the classic diffusion-
limited aggregation model.

BOX 2.7 Continued
Explorations seeking improved understanding of the relative importance of the

various atomistic rate processes important in the initial stages of film growth have
led to discoveries of various ways of rate manipulation to improve the quality of
films grown by vapor-phase epitaxy. For example, any enhancement of downward
diffusion of adatoms below their landing site would improve layer-by-layer or two-
dimensional growth. Increasing the ability of an atom to cross a corner of an island
at which two edges meet would lead to more compact islands. Larger surface
diffusion would lead to earlier achievement of step-flow, hence layer-by-layer
growth. Such insights are already leading to greater control over the precise mor-
phology of thin films to achieve desired structures. The rate of progress in this
area will surely increase as our understanding continues to grow.
FIGURE 2.7.1 Scanning-tunneling microscope images showing the rotational

dynamics of a silicon ad-dimer formed on top of a dimer row in Si(001). (a) The
bond of the ad-dimer (arrow) is parallel to the substrate dimer rows in the 2 × 1
reconstruction, as schematically shown below the image. (b) The same ad-
dimer has rotated by 90 degrees. The two images were taken 40 seconds apart
at room temperature. The orientation in (a) is energetically slightly more stable.
[Reprinted with permission from Z. Zhang and M.G. Lagally, “Atomistic
processes in the early stages of thin-film growth,” Science 276, 377 (1997).
Copyright © 1997 American Association for the Advancement of Science.]

synchrotron sources, as described in Chapter 6. The power of this technique has

just begun to be tapped.
There have been major strides in understanding the kinetics of epitaxial
growth. In silicon molecular beam epitaxy, it has been shown that the notion of
a minimum temperature for epitaxial growth is incorrect, even at a fixed growth
rate. Instead, for all temperatures of the regime studied (30 to 300°C), the
growing epitaxial film becomes amorphous above a limiting thickness. The
epitaxial thickness for the epitaxial-amorphous transition follows an Arrhenius
temperature dependence, depending on the deposition rate. Other systems, in-
cluding gallium arsenide, also exhibit this behavior. Such improved understand-
ing is relevant to the problem of dopant incorporation in silicon epitaxy, in which
controlled growth of a highly doped layer of arbitrary thickness can be achieved
at a temperature low enough to avoid dopant segregation. This low growth tem-
perature approach allows very sharp doping profiles.
The ability to control the structure of inorganic thin films on an unprec-
edented scale has recently been demonstrated using a technique called “glancing
angle deposition,” which maximizes atomic shadowing and minimizes adatom
diffusion. By making use of extremely high adatom angles of incidence, coupled
with substrate rotation (or other motion) around the substrate normal, slanted,
zigzag, helical, or other morphologies have been demonstrated, as shown in
Figure 2.10. The helically structured films have been shown to rotate the plane of
polarization of light in a manner analogous to other chiral media; pitches between
50 and 2000 nm have been demonstrated.
Major progress has been made in substrate engineering and control, along
with understanding of the role of surface properties in film growth, in the last
decade. Compliant substrates allow control of the strain induced by the con-
straint of epitaxy so that the electronic and structural properties of the film can be
tailored to fit the needs at hand. If the substrate is sufficiently thin, or if the top
layer is sufficiently weakly bonded to the rest of the substrate, the substrate can
readily deform elastically when a lattice mismatched material is grown on it. The
extent to which this approach can be reduced to practice is as yet unclear. Epi-
taxy has been shown to be strongly affected by the presence of an adsorbate
(surfactant), which changes the surface properties because of its bonding arrange-
ment, usually accompanied by a change in the surface reconstruction (see Figure
2.11). The saturation of the dangling bonds yields a chemical passivation of the
surface, a change in electronic structure, and a reduction of the surface free
energy, which causes the strong segregation of the surfactant layer. The adlayer
floats on the growing film, and only a small fraction is incorporated. These
properties can have a profound effect on the growth mode of the film, converting
a film that normally grows in an island fashion to layer-by-layer growth. In
heteroepitaxy, interfaces prepared by growth with an adsorbate present, either
hydrogen or a dopant species, remain sharper at a higher growth temperature than
interfaces prepared by growth on a bare surface.

FIGURE 2.10 Films deposited by glancing angle deposition (GLAD): (a) oblique evap-
orated flux at 85 degrees from the substrate normal produces a slanted, porous micro-
structure; (b) periodically alternating the oblique flux from angles of 85 degrees to –85
degrees produces a porous film composed of isolated “zigzags”; (c) rotating the substrate
about an axis normal to the wafer center while maintaining obliquely incident (85 degree)
flux produces isolated helical structures on the substrate. [Reprinted with permission
from K. Robbie and M.J. Brett, “Sculptured thin films and glancing angle deposition:
Growth mechanics and applications,” Journal of Vacuum Science and Technology A 15,
1460 (1997). Copyright © 1997 American Vacuum Society.]

FIGURE 2.11 The use of a surfactant dramatically alters the morphology of a growing
film. In this figure are medium energy ion scattering (MEIS) spectra for germanium films
on Si(111) at 470 °C. Both random (solid line) and channeling (dotted line) data are
shown. (a) Ten monolayers of germanium deposited with no gallium. Note the island
morphology. (b) Twenty monolayers of germanium deposited with one-third of a mono-
layer of gallium as a surfactant. Note the columnar morphology. (c) Twenty-eight mono-
layers of germanium with one monolayer of gallium surfactant. Note the smooth mor-
phology. [Reprinted with permission from J. Falta, M. Capel, F.K. Legroves, and R.M.
Tromp, Applied Physics Letters 62, 2962 (1993). Copyright © 1997 American Institute of
Physics.]

ARTIFICIALLY STRUCTURED MATERIALS

Artificially structured materials—materials whose structure or composition
differs in some intentional way from materials available in nature—have enabled
many of the advances in condensed-matter and materials physics over the past
decade that are described in this report. Such materials are frequently dominated
by interfaces, a feature that often leads to properties very different from those of
bulk materials. Because artificially structured materials are frequently prepared
far from thermodynamic equilibrium, they can exhibit phases or properties that
are not otherwise achievable. Their multilayer structural length may be on the
order of the length-scale characteristic of nonlocal physical phenomena in solids,
making such materials ripe for fundamental investigations. The physical limits to
their fabrication have been pushed to the greatest extent for semiconducting
materials. The coming decade will undoubtedly see the same limits pushed for
other classes of materials as well: complex oxides, polymers, biological materi-
als, and composites are a few of the most exciting.
Many if not most artificially structured materials involve heteroepitaxy, the
crystallographically oriented growth of one material on a dissimilar one. In
nearly all cases, heteroepitaxy involves a lattice mismatch between the different
materials, which produces strain in the initial epitaxial layer. The strain is re-
lieved as the epitaxial film thickness increases, by a roughening of the surface of
the epitaxial layer or by the introduction of defects such as dislocations into the
epitaxial layer or both. Controlling when and how strain relief occurs is a key
issue in heteroepitaxy.
The strained films discussed here are grown near the thermodynamic limit.
Sputter-deposited films, such as those discussed in Box 2.8 and in the section on
magnetic multilayers in Chapter 1, are deposited in the kinetic limit, which is
required for alternating layers of extremely disparate materials.
One distinct trend has been toward the use of more highly strained hetero-
epitaxial combinations, such as InGaAs/GaAs (see Figure 2.12) and SiGe/Si.
Such systems must be approached with great care in order to achieve the opti-
mum structural (and consequently electrical or optical) quality. Morphology-
related strain relief is not a new phenomenon. Mounding in a film may par-
tially relieve elastic stress of the epitaxial material within each mound. Even
though there is additional compression of lattice planes at the grooves between
the mounds, the roughened morphology is energetically favorable because the
volume of material subjected to additional stress is much less than the volume
experiencing partial stress relief. Another very important factor is the surface
free energy. Roughening generally increases this energy, so that roughening is
suppressed until the free-energy reduction in the system by stress relief is
greater than the free-energy increase caused by surface area increase and step
formation.
Strain-induced roughening can be problematic in the fabrication of coher-
ently strained device structures, for which it is important to understand the early

BOX 2.8 Multilayers for X-Ray and Extreme Ultraviolet Optics
Multilayers are artificially structured materials that are periodic in one dimen-
sion in composition or both composition and structure. These layered materials
are, if perfect, equivalent to single crystals in one dimension. Thus the multilayer
acts as a superlattice, diffracting longer-wavelength radiation in a manner directly
analogous to the diffraction of x-rays by crystals. This application of multilayer
structures as dispersion elements for soft x-rays and extreme ultraviolet radiation
was the impetus for the first attempts to synthesize multilayer materials. Many
factors determine the character of the multilayer response to an incident spectrum.
The important parameters are the substrate quality (roughness and figure), the
uniformity and thicknesses of the component layers, the x-ray optical constants of
the component elements, the number of layers in the structure, the interfacial width
between layers (i.e., interfacial abruptness in atomic position and composition),
and roughness at layer interfaces. Many of these factors depend in turn on the
synthesis process and the materials. Therefore, understanding of multilayer per-
formance depends on a knowledge of the relationships among synthesis process,
resultant microstructure, and properties for these engineered microstructure
materials.
The individual layers of the optics have a specific set of properties related to
bulk forms of the materials. Primary issues include the compositions and struc-
tures of the layers, the x-ray optical properties of the layers, and uniformity of the
areal density of atoms in the layers (see Figure 2.8.1). Specific synthesis ques-
tions relate to the film nucleation and growth behavior because deposition of ma-
terial A onto a substrate or layer B may differ substantially from deposition of ma-
terial B onto a substrate or layer A. Interfaces within the multilayer must also be
controlled to an excruciating degree. They must be compositionally abrupt,
smooth, clean, and flat.
Recent work has shown that precise control of sputtering parameters during
multilayer deposition allows control of individual layer thicknesses to an accuracy
of better than ~0.01 nm, which greatly enhances reflectivity for both nickel-carbon
and tungsten-carbon multilayers. Sputter deposition of multilayers typically pro-
duces higher quality structures than thermal source techniques. This has been
attributed to ion bombardment by the sputter plasma resulting in smoother inter-
faces and higher reflectivities. Results of ion beam-assisted deposition support
this proposal. Thermal-evaporation-source synthesized rhodium-carbon multilay-
ers with and without argon ion bombardment (300 eV) at an incidence angle of 10
degrees show the effect. A gain of more than a factor of two in reflectivity was
found for the samples “polished” by the incident ion beam. This increased reflec-
tivity is attributed to smoothing of the interfaces between the carbon and rhodium
by a factor of 30 percent by the ion bombardment. Combining these two improve-
ments in control are likely to facilitate fabrication of higher quality multilayer struc-
tures, particularly of smaller periods.
Multilayer structures may be optimized and engineered for specific spectral
ranges by an analysis for optimum materials on the basis of their x-ray constants
and an assessment of their suitability for multilayer microstructure synthesis. As
an example, there are difficult spectral regions in which the lowest absorption
materials useful as spacer layers are either toxic, such as beryllium, or unstable,
such as lithium. Candidate materials such as magnesium are difficult to deposit as

BOX 2.8 Continued

a uniform thin film because of its low melting point and high vapor pressure. Mg2Si
has been identified as a possible new material for this application, and W/Mg2Si
multilayers have reflectivities that are the highest reported in the 800 to 1300 eV
range.
Multilayer x-ray optics and instrumentation are now mature enough to be both
an enabling technology and an area of scientific investigation in their own right.
The promise that was held for soft x-ray and extreme ultraviolet multilayer optics is
now coming to fruition, and many of the advanced optical systems envisioned in
the late 1970s are becoming reality. Such x-ray optics will likely form the critical
element of vacuum ultraviolet optics for the next generation of lithography in the
semiconductor industry.
0.5
NIST (Tario)
AMP-LLNL (Montcalm)
0.4 Calculation
Reflectivity
0.3
0.2
0.1
0.0
170 180 190 200 210 220
Wavelength (Å)
FIGURE 2.8.1 Transmission electron micrograph of a 6.9 nm period Mo2C/Si
multilayer x-ray mirror (top) and the experimental and calculated reflectivity as a
function of x-ray wavelength (bottom). The experimental reflectivity is 93.5 per-
cent of the calculated values. [Reprinted with permission from T.W. Barbee, Jr.,
and M.A. Wall, “Interface reaction characterization and interfacial effects in multi-
layers,” Proceedings of the SPIE 3113-20, 204 (1997). Copyright © 1997 SPIE.]

FIGURE 2.12 Atomic force micrograph of self-assembled InAs islands deposited by

molecular beam epitaxy on a patterned GaAs(001) surface. The valleys and hills, which
have been defined by optical lithography and etching, have a period of ~240 nm. The
InAs islands, which are formed by deposition of about 1.5 monolayers of InAs on the
corrugated GaAs surface, are preferentially located in the valleys of the surface. The
height and diameter of the InAs islands are 10 nm and ~20 nm, respectively. These
islands will be transformed into quantum dots by in situ overgrowth of a GaAs cladding
layer. (Courtesy of the University of California at Santa Barbara.)
stages of the transition in order to avoid or suppress three-dimensional growth.

On the other hand, the strain-driven transition is beneficial for the self-assembly
of quantum dots, in which it is necessary to control the size distribution and self-
organizing behavior of the islands. It is critical to understand the kinetic path-
ways to island formation.
Recent theoretical investigation suggests that systems with tensile stress
could be more resistant to roughening than those with compressive stress. Recent
work has supported this prediction in, for example, the Si-Ge system. Molecular
dynamics modeling has attributed this observation to an increase in the energy of
certain types of surface steps under tensile strain, which makes it energetically
favorable for the surface to remain planar.
One of the major contributions of scanning-probe microscopies to hetero-
epitaxy has been improved understanding of morphological evolution in hetero-
epitaxy. A general trend in all experiments is the decreasing size of typical
morphological features with increasing misfit stress. In many highly mismatched
systems, surface ripples exhibit a strong tendency to facet along inclined planes,

FIGURE 2.13 Atomic force microscope image of an initially planar 2-nm thick Si0.5Ge0.5
alloy layer on Si(001) after annealing to produce hut-shaped islands caused by strain in
the layer. [MRS Bulletin 21, 31 (1996).]
as in the epitaxial germanium “hut” clusters in Figure 2.13. The presence of

{501} facets appears to be a general feature of strained-layer growth in the Si-Ge
system. It is not understood, however, why such facets are stable and what role
they play in the growth of coherently strained islands. The picture is emerging
that {501} facets are the natural result of the desire to release as much elastic energy
as possible without unduly creating energetically costly surface-step configurations.
During growth, strain relaxation in heteroepitaxial systems can lead to
changes in island shapes. In semiconductor systems, coherent islands are often
faceted and characterized by large aspect ratios [up to a 10:1 base-to-height ratio
in the case of the germanium “huts” and up to 50:1 in silver on Si(100)]. Recent
calculations have shown that strained islands are likely to undergo a shape trans-
formation during growth. Below a critical island size, the energy balance favors
compact, symmetric islands; for large islands, elongated shapes with high aspect
ratios are preferred. This suggests one approach to the challenge of producing
quasi-one-dimensional quantum wire structures.
Turning now to the other major strain-relief mechanism—defects such as

dislocations—we enter an area of research with much longer antecedents. Tradi-

tionally, misfit dislocations have been avoided simply by keeping the film thick-
ness at less than the “equilibrium critical thickness.” More recently, other strat-
egies have been introduced, such as reduced temperature growth or substrate
patterning. When substrate patterning is used to isolate regions of the sample,
relaxation is greatly retarded because most isolated regions contain no heteroge-
neous nucleation sites. These regions can be remarkably stable during thermal
anneal, which shows that controlling nucleation may be the key to controlling, or
even suppressing, relaxation.
One of the most successful methods to date of fabricating quantum dots uses
self-assembly that results from growth kinetics controlled by strained-layer epi-
taxy. A strain-induced transition from two- to three-dimensional growth results
in the formation of coherently strained islands on the surface of the semiconduc-
tor. Using these principles, islands <20 nm in diameter can be fabricated with
size distributions within ±10 percent. The resulting islands are pseudomorphically
strained and dislocation free.
The random distribution of islands can be modified by appropriate control of
their nucleation and growth, kinetics. It was readily apparent early on that pref-
erential nucleation of islands takes place at surface steps. This effect could be
used to order islands. Recent progress in making extremely perfect kinkless steps
over micron distances on Si(111) offers hope of ultimately achieving ordering of
island assemblies by this approach.
Another strategy for ordering the islands is based on the very sharp transition
from two- to three-dimensional growth. A corrugated substrate with concave and
convex areas will tend to flatten and minimize its surface energy during epitaxy
through faster growth of the convex areas. Thus, when depositing a strained layer
over such a surface, the critical thickness will be reached sooner in these areas,
and quantum dots will nucleate preferentially in these regions.
Another promising approach based on strain-induced nucleation allows for
regulating the size and ordering of the islands in the growth direction. If two or
more layers of quantum dots are grown sufficiently close to each other (closer
than 10 nm for InAs/GaAs), it is possible to obtain self-alignment of the islands
in the growth direction.

The examples of new materials and structures presented in this chapter point
out the major themes in the search for new and improved materials and properties
that have characterized the past decade. The themes include the discovery of new
and unexpected materials with novel properties and the use of new tools to
provide improved understanding and control in well-known materials. These
developments foreshadow many of the advances that are likely in the coming
years. It is critical to emphasize, however, that many of the most exciting devel-

opments have been complete surprises; this will almost certainly be true for the
foreseeable future as well.
Materials Properties by Design: Complexity

The ability to tailor materials and structures to obtain a desired set of proper-
ties is in its infancy (see Box 2.9). Band-gap engineering, which has been
achieved by judicious use of strain, alloying, and quantum-size effects, is one
area that has had considerable impact. Control of the microstructure of a mate-
rial, through processing and judicious choice of geometry or neighboring materi-
als, has been used to control the physical properties of some materials. Artifi-
cially layered materials have been given unusual dielectric properties and have
contributed to the search for new high-temperature superconductors.
Future progress will build on these recent accomplishments. Eventually, we
can expect to be able to tailor materials at the molecular level, building up
materials molecule by molecule in three dimensions. This capability will enable
truly three-dimensional designs with as much or as little symmetry as needed. In
the future, a design will be able to incorporate structure at multiple length-scales,
enabling the optimization of multiple properties that involve phenomena operat-
ing at very different dimensions. Today, the most advanced artificially structured
materials utilize individual material constituents of the same or very similar
classes: III-V semiconductors, for example. We can look forward to being able
to use a much more colorful palette, not limited to a single class of materials or
even just to inorganic materials. Polymers, organic molecules, and even biologi-
cal molecules are likely to become integral parts of increasingly complex struc-
tures as we learn more about how to manipulate molecules individually. A
glimpse into the possibilities is described in Box 2.10.
As the structures that we are able to build become more complex, we will
need the tools to be able to see, characterize, and manipulate them. We will need
to be able to work with these structures on all of the length scales that are relevant
for the properties we desire. The scanning-probe microscopies are an important
step in this direction, but more, equally revolutionary advances will be required
to truly take advantage of this new regime of materials design.
Finally, we will need to be able to make predictions about these new materi-
als. Our ability to predict the existence of new materials with interesting proper-
ties is extremely limited. Witness the complete surprise presented by the discov-
ery of high-temperature superconductors or the lack of theoretical guidance
concerning other interesting avenues of inquiry in the search for other high-
temperature superconducting families. Theoretical guidance regarding promis-
ing synthetic routes for fabricating new materials would be most useful to experi-
mentalists trying to prepare them. Finally, improved communication between
theorists and experimentalists might help to shorten the gap between prediction
and fabrication—several decades in the case of C60, for example.

BOX 2.9 Combinatorial Chemistry and the

Search for New Materials
Systematically varying the composition of a multicomponent system to opti-

mize its properties is a time-honored empirical method in materials synthesis. For
example, “phase spreads” of thin films proved powerful in the study of metal-
insulator transitions almost 2 decades ago. Scaling up the approach to allow the
fabrication and testing of tens or hundreds of compositional variants requires the
ability to prepare small volumes of precisely controlled composition under known
preparation conditions as well as the capability to test these miniature samples for
desired properties. Known more recently as combinatorial chemistry, this ap-
proach is used to make a large number of chemical variants in parallel, to screen
them quickly and reliably for chemical activity, and to build a library of information
about the resultant chemical diversity. Until recently, combinatorial chemistry has
been used primarily to transform the way new drugs are discovered, but in the
coming decade, it may have an impact on the search for other classes of new
material as well. The most notable forays of combinatorial chemistry into non-
medical arenas are in the areas of superconducting compounds and phosphors
(see Figure 2.9.1). The applicability of the technique to the search for catalysts is
also being investigated. All these materials share the property of being very com-
plex, containing many elements and eluding prediction of their properties or even
existence using any currently available theories or models. As the entire field of
condensed-matter and materials physics moves toward increasingly complex sys-
tems, techniques such as combinatorial chemistry are likely to make a home for
themselves alongside more traditional techniques such as bulk crystal growth or
physical and chemical vapor deposition. For this promise to be realized, however,
new tools need to be developed that can analyze and sort the large number of
samples that are produced by this powerful technique.
FIGURE 2.9.1 An array of

different combinations of
phosphors being screened
for brightness in ultraviolet
light. [Reprinted with permis-
sion from E.D. Isaacs, M.A.
Marcus, G. Aeppli, X.-D.
Xiang, X.-D. Sun, P. Schultz,
H.-K. Kao, G.S. Cargill III,
and R. Haushalter, “Syncro-
tron x-ray microbeam diag-
nostics of combinatorial syn-
thesis,” Applied Physics
Letters 73, 1820 (1998).
Copyright © 1998 American
Institute of Physics.]

BOX 2.10 Polymers Enable Porous Inorganic

Materials Synthesis to Order
Block copolymers self-assemble into ordered nanostructures consisting of

three-dimensional arrays of spheres, cylinders, lamellae, and even bicontinuous
domains depending on the lengths of the blocks. Polymer physicists have
achieved a remarkably detailed understanding of the interplay between chain ar-
chitecture and thermodynamics that leads to these nanostructures. As useful as
this insight has been for all-polymeric materials, it now promises to be equally
important for the synthesis of inorganics. A long-standing need has been for po-
rous ceramics that have well-defined but large pore sizes (>5 nm). These can now
be achieved using block copolymers as a template. A copolymer with hydrophilic
and hydrophobic blocks is ordered into a nanostructure in which the hydrophobic
block forms aligned cylinders. A ceramic precursor is absorbed preferentially into
the hydrophilic matrix surrounding the cylinders and allowed to condense into a
robust inorganic oxide network. The block copolymer can be extracted, leaving a
ceramic matrix surrounding ordered uniform cylinderical pores, as shown in Figure
2.10.1. Pore size can be controlled between 5 and 30 nm simply by changing the
length of the copolymer, leaving the ratio of blocks the same.
FIGURE 2.10.1 Transmission-electron microscope micrographs of mesoporous

silica with pores sizes 6 and 9 nm. [Reprinted with permission from D. Zhao, D.
Feng, Q. Huo, N. Melosh, G.H. Fredrickson, B.F. Chmelka, and G.D. Stucky,
“Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 ang-
strom pores,” Science 279, 550 (1998). Copyright © 1998 American Association
for the Advancement of Science.]

Synthesis and Processing: Control

To make the increasingly complex materials and structures of the coming
decades, tremendous advances in processing will be required. One can look
forward to the day when arbitrarily complex materials and material combinations
can be made with the same level of control as is possible for semiconductors
today. One of the first classes of material that is likely to see the benefits of
improved processing is the complex oxide family, including high-temperature
superconductors. The complexity of these materials, however, pales in compari-
son with some of the other structures involving vastly different classes of mate-
rial such as biological and inorganic materials. Although demonstrations of
increasingly complex structures designed on the molecular level may be made
using scanning-probe techniques, fabricating structures that can be studied inten-
sively will require faster techniques that can make multiple samples. This almost
certainly calls for a dramatic increase in our understanding of and ability to use
self-assembly and biomimetic techniques to produce and process materials.
In the past decade there has been impressive progress in the understanding
and control of defects—what they are, where they come from, and how to elimi-
nate them or control their placement when they serve a defined purpose—in some
materials systems, especially semiconductors. For other materials to reach the
same level of perfection and processing control, the same level of understanding
will be required.
Nanoscale fabrication and processing, wherein molecular chemistry and
condensed-matter physics merge, will be key to achieving the level of control that
will be needed to realize many of the exciting possibilities posed in this report.
Physics: Understanding
The materials and structures on the horizon offer rich possibilities for
condensed-matter and materials physicists. More perfect materials will enable us
to move toward developing a full understanding of the relationship between the
detailed structure of a material and its properties. The ability to control defects
will enable them to be studied themselves—how they interact with the material
they inhabit and even how judiciously assembled collections of them interact
with one another and with different defects. Advances of the past decade in
probing surfaces and interfaces on the atomic scale offer the possibility that a full
understanding of the initial stages of growth in systems more complex than
silicon may one day truly be possible. Control of the structure of materials on
various length scales simultaneously offers the opportunity to look for effects that
result from the interplay of structure on these different length scales.
Technology: Relevance
Advances in new materials and structures have dramatically improved our

lives in the past, and there is every reason to expect that new advances will have
comparably great impact in the years to come. For this to happen, sustained
research will be needed over many years. This research will need to have a
balance between fundamental investigations into the physical mechanisms at
play and research and engineering aimed at investigating the numerous questions
that must be answered before a material can enter the technological mainstream:
What can the material be used for? Is there a potential market of sufficient size to
pay for the needed research and development? Is the advance so revolutionary,
with improvements in customer capability so great, that it can found a new
industry? If the improvement is in an area already occupied by an existing
technology with significant infrastructure, can the material be integrated with the
existing technology? And if so, is the improvement worth the development cost?
Just as revolutionary advances in new materials and processes enabled the
transistor, the optical fiber, the solid-state laser, and many other technologies that
have improved our lives and strengthened the economy, new developments in
materials and structures hold out the promise of revolutionary breakthroughs in
the twenty-first century.
Outstanding Scientific Questions

• Can we complement empiricism with predictability in our search for new
materials and structures with desired properties? Can we predict the composition
and structure of a new material, its properties, and how to synthesize it?
• Can we develop a full understanding of the initial stages of growth?
• Can we develop a full understanding of the relationship between the
detailed structure of a material and its properties? Can we truly control defects?
Research Priorities
• Tailor materials at the molecular level.
• Use more complex combinations of materials: polymers, organic mol-
ecules, biological molecules, etc.
• Develop new tools to synthesize, visualize, characterize, and manipulate
new materials and structures.
• Make increasingly complex materials and combinations with as much
control as is currently possible in the making of semiconductors.
• Increase our understanding of and the ability to use self-assembly and
biomimetic techniques to produce and process materials.
• Merge molecular chemistry and condensed-matter and materials physics
to understand and control fabrication and processing on multiple length-
scales.
• Integrate processing of new materials and structures with existing tech-
nologies.

Novel Quantum Phenomena
One might imagine that because condensed-matter and materials physics

deals with known objects (atoms) interacting via well-defined and well-under-
stood forces (the Coulomb interaction among charged particles) there are no
surprises and no fundamental intellectual challenges left to be discovered. Noth-
ing could be farther from the truth. Quantum mechanics is a strange business,
and the quantum mechanics of large collections of atoms and molecules can be
stranger still. It inevitably happens that when assembling a collection of atoms to
form a material, the whole is greater than the sum of the parts in the sense that
“emergent phenomena,” such as spontaneously broken symmetries and quantum
or classical phase transitions, often appear in large collections of atoms. For
example, a set of widely spaced copper atoms has an energy gap for charge
excitations and thus is an insulator. This is because the atoms are largely inde-
pendent of each other and retain the discrete spectra of isolated atoms. Even at
absolute zero, compressing the atoms into solid copper causes the electrons to
“melt” into a new “liquid” phase that has no excitation gap and is an excellent
electrical conductor. If the same experiment is carried out with aluminum atoms,
very subtle differences in the atomic properties lead not to an ordinary metal but
to a superconductor. There exist vast families of complex materials, with many
atoms per unit cell, whose surprising properties are still extremely difficult to
predict a priori. This is an especially important challenge for theoreticians in the
coming decade.
The idea of emergent phenomena teaches us that, even though we understand
and can relatively easily compute the properties of individual atoms, materials
constructed from large collections of atoms will routinely surprise us with com-
137

pletely unexpected properties. Living matter and life itself are perhaps the most
spectacular examples of emergent phenomenon; no matter how much we learn
about individual atoms, life cannot be understood or explained in this purely
reductionist manner. One of the biggest surprises of the last decade was high-
temperature superconductivity. It is hard to imagine a less likely candidate for a
superconductor than an insulating ceramic compound with properties similar to
those of a china coffee cup. Yet when chemically doped to introduce charge carriers,
such compounds not only superconduct, they do so at record high temperatures.
The characteristic energy scale for individual atoms is 1 to 10 electron volts
(eV). However, as we look on larger length scales at collections of atoms,
characteristic energies become smaller and smaller, and excitations become more
and more collective. At low energies, the effective elementary degrees of free-
dom may be collective objects very different from individual electrons and at-
oms, and their effective interactions may be very different from the original
“bare” Coulomb interactions. These collective effects are the source of the
surprises that emerge.
It is instructive to compare this situation with that in high-energy elementary
particle physics. There we know the effective degrees of freedom and their
interactions at low energies—it is the world of atoms around us. The intellectual
challenge is to understand degrees of freedom at shorter and shorter length scales
and higher and higher energy scales. This is done by constructing high-energy
particle accelerators to act as microscopes with ever greater magnification, or by
studying extreme conditions in astrophysical systems and the early universe.
This approach is just the reverse of what is done in condensed-matter physics,
where we strive to understand collective effects at longer and longer length
scales. The analog of the particle accelerator is the refrigerator, which lowers
thermal energy scales and increases the distance over which particles suffer in-
elastic collisions. The analog of an extreme astrophysical system is a sample in
a dilution refrigerator. The intellectual challenge is the same in the two fields: to
find correct descriptions of the physics that work over a wide range of scales.
Fifty years ago understanding a novel quantum object known as a “hole” (see
Box 3.1) led to the invention of the transistor. In the past decade there has been
tremendous progress in the discovery and study of a variety of novel quantum
phenomena. This chapter presents brief descriptions of a few examples drawn
from superfluidity, superconductivity, Bose-Einstein condensation, quantum
magnetism, and the quantum Hall effect. It cannot cover many other fascinating
areas of development in the last decade, including significant advances in our
understanding of quantum critical phenomena, non-Fermi liquids, metal-insulator
and superconductor-insulator transitions in two dimensions, quantum chaos and
the role of interactions, coherence, and disorder in mesoscopic systems.
There has been particularly significant progress in this last area, both tech-
nologically and theoretically. For example, electron “wave guides” have been
constructed, and the quantization of their conductance in units of e2/h has been

NOVEL QUANTUM PHENOMENA 139
BOX 3.1 Exotic Quantum Objects in Today’s Technology
Fifty years ago at the time of the invention of the transistor, the hot topic in
condensed-matter physics was an exotic quantum object, the “hole,” whose pre-
dicted existence was one of the great early triumphs of quantum mechanics. The
ability to create and manipulate these “holes” is crucial to the operation of diodes,
transistors, photocells, light-emitting diodes, solid-state lasers, and computer
chips.
To understand the concept of the hole, consider the fact (illustrated schemati-
cally in Figure 3.1.1) that when atoms are assembled into a solid, the discrete
quantum energy levels of the individual atoms smear out into bands of quantum
levels. The Pauli exclusion principle tells us that each band state can hold no more
than one electron. In a semiconductor, the highest occupied band (the valence or
“bonding” band) is separated by a small but crucially important energy gap from
the lowest unoccupied band (the conduction or “anti-bonding” band).
The Pauli exclusion principle has the important consequence that a filled band
is inert. It is impossible to excite the system by moving an electron to a new state
within a band that is already entirely filled up, so the only way to achieve the lowest
energy excitation that can be made in a semiconductor is to lift an electron from the
valence band across the gap to the conduction band. It is easy to visualize the
electron in the conduction band as a particle that can move around, carry current
and so forth. Paradoxically, quantum mechanics also teaches us that the absence
of an electron in the otherwise-filled valence band should be viewed as a hole that
behaves like a kind of anti-particle (much like the positron, which is the anti-particle
of the electron in high-energy physics). Without the hole, the valence band is inert
and carries no charge or current. The electron that was removed had negative
charge and carried some particular current. Hence, we must assign the hole a
positive charge and the opposite current. Without quantum mechanics guarantee-
ing that a filled band is inert, this assignment would not be meaningful.
Introduction of chemical dopants into semiconductors can produce an excess
of electrons (n-type material) or an excess of holes (p-type material). Remarkable
materials physics advances in purification and doping control of silicon now allow
routine inexpensive construction of the special types of junctions between p- and
n-type material that play such a crucial role in today’s solid-state technology. So
next time you turn on your computer, remember quantum mechanics is at work!
conduction band
atom
hole
valence band
FIGURE 3.1.1 Energy bands in solids. [Reprinted with permission from S.M.
Girvin, “Exotic quantum order in low-dimensional systems,” Solid State Commu-
nications 107, 623 (1998). Copyright © 1998 Elsevier Science.]

observed. It is also now possible, for example, to construct mesoscopic grains of

metal large enough to be superconducting but small enough that significant
changes in transport properties are observed depending on whether the number of
electrons on the grain is even or odd. In addition, we now have observations of
interference effects for electrons diffusing in a mesoscopic normal conductor
bounded by segments of superconductors with variable relative phase.
One of the significant characteristics of condensed-matter and materials phys-
ics that is worth emphasizing is the close interaction between experimentalists
and theorists. Unlike many other areas of physics, theorists often collaborate
closely with experimental groups and they frequently jointly publish papers. The
field owes its intellectual vitality to this close collaboration and to a continuous
and exciting stream of quite unexpected experimental discoveries.
Newly uncovered electronic phenomena in complex and strongly interacting
materials have challenged fundamental theoretical paradigms such as the Fermi
liquid. In some cases, such as for the fractional quantum Hall effect, entirely new
concepts (for example, fractionally charged quantum vortices) have been devel-
oped that enriched the foundations of the field and beautifully explained the new
phenomenology. High-temperature superconductivity and heavy-fermion systems
present a bewildering array of paradoxes that have spawned many new paradigms
whose validity is still being sorted out. This challenge will require, and will lead to,
fundamental experimental and theoretical advances in the next decade.
SUPERFLUIDITY AND SUPERCONDUCTIVITY

Superfluids and superconductors have the remarkable property of carrying
matter or charge currents completely without friction. In helium-4, the atoms
undergo Bose-Einstein condensation (see next section) and become superfluid a
few degrees above absolute zero. In a superconductor, pairs of electrons join
together to form an effective boson-like degree of freedom. In an ordinary low-
temperature superconductor, these Cooper pairs of electrons have a diameter
much larger than the spacing between the electrons. Hence, it is not usually
appropriate to view the superconducting phase transition as Bose-Einstein con-
densation, though it is closely related.
The 1996 Nobel Prize in Physics was awarded to Lee, Osheroff, and
Richardson for the discovery of superfluidity in helium-3 (see Table O.1). This
isotope of helium is a fermion, and it is Cooper pairs of helium-3 atoms that just
barely condense at exceedingly low temperatures. Unlike the electrons in an
ordinary superconductor, which form pairs in a state of zero relative angular
momentum, helium-3 atoms pair in a p-wave (l = 1) angular momentum state.
This feature gives superfluid helium-3 many novel properties because the state of
the system is determined not just by the complex phase of the condensate wave
function, but also by the local orientation of the pair angular momentum vector.
The exotic pairing state of helium-3 is naturally connected with high-

temperature superconductors for two independent reasons. First, it has recently

been established via several ingenious experiments that the pairing state in high-
temperature superconductors is d-wave (l = 2), rather than the usual s-wave
(l = 0). Unlike the case of helium-3, however, the direction of the angular
momentum is not free to change but is fixed by the underlying lattice. In fact, as
illustrated in Figure 3.1, the d-wave is actually a standing wave with the angular
positions of its antinodes parallel to the axes of the square copper oxide planes.
FIGURE 3.1 (Left ) The long straight lines mark the boundaries of three substrate stron-
tium titanate films with different crystallographic orientations. The four circles are rings
of the high-temperature superconductor yttrium barium copper oxide, grown epitaxially
on the substrate. The substrate orients the dx2–y2 Cooper pair wave function as indicated
by the four-leaf clovers. At the point where the ring crosses from one substrate to the
next it has a grain-boundary Josephson junction. Cooper pairs moving from the lower
section to the upper left suffer an orientation change of less than 45 degrees and hence
have a positive overlap with their new state. The same is true for tunneling from the
upper left to the upper right. However, the orientation change from the upper right to the
lower section exceeds 45 degrees and hence gives a negative overlap. A Cooper pair
traveling around the central ring thus picks up a net minus sign (a phase shift of p), which
results in destructive interference that raises the energy. The other three rings remain
unfrustrated. The frustration of the central ring can be alleviated if a spontaneous current
begins to circulate, which produces a half quantum of magnetic flux, because the Aha-
ronov-Bohm effect would then introduce an additional ±p phase shift. This saves more
than enough energy to pay for the cost of producing the current. Thus, if the supercon-
ductor is d-wave, the system is unstable to producing half a flux quantum trapped in the
central ring. The bright spot in the central ring is an image based on a scanning-probe
measurement, using superconducting quantum interference devices, of the local magnetic
field. [Reprinted with permission from Barbara Levi, Physics Today 49, 19-22 (1996).
Copyright © 1996 American Institute of Physics.] (Right) The same data are shown but
in a three-dimensional representation. The total integrated flux in the central ring is very
close to half a flux quantum, providing proof that the system is frustrated and is almost
certainly d-wave. [Reprinted with permission from Nature 373, cover page (January 9,
1995). Copyright © 1995 Nature.]

One novel feature of d-wave superconductivity is that scattering at interfaces

and nonmagnetic scattering by disorder can be pair-breaking. This effect has
come to the fore recently because of evidence that has been obtained suggesting
that certain crystal faces of high-Tc materials spontaneously break time-reversal
symmetry by nucleating an additional pairing channel (for which surface scatter-
ing is not pair-breaking) to form a complex gap function.
The second similarity between the oxides and superfluid helium-3 is that both
are strongly correlated systems. The oxides, however, are unusual in that the
coherence length (size of a Cooper pair) is small, comparable to the spacing
between the particles, which means that the transition bears a closer resemblance
to Bose-Einstein condensation. Fluctuation effects are far more important than in
an ordinary superconductor because mean field theory relies for its validity on
there being a very large number of particles within the volume occupied by each
Cooper pair.
Understanding strong correlation effects is an important challenge for both
the superconducting state and the unusual normal state of these materials. At
present there is no clear understanding of the mechanism for high-temperature
superconductivity. We do not know, for example, whether the superconductivity
occurs because of, or in spite of, antiferromagnetism. Indeed, it is not unreason-
able to ask whether the phrase “the mechanism” is even meaningful in this case.
Superfluid helium-3 is a strongly correlated Fermi liquid that just barely
manages to form Cooper pairs. It is not yet clear how to describe the correspond-
ing strong correlations in high-temperature superconductors. The strange proper-
ties of the normal state—for example, the extremely linear temperature depen-
dence of the resistivity—may mean that the standard theory of Fermi liquids
cannot be used to describe them. If so, a totally new paradigm will have to be
developed. Ideally, it will be possible to develop a simple picture that captures
the essential physics and allows us to construct new materials with even higher
critical temperatures, perhaps even higher than room temperature.
The small size of Cooper pairs in high-temperature superconductors has the
benefit that, at least naively, it increases their tolerance for very strong magnetic
fields. However, it may also be one of the many factors that limit the critical
currents in these materials. Despite the technological problems caused by this
latter effect, and despite the difficult materials problems, progress is being made
toward practical applications of high-Tc materials.
Study of the short coherence length and associated strong fluctuations of the
order parameter in high-Tc materials has led to some interesting and fundamental
advances in statistical mechanics. The theoretical ideas that have been developed
are directly relevant to technological problems presented by the strong suppres-
sion of the critical current by magnetic fields. Because of their short coherence
length, high-Tc superconductors are strongly type-II. This means that an applied
magnetic field penetrates the sample relatively uniformly, inducing a high den-
sity of vortex lines.

Application of a current produces a driving force that pushes the vortices

sideways, leading to dissipation of energy. Naturally occurring or artificially
introduced disorder produces random traps that tend to impede the motion of the
vortices. One of the deep questions about this random statistical mechanical
system is whether, in the limit of a weak driving force, the vortices are perfectly
pinned. That is, is the linear response resistivity ever truly zero at any finite
temperature? More colloquially, is a superconductor in a magnetic field really a
superconductor?
For many years it was thought that the answer to this question was no. The
rate of vortex “creep” was known to become extremely small at low tempera-
tures, but it was believed to be thermally activated, giving a never-vanishing
resistivity of the form ρ ~ e−ε/kBT. The physical picture behind this is that there is
a characteristic energy barrier ε, associated with the random pinning, which is
finite and can be overcome by thermal fluctuations.
In low-temperature superconductors this question, although important in prin-
ciple, is nearly moot in practice because the barrier ε tends to be large relative to
typical thermal energies at Tc. The pinning is thus extremely effective at all
temperatures where superconductivity exists. In high-Tc materials, the pinning
barrier ε is smaller (another side effect of the short coherence length) and Tc is
much larger. Hence, magnetic fields induce high dissipation rates, which allows
the temperature dependence to then be followed over a significant range below
the zero-field Tc.
It is now understood that the correct answer to our question—Is a supercon-
ductor in a magnetic field really a superconductor?—is yes. As the temperature
is lowered, the highly fluctuating “tangled spaghetti” of vortex lines begins to
exhibit collective correlations over a length scale ξ that diverges at a characteris-
tic “vortex glass” temperature Tg.
Associated with this diverging length is a divergence in the effective collec-
tive pinning barrier ε ~ |T – Tg|–θ. Below this temperature the barrier is infinite
and cannot be overcome by (equilibrium) fluctuations. The linear-response resis-
tivity is thus truly zero, not merely small.
The existence of a distinct vortex glass phase, as shown in Figure 3.2, makes
clear the point that the upper critical field Hc2 is a purely mean-field concept. In
mean-field theory, the sample is “normal” for H > Hc2 and “superconducting” for
H < Hc2. We now understand that Hc2 is merely a crossover scale below which
the order parameter rapidly becomes large. Because of the strong fluctuations in
high-Tc materials, there is a “vortex liquid” regime in which the resistivity is
finite even though the superconducting order parameter is large. Only when the
system enters the frozen vortex glass phase does a true phase transition occur.
Only when the vortices are frozen in place does the dissipation vanish.
Because of the “floppiness” of vortex lines in high-Tc materials (because of
the short coherence length and the extremely weak coupling between copper
oxide planes along the c axis), random point defects are not very effective at

FIGURE 3.2 One can interpret classical superconductor vortex lines as world lines of
quantum bosons moving in two space dimensions and one time dimension. In the Feyn-
man-path-integral formulation of quantum statistical mechanics, the trajectories of the
bosons must be followed over a time interval h/kBT. Hence the thickness of the supercon-
ducting sample determines the inverse “temperature” of these fake quantum bosons. No-
tice that the columnar defects constitute a potential for the bosons that is random in space
but constant in time. Thus we have the quantum mechanics of bosons in two dimensions
in the presence of a static random potential. There has been a great deal of interest in the
last decade in this “dirty boson” problem as a model for helium in porous media (or
adsorbed on surfaces) and for modeling the superconductor-insulator transition in metal-
lic films (viewing the Cooper pairs as bosons). There are two different phases at zero
temperature: at low densities or strong disorder, the bosons are localized in an insulating
“Bose glass” phase; at high densities or weaker disorder, the bosons are condensed into a
superfluid state. We can now map these pictures back onto the vortex system: The
“insulating Bose glass” phase is superconducting because the vortices are localized. The
“superfluid” state of the bosons means that the vortices are freely moving (even though
they are highly entangled). Thus the “vortex liquid” has dissipation and represents the
nonsuperconducting state. This “Bose glass” generalization of the vortex glass idea can
be pursued further to include analogs of the Mott-Hubbard Bose insulator, Mott variable
range hopping, and boson tunneling between localized states. Furthermore, our knowl-
edge of the dynamical structure factor for quantum bosons makes predictions for the
static structure factor for the vortex fluctuations that have been confirmed by small-angle
neutron scattering experiments.

pinning. The vortex glass phase does not exist in two dimensions, and it exists in
three dimensions only in the absence of magnetic screening (so that collective
effects are sufficiently strong).
The pinning efficiency for extended columnar defects is much better. These
can be constructed using the linear damage tracks produced by fast-moving heavy
ions from an accelerator. The statistical mechanics of fluctuating vortices in this
situation has an elegant interpretation by means of an analogy with the quantum
mechanics of a Bose liquid (see Figure 3.2).
This quantum boson analogy clearly demonstrates the existence of a phase
transition in which the vortices can become localized by columnar pins leading to
a state with truly zero resistivity in linear response.
The relatively small size of the Cooper pairs in high-temperature supercon-
ductors puts the superconducting transition in a new regime, closer to the Bose-
Einstein condensation limit.
The most extreme regime of Bose-Einstein condensation has recently been
achieved with the creation of condensates in gases of alkali metal atoms held in
atom traps and cooled to nanokelvin temperatures. These are analogous to
helium-4 in the sense that the particles are bosonic, but in this case the gas is
dilute—the spacing between particles is much larger than the scattering length—
and, hence, represents the nearly ideal case of pure Bose-Einstein condensation.
BOSE-EINSTEIN CONDENSATION IN ATOM TRAPS

Tremendous excitement has been generated by the recent success of the
atomic physics community in creating Bose-Einstein condensates (BECs) in di-
lute gases of alkali atoms. A BEC is a coherent state of matter (see Figure 3.3)
in which a finite fraction of the particles occupy the same quantum state. The
indistinguishability of the particles and the fact that below the critical tempera-
ture their thermal de Broglie wavelengths exceed their spacing are central to the
phenomenon. Using a two-stage process of laser cooling followed by evapora-
tive cooling to temperatures on the order of 100 nanokelvin, it is now possible to
produce condensates containing a few million atoms in an atomic trap.
BECs have been important in condensed-matter and high-energy physics for
many years. BECs were first observed in superfluid helium in 1938. More
recently, evidence has been obtained for condensation of excitons in semiconduc-
tors. BEC is also believed to provide the mechanism for generating the masses of
the hadronic elementary particles.
What is new here is the parameter range; atomic vapors represent an unprec-
edented low-density regime in which the scattering length (the effective size of
the particles) is much smaller than the typical particle spacing. This opens up a
new range of possible experiments in which one can control the number of
particles, the density, and the atomic species, thereby giving the possibility of
varying, and therefore studying, effective interaction strengths in ways that have

a)
b)
FIGURE 3.3 A laser produces coherent light, which we can think of as Bose condensate
of photons. Understanding what this means can help us understand Bose-Einstein con-
densates (BECs) and atom lasers. Laser light wave oscillations are very similar to the
waves produced by an ordinary radio transmitter, as shown in a. Because nothing fixes
the phase of an oscillator, the phase undergoes a slow random walk, but the amplitude
fluctuates very little. The random walk of the phase introduces a finite correlation time
and hence a small but finite spectral bandwidth. A thermal source of the same bandwidth
could be obtained by passing black-body radiation through a narrow filter. The resulting
wave would look something like that shown in b. The large amplitude fluctuations are a
result of interference among the different Fourier components, each of which has a ran-
dom amplitude and phase. If the intensity and bandwidths are the same, the autocorrela-
tion functions will be very similar. To distinguish coherent light from incoherent, we
therefore have to look at fluctuations. For a perfectly coherent state there are no fluctua-
tions: 〈ψ†ψ†ψψ〉 – 〈ψ†ψ〉2 = 0. The quantum mechanical interpretation of this is that the
photons are Poisson distributed independently of each other, so that there is no bunching.
For a thermal source, the fields are gaussian random variables and Wick’s theorem tells
us that 〈ψ†ψ†ψψ〉 = 2! 〈ψ†ψ〉2, so that there are very large intensity fluctuations. The
quantum interpretation is that there is excess “noise” or “bunching” in the photon distri-
bution. In the atom trap, the potential energy of the short-range interacting bosons is
given by the probability of finding two bosons at the same place at the same time,
〈V〉 ∝ 〈ψ†ψ†ψψ〉. Experiments comparing the normal and condensed states at the same
density have shown that, just as expected, 〈V〉normal/〈V〉condensed = 2!. The atomic vapor is
unstable to decay into bound atom pairs, which fall (literally) out of the trap. Because
a third body is needed to carry off the binding energy, the decay rate obeys
〈ψ†ψ†ψ†ψψψ〉normal/〈ψ†ψ†ψ†ψψψ〉condensed = 3!. Remarkably, this third-order coherence
effect has also been observed experimentally. Thus an atom trap emitting a coherent
beam of alkali atoms (a “boser”) has all the coherence properties of a laser.
not been possible in traditional condensed-matter systems. In addition, some of

the characteristic timescales are extremely slow (fractions of a second) opening
up the possibility of studying macroscopic quantum coherence effects in a totally
new time domain.
The other aspect that is new is the unprecedented ability to dynamically
change the trap parameters and optically probe the detailed response of the
condensate. It is now possible, for example, to measure such quantities as the

potential energy stored in the condensate and the momentum distribution func-
tion. In addition, it is possible to suddenly remove a barrier between two
condensates and directly see the quantum interference fringes that result from
their overlap. In the future it will likely be possible to extend these results
to multicomponent condensates and study the separate response of each
component.
Atomic condensates have played a truly useful role in promoting cross-
disciplinary communication and productive interactions among the condensed-
matter, atomic-physics, and quantum-optics communities. The condensed-mat-
ter theory community is supplying expertise in two areas: many-body calculation
techniques and experience with the study of collective effects. It turns out that in
this low-density regime, straightforward and standard mean-field theory calcula-
tion methods appear to be quite accurate for low temperatures, so there appear to
be few theoretical challenges in this regard (except for questions of metastability
for systems with negative scattering lengths that have not yet been fully settled).
On the other hand, there remain quite a few challenges in understanding collec-
tive effects. These include the mechanism for damping of collective modes at
finite temperatures, two-fluid hydrodynamics, effects of the spin degrees of
freedom, the details of the different time regimes in the dynamics of condensate
formation, and how the systems carry angular momentum via vortices and multi-
pole shape distortions. There are connections with models of nuclei here.
Fermi systems are also of considerable interest. Because Pauli exclusion
limits the phase space available for scattering, the two-body collision rate drops
rapidly as the temperature is lowered, and it is difficult to cool and equilibrate a
Fermi system in isolation. (In a degenerate Fermi system the Fermi energy is
much larger than the temperature. Evaporation carries away highly energetic
particles, but this mostly results in lowering the Fermi energy, rather than cooling
the system.) However, sympathetic cooling in Bose-Fermi mixtures is possible
because the Bose-Fermi collision rate is not limited by the Pauli principle. The
fermions cool by losing energy to the bosons, which are in turn cooled by the
usual evaporative means. This opens up new possibilities similar to those studied
in superfluid 3He-4He mixtures but now in a very different regime.
A profound physical problem that the atomic BECs seem well suited to
address is that of the dynamics of a macroscopic quantum system approaching an
equilibrium state with long-range phase coherence. This physics is important
both in connection with the dynamics of the cooling process and for the develop-
ment of atom lasers (“bosers,” see Figure 3.3). Similar questions have been
addressed in the condensed-matter literature—for example, in connection with
the development of nematic order in liquid crystals quenched from high tempera-
tures. The theory of such ordering kinetics is reasonably well developed. How-
ever, the experimental systems studied so far are all well described by a classical,
overdamped dynamics; that is, their time evolution consists merely of a frictional
descent into the nearest local energy minimum. The theoretical analyses have

also all been for purely relaxational models. The dynamics of the atomic BEC
systems is clearly not in this regime, as the unitary time evolution of Schrödinger’s
equation is surely important in the development of macroscopic phase coherence.
Experimental and theoretical studies examining these fundamental issues are
beginning, and their rapid advancement offers exciting prospects for the future.
QUANTUM SPIN CHAINS AND LADDERS

The study of quantum magnetism has experienced a resurgence in the last
decade with the synthesis of whole new families of organic and inorganic com-
pounds containing spin-1/2 and spin-1 degrees of freedom. One very important
consequence of the discovery of high-temperature superconductors has been
progress in the synthesis of oxide compounds having spins arranged in two-
dimensional planes, one-dimensional chains, quasi-one-dimensional ladders with
both even and odd numbers of legs, and even two-dimensional arrays of intersect-
ing one-dimensional chains. These new systems have fascinating properties and
provide an excellent testing ground for theories of strongly correlated electronic
systems. The fact that some of these ladders can be doped provides a testing
ground for ideas about high-temperature superconductors in a simplified quasi-
one-dimensional setting. There may also be even more direct connections be-
cause of the existence of quasi-one-dimensional domain wall structures in the so-
called “striped phase” of nominally two-dimensional high-Tc materials. Spin-1/2
is the most quantum-mechanical spin length and had previously been available
for study only in complicated organometallic compounds. In those materials, the
very weak coupling between spins makes the interesting quantum effects only
occur at extremely low temperatures.
Paradoxically, magnetism arises from electrostatic not magnetic forces. Mag-
netic dipole forces are weak and generally detrimental to the creation of magnetic
alignment. Instead, it is the Coulomb interaction, combined with the Pauli prin-
ciple, that can lead to spin alignment and, hence, to magnetism. The overall
antisymmetry of the quantum wave function for a pair of electrons requires that
the spatial wave function be symmetric for the spin singlet and antisymmetric for
the spin triplet. If the spatial wave function is antisymmetric, it vanishes when
two electrons are at the same location; thus the probability of close approach is
reduced. This in turn reduces the mean Coulomb repulsion. However, this
reduction in the potential energy comes at the expense of increased kinetic energy
associated with the extra nodes in the spatial wave function. Roughly speaking,
if the potential energy term dominates, the system will have a ferromagnetic
ground state. If the kinetic energy dominates, the system will have an antiferro-
magnetic ground state.
Classically, it makes no formal difference to the statistical mechanics whether
a local moment system is ferromagnetic or antiferromagnetic (as long as we
consider a bipartite lattice so that the antiferromagnetism is not frustrated) or has

a large or a small spin angular momentum (say, S = 5/2 or S = 1/2). A classical

spin can point in any direction, and its dynamics can be understood in terms of a
simple gyroscope precessing under the influence of torques as a result of interac-
tions with its neighbors. This mutual precession leads to the existence of a
continuum of spin waves with precession frequencies proportional to the square
of the wave vector in ferromagnets and linear in the wave vector for antiferro-
magnets.
A quantum spin is a very strange and different beast. If its component in
a particular direction is measured, it will always be found to be one of a discrete
set of only 2S + 1 values: –S, –S + 1, . . . , S – 1, S. This discreteness suggests
that quantum magnets could be very different, perhaps having a discrete
excitation gap or other properties that depend in detail on the particular value
of S.
At the same time, quantum mechanics has another novel feature that opposes
this discreteness. Quantum mechanics allows for the possibility of uncertainty as
to which state a spin is in. In fact, there exists a continuum of “coherent states”
that are linear superpositions of the 2S + 1 discrete basis states. This continuum
of possibilities allows the quantum spin to act somewhat classically. Thus, for
example, a spin-1/2 can be chosen to be in a linear combination of “up” and
“down” that is pointing in some arbitrary transverse direction. This competition
between discrete and continuum pictures, which in a sense is analogous to the
usual wave-particle duality of quantum mechanics, leads to very rich physics in
quantum magnets.
Many spin systems can, to a good approximation, be represented by a quan-
tum Heisenberg model. In spatial dimensions greater than 1, it turns out that for
this model, the particular length and discrete nature of the spin is not very crucial,
but there is still a major distinction between ferromagnets and antiferromagnets.
The ferromagnet has a purely “classical” ground state, in which the spins are fully
aligned in some arbitrary direction. The low-lying excited states are spin waves
carrying S = 1 and behaving approximately like free bosons whose energy
increases quadratically with momentum. The antiferromagnet (whose order pa-
rameter is the staggered magnetization) is somewhat different: quantum fluctua-
tions reduce the order parameter below the classical value even at zero temper-
ature; hence, the exact ground state is not known. The low-lying excitations are
nevertheless spin waves carrying S = 1 and having an energy linear in the mo-
mentum, just as the classical precession frequency is linear rather than quadratic
in the wave vector.
These simple pictures break down completely for the case of one-dimensional
antiferromagnets, for which quantum fluctuations are especially severe. In particu-
lar, there is no long-range order in the staggered magnetization even at zero tem-
perature (the spin-spin correlation functions fall off algebraically at zero tempera-
ture and exponentially at finite temperature). For S = 1/2, it turns out that the naive
spin wave picture fails because the S = 1 bosonic spin wave “fractionalizes” into

(a)
(b)
(c)
FIGURE 3.4 Spin fractionalization process in which a ∆S = 1 spin flip in a spin chain
breaks up into two domain walls each carrying spin-1/2. (a) Perfectly ordered antiferro-
magnetic configuration for a spin-1/2 chain. (b) The circled spin has been flipped.
(c) Adjacent pairs of spins mutually flip producing a pair of domain walls (indicated by
the dashed lines) separating perfectly ordered antiferromagnetic configurations. These
domain walls (“spinons”) are unconfined and free to move independently.
two independent S = 1/2 objects known as “spinons.” A graphic depiction of the

fractionalization process is shown in Figure 3.4. The first row shows a perfect
antiferromagnetically ordered array of spins. In the second row, angular momen-
tum S = 1 has been added to the array by flipping a single spin in the center. The
third row shows the time-evolved state obtained by an angular momentum conserv-
ing mutual spin flip of the pair of spins just to the left of the center spin and the pair
just to the right. We now see that the original flipped spin has broken up into a pair
of “domain walls,” which can separate indefinitely because the interior region
between the walls is still perfectly ordered antiferromagnetically. It is possible to
show that each of these domain-wall defects acts like a quantum particle carrying
half of the S = 1 angular momentum of the original spin flip.
An immediate experimental consequence of the spin-wave fractionalization
is that there is much more phase space available for spin excitations. An ordinary
spin wave has a definite energy associated with each momentum. A pair of
spinons, however, can be in many different individual momentum states for a
given total momentum. This results in a band of possible energies, rather than a
single energy, for a given momentum (see Figure 3.5).
The picture we have just described for one-dimensional spin-1/2 chains ap-
plies mutatis mutandis to the case of all odd-half-integer spins (1/2, 3/2, 5/2, . . .).
However, the case of integer spin values is radically and surprisingly different. It
turns out that integer spin chains described by the Heisenberg model have an

FIGURE 3.5 Spinon production observed by spin-flip inelastic neutron scattering. There
is much more phase space available for spinons than for ordinary spin waves. The curve
with period π in the upper panel is the single spinon dispersion curve. The curve with
larger amplitude and period 2π is the upper bound on the range of allowed energies for a
pair of spinons of total momentum Q. The parabolic curve in the upper panel is the
kinematically allowed momentum and energy transfer to the scattered neutrons. The
lower panel shows large peaks in the cross section at energies correctly predicted by the
picture in which a single flipped spin decays into a pair of independent spinon excitations.
Ordinary spin wave theory would predict zero intensity in the first and third peaks. [Phys-
ical Review Letters 70, 4003 (1993).]

FIGURE 3.6 Typical spin configuration in the ground state of the Affleck-Kennedy-
Lieb-Tasaki (AKLT) model. The symbols refer to the z component of the spin at each
site. Notice that, if the zeros are ignored, the state has perfect antiferromagnetic order.
apparently featureless “spin liquid” ground state with an excitation gap and spin
correlations that decay exponentially with distance even at zero temperature. The
spin degrees of freedom seem to have disappeared because of some “confine-
ment” mechanism.
The origin of the excitation gap is a novel “hidden” topological order not
visible in the ordinary spin-spin correlation function. This order is best under-
stood by studying the Affleck-Kennedy-Lieb-Tasaki (AKLT) model, which is
closely related to the Heisenberg model but whose ground state is more readily
soluble. Figure 3.6 shows a typical configuration (in the Sz basis) of the spins in
the ground state of the AKLT model. We see that an up spin can be followed by
an arbitrary number of zeros (“sideways spins”) but then must be followed by a
down spin. That is, if we removed all the zeros, there would be perfect antiferro-
magnetic order. This novel order is completely invisible to the ordinary, experi-
mentally measured, spin correlation function and can only be detected theoreti-
cally using a nonlocal “string order” correlation function that includes a factor of
–1 for each of the nonzero spins within the string of spins connecting two sites.
The most obvious experimental manifestation of this hidden topological order is
that it costs a finite amount of energy to break it; hence, the system has a spin
excitation gap.
The origin of the excitation gap can also be understood by examining a
different graphic of the AKLT ground state shown in Figure 3.7a. Each S = 1 spin
on a site is visualized as being made up of a pair of spin-1/2 particles. These
spins are formed into singlet bonds with their neighbors to create a “valence bond
solid” as shown. Enforcing the rule that the state be symmetric under interchange
of the pair of spins on a site guarantees that they will form a triplet and correctly
represent the S = 1 on that site (see Figure 3.8).
Just as in the case of the spin-1/2 chain, it is possible to split a single spin flip
with ∆S = 1 into a pair of spinon excitations each carrying S = 1/2. This is
illustrated in Figure 3.7b. Notice now, however, that in order to avoid generating
more unpaired spins, the two sites containing the unpaired S = 1/2 spins are
connected by a “string” of alternating double bonds and missing bonds. There is
a finite “string tension,” meaning there is a finite energy cost per unit length to
produce this string. Thus, in contrast to the S = 1/2 chains, the spinons are
confined (much as quarks are) and the resulting excitation (“meson”) has a finite
minimum energy cost. It can be shown that this excitation breaks the topological
order discussed above. The situation for larger integer spins is similar, but the

(a)
(b)
FIGURE 3.7 (a) Valence bond solid picture of the same Affleck-Kennedy-Lieb-Tasaki
(AKLT) model ground state shown in Figure 3.6. The dots represent a site that contains a
single spin S = 1. This is viewed as being made up of a pair of spin-1/2 particles, each of
which forms a singlet bond (solid line) with one of its neighbors. (b) An excited state of
the AKLT model. Because sites are viewed as containing two spin-1/2 particles, there
must be either two bonds or one bond and an unpaired spin on each site. Thus there are
two spin-1/2 particles liberated here. The string of alternating double and zero bonds
costs a finite energy per unit length. This “string tension” confines the spin-1/2 particles
together much as quarks are confined.
gap must become exponentially small in order to match onto the gapless classical
limit at S = ∞.
A great deal of theoretical progress has been made in understanding the role
of disorder in one-dimensional quantum spin chains for both S = 1/2 and S = 1.
The S = 1/2 system develops into a random singlet phase in which there are strong
singlet bonds over short distances and arbitrarily weak bonds over arbitrarily long
distances. The S = 1 chain is quite different because it is initially gapped and,
therefore, stable against weak disorder. For moderately strong disorder, the gap
is destroyed, but the topological order remains in a “Griffiths” phase. Thus,
paradoxically, the spins that disappeared at low energies in the clean system can
be made to reappear by the addition of strong nonmagnetic impurity disorder.
This is illustrated in Figure 3.9, which shows a segment of an S = 1 chain cut off
from the rest of the chain by a nonmagnetic impurity at each end. The disruption
of the valence bond solid ground state liberates a nearly free spin-1/2 at each
end of the segment. This is manifested experimentally in the magnetic suscepti-
bility, which becomes algebraic rather than exponential at low temperatures.
There are many open questions still to be addressed. In two and three
dimensions there are a rich variety of highly frustrated lattices such as the kagome
for which we still lack a complete understanding of the low-energy physics.
Debate continues as to whether high-temperature superconductivity occurs be-
cause of, or in spite of, antiferromagnetism in the insulating parent compounds.
Mixtures of itinerant electrons and local moments occur in heavy fermion, Kondo
lattice, and disordered systems near the metal-insulator transition. These con-
tinue to be dauntingly complex theoretical and experimental challenges. In addi-
tion, the entirely new classes of oxide systems now being synthesized will pro-
duce fascinating new realizations of ladders, chains, and planes of spins, which
will doubtless raise new theoretical and experimental challenges.

J1 J2 J1 J2 J1 J2 J1 J2
∆
Dimerization gap
Haldane gap
0 1 J2 /J1
FIGURE 3.8 There is a connection between the gap seen in S = 1 (and other integer)
chains and the gap seen in dimerized systems. (Upper) Consider the S = 1/2 chain with
alternating weak and strong bonds. In the limit J2 = 0, the exact ground state is a “valence
bond solid” (VBS) of singlets on the J1 bonds. For J2 nonzero, the bonds begin to
fluctuate, but the VBS state still captures the essential physics, and the gap survives
throughout the region J2 ≠ J1. (Lower) The gap persists even as the strength of the weak
bond passes through zero and changes sign to become ferromagnetic. As these bonds
become infinitely ferromagnetic, the associated pairs of spins become locked into triplet
states, and one recovers the S = 1 spin chain description. Because the gap never closes
during this process, the system does not undergo any phase transition as the dimerization
is varied adiabatically. It follows that the dimer system has the same type of topological
order, measured by the “string” correlation function, as the S = 1 system and that the
Haldane gap in an S = 1 system is a special limit of the dimerization gap in an S = 1/2
system. [Reprinted with permission from S.M. Girvin, “Exotic quantum order in low-
dimensional systems,” Solid State Communications 107, 623 (1998). Copyright © 1998
Elsevier Science.]
FIGURE 3.9 Nonmagnetic impurities (denoted by crosses) liberate spin-1/2 degrees of

freedom in a gapped spin-1 chain. This follows from the fact that every site must have
either two bonds or one bond and a free spin. These liberated spins are only weakly
coupled to each other and hence produce low-energy excitations inside the Haldane gap.
They are experimentally observable via their Curie-like contribution to the susceptibility.

THE QUANTUM HALL EFFECT

The various quantum Hall effects are arguably among the most remarkable
many-body phenomena discovered in the second half of the twentieth century,
comparable in intellectual import to superconductivity and superfluidity. They
are an extremely rich set of phenomena with deep and truly fundamental theoreti-
cal implications. The integer effect, whose discovery was awarded the 1985
Nobel Prize (see Table O.1), has revolutionized our understanding of localization
and transport in high magnetic fields. The fractional effect, whose discovery and
theoretical explanation was awarded the 1998 Nobel Prize (see Table O.1), has
yielded new paradigms of fractional charge, spin, and statistics as well as unprec-
edented order parameters. There are beautiful connections with a variety of
different topological and conformal field theories studied as formal models in
particle theory, each here made manifest by the twist of an experimental knob.
Where else but in condensed-matter physics can an experimentalist change the
number of flavors of relativistic chiral fermions, or set the Chern-Simons angle
by hand?
Some of the themes discussed above for quantum spin chains reappear here.
The gapped-spin liquid with hidden topological order is replaced by a gapped-
charge liquid, which also has a novel form of hidden topological order. The
concepts of quantum number fractionalization and confinement and deconfine-
ment of quasiparticle excitations also reappear.
Because of the recent technological advances in molecular beam epitaxy and
the fabrication of artificial structures, the field continues to advance with new
discoveries, even well into the second decade of its existence. Experiments in the
field were limited for many years to simple transport measurements that indi-
rectly determine charge gaps. However, recent advances have led to many suc-
cessful optical, acoustic, microwave, specific heat, and nuclear magnetic reso-
nance (NMR) probes that continue to advance our knowledge as well as raise
intriguing new questions.
The quantum Hall effect takes place in a two-dimensional electron gas sub-
jected to a high magnetic field. In essence, it is a result of commensuration
between the number of electrons, N, and the number of flux quanta in the applied
magnetic field, NΦ. The electrons undergo a series of condensations into new
states with highly nontrivial properties whenever the filling factor ν = N/NΦ takes
on simple rational values. The original experimental manifestation of this effect
was the observation of an energy gap yielding dissipationless transport (at zero
temperature) much like in a superconductor. The Hall conductivity in this
dissipationless state is universal, given by σxy = νe2/h independent of microscopic
details. As a result of this, it is possible to make a high-precision determination
of the fine-structure constant and to realize a highly reproducible quantum-
mechanical unit of electrical resistance, now used by standards laboratories
around the world to maintain the ohm.

The integer quantum Hall effect (IQHE) owes its origin to an excitation gap
associated with the discrete kinetic energy levels (Landau levels) in a magnetic
field. The fractional quantum Hall effect (FQHE) has its origins in very different
physics of strong Coulomb correlations that produce a Mott-insulator-like ex-
citation gap. In some ways, however, this gap is more like that in a superconduc-
tor because it is not tied to a periodic lattice potential. This permits uniform
charge flow of the incompressible electron liquid and, hence, a quantized Hall
conductivity.
The microscopic correlations leading to the excitation gap are captured in a
revolutionary wave function, developed by R.B. Laughlin, that describes an in-
compressible quantum liquid. The charged quasiparticle excitations in this sys-
tem are “anyons” carrying fractional statistics, intermediate between bosons and
fermions, and fractional charge. This sharp fractional charge, which despite its
bizarre nature has always been on solid theoretical ground, has recently been
observed directly in two different ways. The first is an equilibrium thermody-
namic measurement using an ultrasensitive electrometer built from quantum dots
(see Figure 3.10). The second is a dynamical measurement using exquisitely
sensitive detection of the shot noise for quasiparticles tunneling across a quantum
Hall device.
Quantum mechanics allows for the possibility of fractional average charge in
both a trivial way and a highly nontrivial way. As an example of the former,
consider a system of three protons, arranged in an equilateral triangle, and one
electron tunneling among their 1S atomic bound states. The electronic ground
state is a symmetric linear superposition of the quantum amplitudes for being in
each of the three different 1S orbitals. In this trivial case, the mean electron
number for a given orbital is 1/3. This is a result of statistical fluctuations,
however, because a measurement will yield electron number 0 two-thirds of the
time and electron number 1 one-third of the time. These fluctuations occur on a
very slow timescale and are associated with the fact that the electronic spectrum
consists of three very nearly degenerate states corresponding to the different
orthogonal combinations of the three atomic orbitals.
The ν = 1/3 quantum Hall effect has charge-1/3 quasiparticles, but it is
profoundly different from the trivial scenario just described. An electron added
to a ν = 1/3 system breaks up into three charge-1/3 quasiparticles. If the locations
of the quasiparticles are pinned by, say, an impurity potential, the excitation gap
still remains robust and the resulting ground state is nondegenerate. This means
that a quasiparticle is not a place (like the proton above), where an extra electron
spends one-third of its time. The lack of degeneracy implies that the location of
the quasiparticle completely specifies the state of the system; that is, it implies
that these are fundamental elementary particles with charge 1/3. Because there is
a finite gap, this charge is a sharp quantum observable that does not fluctuate (for
frequencies below the gap scale).
To understand this better, imagine that you are citizen of Flatland, living in

FIGURE 3.10 (Left) Variation of the conductance for tunneling through a quantum dot
as a function of bias voltage on the dot. The oscillations indicate the discrete charging of
the dot under quasi-thermodynamic equilibrium conditions. The period of the oscillations
for the ν = 1/3 quantum Hall plateau is three times smaller than for the ν = 1 plateau,
indicating that the quasiparticle charge is one-third that of an electron. (Right) Absolute
shot noise for currents tunneling through a ν = 1/3 Hall fluid. The deviation from linear-
ity at low currents is the crossover from shot noise to thermal Nyquist noise. Both the
intensity of the noise and the location of the crossover from shot noise to Nyquist noise
are in quantitative agreement with the quasiparticle charge being e* = 1/3. The dashed
line shows the predicted shot noise if the current were carried by objects with charge e
instead of e/3. [Right: Reprinted with permission from R. De-Picciotto, M. Reznikov, M.
Heiblum, V. Umansky, G. Bunin, and D. Mahalu, “Direct observation of a fractional
charge,” Nature 389, 163 (1997). Copyright © 1997 Nature.]
the cold world of a two-dimensional electron gas in a high magnetic field.

Flatland cosmologists have theorized that the charged particles seen drifting
around are topological defects left over from the Big Chill at the beginning of the
universe. Flatland particle theorists decide that the apparently featureless vacuum
in which everyone lives each day is actually a roiling sea, filled with strange but
invisible objects that have precisely three times the charge of one of these quasi-
particles. To study this possibility, a Flatland high-energy particle accelerator is
constructed that can reach the unprecedented energy scale of 10 K. On smashing
together three charged particles, it is found that they do indeed temporarily coa-
lesce into an object with the bizarre property of having integer charge. It is
decided to name this short-lived object “the electron.”
The message here is that the charge of the quasiparticles is sharp to the
observers so long as the gap energy scale is considered large. If the gap were 10
GeV instead of 10 K, we (living at room temperature) would have no trouble
accepting the concept of fractional charge.

Composite Particles
It is a peculiarity of two dimensions that the ν = 1/3 vacuum represented by
the Laughlin wave function can be viewed in more than one way in terms of
composite particles. One way is to make a singular gauge transformation that
attaches three quanta of magnetic flux to each electron. This induces an
Aharonov-Bohm phase of 3π when two particles are interchanged. The physics
will therefore remain invariant if we change the particle statistics from fermion to
boson to cancel this phase change. At ν = 1/3 there are three flux quanta from the
externally applied uniform magnetic field for each particle. Thus, if we make a
mean-field approximation in which the flux quanta attached to the particles are
smeared out into a uniform field, they will precisely cancel the external field,
leaving a theory of composite bosons in zero (mean) magnetic field, as illustrated
schematically in Figure 3.11. The condensate wave function of these bosons
defines a hidden off-diagonal long-range order not visible in the ordinary correla-
FIGURE 3.11 Illustration of the condensation of composite bosons in the ν = 1/3 frac-
tional quantum Hall effect. The three flux quanta attached to the electrons convert them
into bosons moving in zero average field. Vortices in the condensate are the Laughlin
quasiparticles carrying charge ±1/3.

tion functions of the original electron variables. (There are deep analogies here
with the hidden string order in quantum spin chains discussed previously.)
The natural excitations in a bosonic condensate are (Goldstone mode)
phonons and vortices. The analogs here (“magnetophonons”) have recently been
observed directly in Raman scattering. Vortices in two dimensions normally cost
a logarithmically divergent amount of energy and are confined in neutral pairs at
low temperatures. In the FQHE, however, something peculiar happens. Because
each composite boson carries three flux quanta, binding one-third of a charge to
the vortex is equivalent to binding one quantum of flux to the vortex. Just as in a
type-II superconductor, this quantized flux screens out the currents at large dis-
tances and removes the divergence in the energy. Thus in this picture, the
Laughlin quasiparticles are topological defects, and the same mechanism that
gives them fractional charge also deconfines them. By analogy with type-II
superconductors, the magnetophonon acquires a mass gap, which was predicted
theoretically and has been observed experimentally.
An alternative picture of the ν = 1/3 vacuum can be developed by attaching
two rather than three flux quanta to each particle. These composite objects
remain fermions and see a mean magnetic field of one flux quantum per particle,
as illustrated schematically in Figure 3.12. Thus the ν = 1/3 FQHE is mapped
onto the IQHE at νeff = 1. The Laughlin quasiparticles become additional com-
posite fermions added to the next Landau level. In this formulation the off-
diagonal long-range order remains hidden, but there are two significant advan-
tages. First, accurate variational wave functions for various hierarchical quantum
Hall states at different rational filling fractions can be written down explicitly and
studied numerically with relative ease. Second, the special case of ν = 1/2 is
naturally described as composite fermions in zero mean magnetic field. The
characteristic Fermi surface wave vector 2kF of these composite fermions has
been observed in surface acoustic wave attenuation experiments. If the mean
field picture is taken literally, then moving slightly away from ν = 1/2 puts
the composite fermions in a weak magnetic field that should cause the quasipar-
ticles to follow curved trajectories. Remarkably, this too has been observed
experimentally.
It should be emphasized that experiments to date have all dealt with the
kinematics of the composite fermions and the associated length scales, not their
dynamics and the associated frequency scales. Hence, there is no unambiguous
evidence for long-lived Fermi liquid-like quasiparticles above a sharply defined
Fermi surface, as opposed to well-defined length scales at the Fermi surface.
There is great theoretical interest currently in trying to understand the nature of
fluctuations around the mean-field solution and their effect on the composite
fermions. Considerable progress has been made, but many questions still remain
to be definitively settled.

FIGURE 3.12 Illustration of the formation of composite fermions in the ν = 1/3 frac-
tional quantum Hall effect. The two flux quanta attached to the electrons turn them into
fermions moving in an average field corresponding to the ν = 1 integer quantum Hall
effect. A Laughlin quasiparticle is represented by a composite fermion in the next
Landau level.
Edge States
At low energies, the bulk of an FQHE system appears as a featureless vacuum
with an excitation gap; however, very unusual gapless modes exist at the edges.
These are shape distortions that preserve the area of the incompressible fluid. In
a certain sense, the quantized-edge density fluctuations can be viewed as a gas of
Laughlin quasiparticles liberated from the bulk gap.
Because these objects carry fractional charge and statistics in the bulk, they
do not form an ordinary Fermi liquid at the edge. Instead, they constitute a nearly
ideal realization of a chiral Luttinger liquid. The edge modes are chiral because
they propagate in only a single direction, controlled by the direction of E × B drift
in the edge-confinement potential. The density of states for tunneling an ordinary
electron into a Luttinger liquid vanishes with a power-law singularity at low
energies because of an orthogonality catastrophe that results from the fact that the
electron must break up into fractionally charged quasiparticles. Recent progress

n+
quantum well 2DEG
cleaved edge barrier
overgrowth
FIGURE 3.13 (Left) Schematic of a device produced by cleaved-edge overgrowth meth-

ods to measure tunneling into the edge of a two-dimensional electron gas. (Right) Non-
linear current-voltage response for tunneling an electron into a fractional quantum Hall
effect edge state. Because the electron must break up into three fractionally charged
quasiparticles, there is an orthogonality catastrophe that leads to a power-law density of
states. The flattening at low currents is caused by the finite temperature. [Physical
Review Letters 77, 2538 (1996).]
in sample fabrication using cleaved-edge overgrowth techniques has made it

possible to observe the resulting singularity experimentally in the tunneling
current-voltage characteristic, as shown in Figure 3.13.
The various power-law correlations in a Luttinger liquid are characterized by
a critical exponent g, which normally is continuously variable, depending on the
details of the particle interactions. The value of g is therefore nonuniversal and
can only be roughly estimated theoretically. According to current theory, one of
the most important features of the chiral Luttinger liquids realized at the edge of
FQHE systems is that g is universal, dependent only on the quantized value of the
Hall conductivity in the bulk and independent of all details of the electron inter-
actions. In particular, this makes the temperature and voltage dependence of the
tunneling current have a power-law form that is universal and independent of all
microscopic details. The theory works extremely well on the 1/3-quantized Hall
plateau, but the unexpectedly smooth variation of the exponent with magnetic
field away from the plateau shown in Figure 3.13 is not yet understood.

Magnetic Order of Spins and Pseudospins

At certain filling factors (ν = 1 in particular), quantum Hall systems exhibit
spontaneous magnetic order. For reasons peculiar to the band structure of the
gallium arsenide host semiconductor, the external magnetic field couples excep-
tionally strongly to the orbital motion, giving a large Landau level splitting, and
exceptionally weakly to the spin degrees of freedom, giving a very small Zeeman
gap. The resulting low-energy spin degrees of freedom of this ferromagnet have
some rather novel properties, which have recently begun to be probed by NMR,
specific heat, and other measurements.
Because the lowest spin state of the lowest Landau is completely filled at
ν = 1, the only way to add charge is with reversed spin. However, because the
exchange energy is large and prefers locally parallel spins, and because the
Zeeman energy is small, it is cheaper to partially turn over several spins, forming
the topological spin texture shown in Figure 3.14. Because this is an itinerant
magnet with a quantized Hall conductivity, it turns out that this texture (called a
skyrmion by analogy with the corresponding object in the Skyrme model of
nuclear physics) accommodates precisely one extra unit of charge. NMR Knight
shift and other measurements have confirmed the prediction that each charge
added or removed from the ν = 1 state flips over several spins—from 4 to 30,
depending on the pressure. In the presence of skyrmions, the ferromagnetic order
FIGURE 3.14 Skyrmion spin texture in a quantum Hall ferromagnet. Note that the spins
are all up at infinity but down at the origin. At intermediate distances they have a vortex-
like configuration. Because of the quantized Hall conductivity, these objects carry quan-
tized charge. [Reprinted with permission from S.M. Girvin, “Exotic quantum order in
low-dimensional systems,” Solid State Communications 107, 623 (1998). Copyright ©
1998 Elsevier Science.]

is no longer collinear, leading to the possibility of additional low-energy spin

wave modes that remain gapless even in the presence of the Zeeman field (some-
what analogous to an antiferromagnet). These low-frequency spin fluctuations
have been indirectly observed through a dramatic enhancement of the nuclear
spin relaxation rate 1/T1. In fact, under some conditions T1 becomes so short that
the nuclei come into thermal equilibrium with the lattice via interactions with the
inversion layer electrons. This has recently been observed experimentally through
an enormous enhancement of the specific heat by more than five orders of mag-
nitude (see Figure 3.15).
Spin is not the only internal degree of freedom that can spontaneously
order. There has been considerable recent progress experimentally in overcom-
ing technical difficulties in the molecular beam epitaxy fabrication of high-
quality multiple-well systems. It is now possible, for example, to make a pair
of identical electron gases in quantum wells separated by a distance of about
100 Å—comparable to the electron spacing within a single quantum well.
Under these conditions strong interlayer correlations can be expected. One of
the peculiarities of quantum mechanics is that it is possible, even in the absence
of tunneling between the layers, for the electrons to be in a coherent state in
which their layer index is uncertain. To understand the implications of this, we
can define a pseudospin that is up if the electron is in the first layer and down if
it is in the second. Spontaneous interlayer coherence corresponds to spontane-
ous pseudospin magnetization lying in the x-y plane (corresponding to a coher-
ent mixture of pseudospin up and down). If the total filling factor for the two
layers is ν = 1, then the Coulomb exchange energy will strongly favor this
magnetic order, just as it does for real spins. This long-range transverse order
has been observed experimentally through the strong response of the system to
a weak magnetic field, applied in the plane of the electron gases, in the pres-
ence of weak tunneling between the layers. Very recent work indicates that a
two-layer quantum Hall system at filling factor ν = 2 may even allow for an
antiferromagnetic or a canted spin phase, further demonstrating the complexity
and richness of the magnetic phase diagrams of quantum Hall systems.
Another interesting aspect of two-layer systems is that, despite their extreme
proximity, it is possible to make separate electrical contact to each layer and
perform drag experiments in which current in one layer induces a voltage in the
other as a result of Coulomb or phonon-mediated interactions.
The many-body physics of two-layer systems can also be found in wide
single-well systems with the two (nearly degenerate) lowest electric sub-band
states playing the role of the pseudospin degrees of freedom.
Stacking together many quantum wells gives an artificial three-dimensional
structure analogous to certain organic Bechgaard salts in which the quantum Hall
effect has been observed. Interest has been growing recently in the bulk and edge
(“surface”) states of such three-dimensional systems and in the nature of possible
Anderson localization transitions.

GaAlAs GaAs
200nm 20nm
104
104
C (10-9 J/K)
103
Heat capacity (10-9 J/K)
0
102 0.03 0.04 0.05
T (K)
10
θ = 0°
T -2
0.01 0.1 1
Temperature (K)
FIGURE 3.15 Even in a sample with many quantum wells, there are not enough nuclei
in the 20-nm-thick wells to do an ordinary nuclear magnetic resonance (NMR) experi-
ment. The technique of optically pumped NMR therefore had to be developed [Barrett et
al., Physical Review Letters 74, 5112 (1995); Tycko et al., Science 268, 1460 (1995)].
(Upper) Circularly polarized light above the gallium arsenide (GaAs) band gap but below
the band gap of gallium aluminum arsenide (GaAlAs) is absorbed only in the quantum
wells. The angular momentum of the photons is transferred to the orbital motion of
excited electrons and then, via the spin-orbit interaction, to the electron spins. Finally, the
hyperfine interaction transfers the polarization to the nuclei in the quantum wells. This
polarization enhancement allows the NMR signal to reach detectable levels for samples
with as few as 10 wells. NMR experiments clearly demonstrate the existence of skyrmi-
ons—collective excitations with charge ±e and large-spin S. These objects enhance the
nuclear relaxation rate, bringing T1 down from many hours to about 20 seconds. (Lower)
With the nuclei in thermal equilibrium, the specific heat is enhanced by many orders of
magnitude, rising from picojoules to microjoules per kelvin. [Physical Review Letters 76,
4584 (1996) and 79, 1718 (1997).]

Although the quantum Hall effect is extremely well understood at this point,
there remain some important mysteries yet to be resolved. In the IQHE, the main
question continues to be the nature of the delocalization transition in which the
Hall conductivity jumps from one quantized value to the next. The general
scenario by which this happens is well understood; it is almost certain that there
exists a critical point near the center of each Landau level at which the localiza-
tion length diverges, and numerical estimates of the critical exponent agree well
with experiment—in selected samples, at least. It is not understood at present,
however, why generically there are often deviations from the expected scaling
behavior (although the answer probably has to do with macroscopic inhomogene-
ities). One problem only just beginning to be addressed is the possible relevance
of Coulomb interactions to the transition. In addition, despite valiant efforts,
there does not yet exist a simple quantum field theory for this transition from
which we can analytically compute the critical exponent. Finally, there remains
an interesting set of puzzles about what happens at weak magnetic fields as
Landau level mixing becomes strong and direct transitions apparently occur from
quantum Hall effect states to insulating states.
In general, the ordering that produces the hierarchy of fractionally quantized
states is very well understood. The most interesting remaining problem is to
understand the physics of the ν = 1/2 state, which in the composite fermion
picture is a Fermi liquid-like state with zero mean magnetic field. The nature and
effect of fluctuations around the mean field still need to be better understood.
The theory of quantum Hall edge states has successfully made detailed pre-
dictions of the observed temperature and voltage dependence of the tunneling
current-voltage characteristics of the ν = 1/3 fractional plateau edge. One unex-
pected experimental discovery, however, has been that the edge-tunneling den-
sity of states has a power law-form over a wide range of magnetic fields, not just
on the plateaus. Furthermore, as shown in Figure 3.15, the exponent of the power
law varies continuously and linearly with magnetic field and seems quite insensi-
tive to whether the bulk of the sample is in a quantized Hall state or not. Current
theory predicts that the exponent should be quantized, just as the Hall conductiv-
ity is, and should vary discontinuously with magnetic field.
Another significant question involves the sharp peak in the specific heat
shown in Figure 3.15. The large linear region in the plot is explained quantita-
tively by the Schottky anomaly of the nuclei in the quantum wells. The extra
peak is known to involve the additional nuclei in the barriers between the quan-
tum wells, but the mechanism that gives rise to a sharp feature is not understood
at present. It may be related in some way to the freezing of the skyrmions.

SUMMARY
The committee has detailed here just a small sampling of the wide variety of
novel quantum effects that have been explored successfully in the past decade.
Some of the major accomplishments are listed below:
• The discovery of high-temperature superconductivity and identification of

the symmetry of the order parameter and elucidation of novel vortex fluctuations.
• Discovery of quantum phase transitions in two dimensional systems
such as antiferromagnets in high-temperature superconductors, the supercon-
ductor-insulator phase transition in metal films, the metal-insulator transition in
two-dimensional electron gases, and a wide variety of novel quantum Hall
transitions.
• Observation of Bose-Einstein condensation and macroscopic coherence
effects in atom traps.
• Synthesis of new families of spin-1 and spin-1/2 quantum magnets with a
variety of novel geometries, progress in understanding dynamics in disordered
one-dimensional magnets, and the development of giant and colossal magnetore-
sistance materials.
• Numerous new discoveries in quantum Hall physics including direct ob-
servation of the fractional charge of quantum Hall effect quasiparticles, compos-
ite particles, edge-state modes, Raman observation of the fractional quantum Hall
effect neutral excitation gap, discovery of drag and spontaneous coherence in
double-layer systems, and NMR and nuclear specific heat anomalies due to
skyrmions.
• Mesoscopic device physics observations of conductance quantization in
electron wave guides, parity effects in superconducting grains, and Andreev re-
flection in disordered systems.

The novel discoveries of the last decade have raised many new questions and
issues that require further exploration both theoretically and experimentally:
• New tools and paradigms for studying the interplay between interactions
and disorder in quantum systems would shed light on phenomena like the re-
cently discovered metal-insulator transition in two-dimensional electron gases.
• Carbon nanotubes are likely to present a great opportunity for study of
novel electronic properties.
• Many of the remarkable quantum effects discovered in the last decade
have been observable only at relatively low temperatures. Can quantum energy
scales be boosted so that, for example, room-temperature mesoscopic and single-
electron devices can be constructed?

• Can we develop practical theoretical tools to describe real-time dynamics

and nonlinear response of interacting quantum systems as well as their electronic
structure?
• Can we develop general principles to guide us in the study of modern
materials that are vastly more complex than materials of the past?
• What is the physics of the normal and condensed states of high-tempera-
ture superconductors? Can we synthesize room-temperature superconductors
and overcome practical materials difficulties?
• Finally, if the past is any guide, we will be faced with completely unex-
pected and surprising quantum phenomena as new materials are synthesized.
What new techniques will have to be developed to deal with these surprises?

Nonequilibrium Physics
The term “nonequilibrium physics” means “the study of physical systems

that are not in mechanical and thermal equilibrium with their surroundings.” In
some cases, these are systems spontaneously approaching equilibrium, such as a
molten metallic alloy being allowed to cool and solidify. In other cases, they are
systems changing their shapes or properties as forces are exerted on them, heat
applied to them, or their states of repose are otherwise disturbed. Examples
include flowing fluids driven by thermal or pressure gradients, solid materials
deforming or breaking under the influence of external stresses, or quantum sys-
tems—atomic spins, perhaps—being driven by oscillating electromagnetic fields.
As a field of research, nonequilibrium physics is simultaneously very new
and very old. The natural origins of complex patterns such as dendritic snow-
flakes or chaotic motions such as those of turbulent fluids have puzzled human
beings since the dawn of history, but it is only in the last decade or so that we
have begun to understand these phenomena in any depth. This field is also
simultaneously very pure and very applied. The processes used to produce indus-
trial materials—for example, casting alloys for jet engines or fabricating micro-
scopically small features of computer chips—are all applications of nonequilib-
rium physics. In many cases, however, the fundamental research needed to
predict and control these processes with the precision necessary for advanced
technologies has yet to be done.
It is in this area of research, also, that condensed-matter and materials phys-
ics interact especially strongly with other scientific disciplines. Nonequilibrium
physics is inherently interdisciplinary. It has involved engineers, mathemati-
cians, and chemists in addition to physicists since it emerged as a recognized
168

NONEQUILIBRIUM PHYSICS 169
specialty about a generation ago. In recent years, the same nonequilibrium con-
cepts being tested in the design of alloys are also being applied to galaxy forma-
tion in the cosmos, climatic changes on the Earth, and the growth of forms in
biological systems.
The Brinkman report1 was remarkably prescient in its discussion of nonequi-
librium physics. Its authors recognized the growing importance of topics such as
pattern formation, chaotic behavior, turbulence, and fractal geometries. Under-
standably, they missed today’s emerging interests in friction, fracture, and granu-
lar materials and the speculations that some of these spatially extended chaotic
phenomena might be exhibiting previously unanticipated collective behaviors.
They also could not have predicted the invention of the scanning-probe micro-
scopes and optical tweezers that are only just now beginning to open the world of
biological phenomena to first-principles physical investigations.
In the last decade or so—the period since the Brinkman report—important
progress has been made in many of these areas. We now understand in much
more systematic ways how complex patterns emerge from simple ingredients in
hydrodynamic, metallurgical, and chemical systems. Notable progress has been
made in sorting out the mechanisms that control pattern formation, for example,
in convecting liquid crystals, on the surfaces of vibrating fluids, in chemical
reaction-diffusion systems, and in some biological phenomena such as cellular
aggregation and membrane morphology. New understanding of spiral waves in
active media has found application in the analysis of cardiac arrhythmia. We are
beginning to understand how complex systems—for example, those in which
fluid flow and chemical reactions are occurring simultaneously—sometimes be-
come intrinsically self-organized, sometimes exhibit large critical fluctuations,
sometimes become chaotic, and sometimes do all three of those things at the
same time.
Nonequilibrium physics has grown into a major enterprise, one that cannot
be described fully in this report. The committee has therefore selected a special
set of topics as illustrative examples of the themes and issues to emphasize. The
first of these topics is pattern formation and turbulence in fluid flow. The next
two are in the areas of processing and performance of structural materials, spe-
cifically, microstructural pattern formation in solidification and a group of topics
in solid mechanics: friction, fracture, granular materials, and polymers and adhe-
sives. The final section includes some brief remarks about nonequilibrium phe-
nomena in biology and in the quantum domain. Each of these topics, in different
ways, illustrates the four themes listed below:
1. Much of the most important progress in recent years has consisted simply
of recognizing that fundamental questions remain unanswered in the physics of

familiar situations. We regularly see turbulent fluids in the atmosphere and in

our kitchen sinks, as well as in a wide variety of less obvious but equally impor-
tant engineering applications. Snowflake-like solidification patterns are familiar
to us and are even more common than most of us realize because they occur on
microscopic scales within most structural metals and alloys. We deal with fric-
tion, fracture, and the mechanical performance of solid materials in essentially
every action that we take in our daily lives. Yet, as we shall point out in this
chapter, our basic scientific understanding of these phenomena remains incom-
plete and is inadequate for many practical purposes.
2. Nonequilibrium systems that form patterns or exhibit complex, perhaps
chaotic, behaviors are especially sensitive to small perturbations; thus their
detailed behavior may be extremely difficult to predict or control. As a general
rule, complex patterns form in simple systems when they undergo instabilities.
For example, smoothly flowing fluids become turbulent, or smooth solidification
fronts sprout branches. In a technical sense, the term “instability” is synonymous
with extreme sensitivity; a system is said to be “unstable” when it requires only
an infinitesimally small perturbation to cause a qualitative change in its behavior.
Turbulent eddies and dendritic branches are triggered by tiny fluctuations in their
surroundings, and their subsequent development is also controlled sensitively by
those fluctuations. It is in this sense that the properties of these systems are often
extremely difficult to predict. One of the biggest challenges to condensed-matter
and materials physics in the next decade may be to understand the intrinsic
limitations, if any, on the quantitative scientific analysis of such phenomena.
3. Progress in nonequilibrium physics will depend in many cases on our
ability to bridge length scales and timescales. For example, solidification is
controlled both by mechanisms of molecular attachment at crystal surfaces and
by heat diffusion across large ingots. Fracture is controlled both by breaking of
molecular bonds at crack tips and by the macroscopic flow of elastic energy in
solids. In general, we need to understand the interrelations between phenomena
at scales ranging from atomic and molecular all the way up to fully macroscopic.
4. Progress in nonequilibrium physics, as in all of condensed-matter and
materials physics, will depend on our ability to bridge cultures. We shall have to
understand the importance of, and the impediments facing, our efforts to bring
new science to bear on technology and to take advantage of new technologies to
advance basic science.
PATTERN FORMATION AND TURBULENCE IN FLUID DYNAMICS
Nonequilibrium Phenomena in Fluids

When a fluid system is driven far from mechanical or thermodynamic equi-
librium, it has a spontaneous tendency to form patterns and defects. Some ex-
amples are the spiral waves and ordered oscillations in reaction-diffusion sys-

tems; rolls, hexagons, and plumes in thermal convection of fluid layers; turbulent
“spots” in the transition from the laminar state to turbulence in a boundary layer;
and large-scale circulation patterns in the atmosphere. It is likely that, at least to
some extent, living organisms are the result of this tendency for nonequilibrium
systems to self-organize. This pattern-forming tendency owes its existence to
nonlinearities that dominate the dynamics under conditions of strong forcing.
Although patterns found in nonequilibrium systems are varied in character
and combine an astonishing labyrinth of order and disorder, they do share some
common features. For example, the details of pattern formation are generally
sensitive to small perturbations. In small systems, boundary conditions deter-
mine the positions and orientations of patterns. The nonlinearities in pattern-
forming systems often produce intermittency; that is, such systems may undergo
irregular, large excursions away from their most probable states.
It is only natural, then, to think that these common features might imply a
deeper layer of truth, and that there might exist a general theory of nonequilib-
rium phenomena. Such a theory, if it exists, is still outside our reach; but we have
made substantial progress in developing special theories for some particularly
simple cases. Examples include liquid-crystal hydrodynamics, Rayleigh-Benard
convection, Taylor-Couette flow, and fully developed turbulence in boundary
layers. The main advantage of studying simple-fluid systems, as opposed to
more complex-fluid systems such as those used in industrial processes, is that the
laws of motion for the simple fluids are well known. If there exist common
underlying principles, they will be most easily discovered in simpler systems.
Specific examples will continue to provide useful insights, and the methods of
analysis that they generate will find broad utility. What is unclear is whether a
deep general theory will emerge from the knowledge acquired by studying spe-
cial systems; whether nonequilibrium phenomena, like thermodynamic critical
phenomena, fall into a small number of universality classes; and whether a broad-
based understanding will eventually enable us to predict and control complex,
technologically important processes.
Pattern Formation
Consider the simple case of Rayleigh-Benard convection. When a fluid,
initially at rest between two horizontal plates, is heated from below, it experi-
ences a temperature gradient. For small gradients, the heat transfer from the
bottom to the top occurs purely by conduction—that is, by molecular collisions.
When the gradient exceeds a certain threshold, however, the conductive state
becomes unstable and yields to convective states involving bulk motion of the
fluid. If the system is confined so that the fluctuations are correlated across the
entire system, or if the system is modulated externally, the convective dynamics
is largely temporal rather than spatial in character; one then observes a variety of
universal properties associated with temporal chaos of low-dimensional systems.

Universality here pertains to quantitatively identical dynamics in apparently dis-

similar systems.
Most systems are loosely confined, or unconfined for all practical purposes,
and so the dynamics has a strong spatial complexion. This appears in the form of
cellular structures such as squares, hexagons, rolls, and traveling waves whose
properties depend on features such as boundary conditions or the strength of the
forcing. In principle, these features of “collective behavior” are fully described
by the Navier-Stokes equations. Unfortunately, the latter are rather complex and
cannot be used directly for studying the conformation and dynamics of patterns.
Much recent progress has come via the study of relatively simple, so-called
“amplitude equations” that accurately approximate the full Navier-Stokes equa-
tions near the onset of instability where the nonlinearity is weak.
The amplitude equations are closely related to the Ginzburg-Landau equa-
tions that describe the behavior of order parameters in transitions from one state
to another. They have been used successfully to describe major features of pat-
tern formation, including defects, that occur in weakly nonlinear regimes. For
systems where the initial instability is a traveling wave, as in binary mixtures, the
dynamics can be described by means of the complex Ginzburg-Landau equation.
This equation is rich in character; features such as “defect mediated turbulence”
also appear to be contained in it. However, not all of its facets have yet been
explored. Other complexities arise in spatially extended systems where, for
example, the phases of the patterns may vary slowly in time and space. Equations
for this kind of dynamics have been written and their outcome verified for special
cases where the basic patterns are known and their shapes do not change. Again,
much work remains to be done.
One of the grand unifying principles in equilibrium statistical mechanics is
the minimization of free energy. Much thought has been expended on possible
analogies in nonequilibrium phenomena. Although a suitable integral of the
amplitude function and its gradient serves as an approximate free energy in some
cases, this is not a viable procedure in general. A class of pattern formation
problems that has not been fully explored is the nucleation and growth of turbu-
lent “spots” in boundary layers (or “slugs” and “puffs” in pipe and channel
flows). A spot is a compact object of well-defined shape; it moves in the flow
direction at a specific speed; the flow within the spot is turbulent; and the distinc-
tion between its inside and outside is generally unambiguous. The spot preserves
its characteristic shape as it grows, and the growth rate increases as the Reynolds
number (a measure of the flow strength) grows beyond a critical value. A suit-
ably defined length scale seems to diverge at the critical Reynolds number. Al-
though there is a random element to the initiation of the spot in space and time,
morphological characteristics such as its shape and growth rates seem universal.
These and some other facets of turbulent spots bear superficial resemblance to
critical phenomena and to growth processes like diffusion-limited aggregation or
directed percolation. How to bring these similarities to bear quantitatively on the

formation of spots has eluded us so far. Although there is a large body of

engineering literature on this problem, very little of it is motivated by the more
general considerations of nonequilibrium physics.
Turbulence
More complexities develop as one increases the stress applied to a fluid
system at its boundaries, for example, by increasing the heat flux or the shear
rate. (“Increasing the stress” means increasing the Reynolds number.) Among
the complexities are the decay of the long-range order of the patterns, the devel-
opment of new length scales, and the appearance of a strong flux of energy across
the range of length scales (the “inertial range”) on which turbulent motion is
occurring. The scale range increases with the Reynolds number and is bounded,
on the one hand, by the characteristic size of the system (the “large scale”) and,
on the other, by the small “dissipation scale” at which viscous effects become
dominant. The flow is said to be fully turbulent when the scale range is large.
Well-developed turbulence has some interesting and important features. A
tracer substance such as a dye, when injected into a turbulent flow, is mixed
efficiently and diffused at unusually high rates; isosurfaces of the dye concentra-
tion are fractal; the small scales are spatially intermittent and amenable to
multifractal description and modeling; correlations and fluctuations are anoma-
lously large; and externally imposed perturbations decay slowly. These features
are characteristic of phenomena far from equilibrium.
A quantitative theory of turbulence is likely to be valuable in the study of
other nonequilibrium phenomena. This is why turbulence merits some attention
and discussion here; indeed, until the 1960s, fluid turbulence was the clearest
example of a phenomenon in which a large range of length scales are simulta-
neously important (see Box 4.1). The successful application of scaling, univer-
sality, and renormalization group theory to thermodynamic critical phenomena
has altered this situation, but turbulence still offers one of the cleanest examples
of scaling behavior in nonequilibrium physics.
Physicists generally like to focus on “universal” aspects of the phenomena
they are studying. The conventional wisdom in turbulence theory is that small-
scale turbulence possesses universal properties that are independent of specific
large-scale flows. However, the notion of absolute universality, initiated bril-
liantly by Kolmogorov and others, is not strictly valid for turbulence, let alone for
all nonequilibrium systems. Universality may pertain, at best, only to certain
scaling exponents. The universality of scaling exponents is a compelling no-
tion—one that clearly invites comparisons with other nonequilibrium problems—
and principal questions regarding them are just beginning to be resolved. There
are lingering impediments. For example, at present there is no theory in turbu-
lence for effects of finite Reynolds number or finite shear. Despite advances in
modern experimental methods, properties of turbulence continue to be probed

BOX 4.1 Length Scales in a Turbulent Jet
Figure 4.1.1 illustrates one essential feature of turbulent flows—namely, the

coexistence of many superimposed length scales. The present example is a tur-
bulent jet in which a small amount of fluorescent dye has been mixed. The dye
concentration has been mapped by the so-called “laser-induced fluorescence”
technique. Different scales of the dye concentration field have been extracted by
convolving the data with wavelets of different sizes. That is, from top left to bottom
right, we see pictures of the same flow pattern in which the size of the features
being resolved has been reduced by a factor of 2 from frame to frame. Note that,
the smaller the structure, the more string-like it becomes. There is no apparent
self-similarity and, in contrast to earlier ideas, individual structures do not become
more isotropic at smaller length scales. Note, however, that the anisotropy of
individual structures does not necessarily preclude statistical isotropy.
The jet shown here has a Reynolds number of about 4000. This is rather low,
and so the scale range is not large. In Earth’s atmosphere at a height of 30 m, the
scale range is about 105, yielding 1015 degrees of freedom in three dimensions. If
the equations of motion are to be solved explicitly on a computer, the memory
requirements grow roughly as the cube of the Reynolds number. This feature
limits the Reynolds numbers at which turbulent solutions can be obtained by
numerical techniques. There are also inherent complications such as sensitivity to
initial conditions, but the statistical averages are believed to be independent of them.
FIGURE 4.1.1 Depiction of the coexistence of many superimposed length scales.

[Reprinted with permission from R. Everson, L. Sirovich, and K.R. Sreenivasan,
“Wavelet analysis of the turbulent jet,” Physics Letters A 145, 314 (1990). Copy-
right © 1990 Elsevier Science.]

only partially at high Reynolds numbers, and quantities of theoretical interest can
be measured only approximately. A major advance in this regard is the use of
powerful computers to solve the equations of motion explicitly and thus elucidate
spatio-temporal details of turbulent solutions. The Reynolds numbers of the
numerical solutions are approaching the range of interest for addressing impor-
tant issues.
An interesting question is whether the coherence of the small-scale motion,
in the form of elongated and anisotropic vortex structures, is consistent with the
universal scaling presumed to exist in fully developed turbulence. In an anisotro-
pic ferromagnet near its critical point, for example, the critical indices do not
depend on the magnitude of the anisotropy (although they are different for iso-
tropic and anisotropic cases). In turbulence, however, the critical indices may, in
some instances, depend on the magnitude of the anisotropy. The relation be-
tween scaling, which emphasizes the sameness of various scales, and structure,
which becomes better defined and topologically more anisotropic for larger am-
plitudes, is at present quite obscure.
In summary, the issues considered here are the changes occurring in a fluid
flow that is increasingly stressed at its boundary. The stresses may be applied by
mechanical, thermal, or other means. The changes include instabilities, bifurca-
tions, temporal chaos, pattern formation, phase modulations, defects, growth of
localized structures, interactions among dissimilar length scales and timescales,
universal and anomalous scaling, intermittency, anomalous transport, and the
like. These phenomena have strong similarities to those that are seen in other
nonequilibrium systems. If these similarities can be exploited intelligently, there
will be many new opportunities for understanding turbulence better. Conversely,
turbulence poses a rich variety of problems and has an array of tools of analysis
that should be useful to other branches of nonequilibrium physics.
Fluid turbulence is a difficult problem with a long history, but the pace of
progress has accelerated in recent years. Much of the recent progress is the result
of a powerful combination of modern experimental methods, computer simula-
tions, and analytical advances. The present picture of turbulence is generally
self-consistent despite lingering uncertainties, and recent advances have further
improved our qualitative and quantitative understanding. That the qualitative
understanding should impact practical and industrial problems is substantially an
article of faith; much remains to be bridged between the fundamental develop-
ments of recent years and practical problems of industrial relevance. To some
extent, this is a problem of bridging cultures. To a larger extent, however, this is
a reflection of the difficulties of strongly nonlinear problems that occur far from
equilibrium.
What matters in turbulence is the ability to quantify properly the mix of the
universal and system-specific aspects and to describe that mix economically.
Such an understanding will propel forward not merely the study of fluid turbu-
lence but the entire subject of nonequilibrium physics.

PROCESSING AND PERFORMANCE OF STRUCTURAL

MATERIALS: METALLURGICAL MICROSTRUCTURES
The nature of nonequilibrium physics in condensed-matter and materials
physics—its intellectual vitality, its technological potential, and some of the
difficulties it faces—is concisely illustrated by the history of our understanding
of dendritic solidification patterns and their relevance to the microstructural prop-
erties of metallic alloys. In more familiar terms, this is the “snowflake’’ problem.
Only in the past few years have we finally learned how these elegant dendritic
crystals emerge literally out of thin air, and why they occur with such diversity
that no two seem to be exactly alike.
Much of the research on dendritic crystal growth has been driven not only by
our natural curiosity about such phenomena, but also by the need to understand
and control metallurgical microstructures. The interior of a grain of a freshly
solidified alloy, when viewed under a microscope, often looks like a collection
of overly ambitious snowflakes. Each grain is formed by a dendritic (tree-like)
process in which a crystal of the primary composition grows out rapidly in a
cascade of branches and sidebranches, leaving solute-rich melt to solidify more
slowly in the interstices. The speed at which the dendrites grow and the regular-
ity and spacing of their sidebranches determine the observed microstructure
which, in turn, governs many of the properties of the solidified material such as
its mechanical strength and its response to heating and deformation.
One logical and possibly realistic goal for research in this area might be the
development of quantitative methods for predicting the metallurgical microstruc-
tures that emerge in the processing of industrial materials. An especially impor-
tant class of examples includes the materials used for high-temperature applica-
tions such as gas turbines and jet engines. It would be useful to be able to develop
predictive models for forging turbine disks, or for casting complex shapes such as
turbine blades, or for the vapor deposition processes used to apply thermal barrier
coatings to those blades. In principle, industrial laboratories could benefit greatly
if they were able to design such processes cheaply and quickly by computer
rather than by expensive, time-consuming trial-and-error methods. We now have
in hand some of the conceptual bases for such calculations, and our computa-
tional capabilities continue to grow exponentially. Let us ask, therefore, what
will be needed—what new experiments, new theory, new mathematics—in order
to write usefully predictive computer codes to design and control such manufac-
turing processes.
Because many of these processes involve dendritic crystal growth, we know
that one starting point must be an understanding of the dynamics of isolated,
freely growing dendrites. Box 4.2 describes some of the remarkable progress
made in the last few years. The free-dendrite problem is most easily defined by
reference to the xenon dendrite shown in the figure in Box 4.2, a pure single
crystal growing into its liquid phase. The speed at which the tip advances, the
radius of curvature of the tip, and the way in which the sidebranches emerge

behind the tip are all determined uniquely by the degree of undercooling—
that is, by the degree to which the liquid is colder than its freezing temperature.
The question is, How? (An equivalent problem is one in which the dendritic
behavior is controlled not by the temperature but by the degree of chemical
supersaturation.)
As described in Box 4.2, a rich understanding of the behavior of isolated
dendrites has been found in theories of morphological instability and the discov-
ery that very weak forces—crystalline anisotropy of surface energies, for ex-
ample, or even atomic-scale thermal fluctuations in some cases—can completely
control the patterns that emerge from these instabilities. These new conceptual
developments, however, still leave us very far from being able to predict metal-
lurgically relevant microstructures. Current simulations of casting, for example,
include heat flow and fluid convection in complex geometries but succeed in only
very rudimentary ways in coupling those effects to the formation of dendritic
microstructures.
Perhaps the most important theoretical challenge is a quantitative under-
standing of what is called the “mushy zone”—the region between the fully
formed solid and the molten fluid where the dendrites are forming and interact-
ing among themselves. Within this region, the thermal, chemical, and hydrody-
namic degrees of freedom of the system are all active. Even if each dendrite is
behaving according to the rules already discovered, it is doing so in an environ-
ment where the local growth conditions are determined by its neighboring
dendrites and their associated diffusion and flow fields. This behavior is al-
most certainly chaotic, and therefore most likely will have to be described in
probabilistic rather than deterministic terms. We know that the mushy zone has
its own collective instabilities that can produce fatal structural defects in the
solidified materials.
The situation in the real world is even more complicated. In many casting
processes, new dendrites nucleate at impurities throughout the molten fluid as it
cools. Thus these processes are highly sensitive to the purity of the materials.
Moreover, heterogeneous nucleation of this kind is extremely difficult to predict
or control, even under ideal conditions. Other complications arise from the fact
that, in welding, for example, the molten fluid itself is turbulent.
Can such behavior be modeled in a usefully predictive way? Can the rel-
evant dynamics be described with sufficient accuracy by some coarse-grained,
many-dendrite theory; or will there be such sensitivity to details and such a huge
variety of possibilities that this problem will forever be beyond our reach? And
even if we can make substantial progress, will we be able to translate our theoreti-
cal understanding into decision-making tools that will be applicable to real-life
manufacturing?
These questions regarding intrinsic limits of predictability are unavoidable.
Nevertheless, we should be able to do better than we can at present. We already
know enough about these systems to recognize that a coordinated experimental

BOX 4.2 The Free Dendrite Problem
Under most metallurgical processing situations, dendritic growth is controlled

by diffusion—either the diffusion of latent heat away from the growing solidification
front or the diffusion of chemical constituents toward and away from that front.
These diffusion effects very often lead to shape instabilities; small bumps grow out
into fingers because, like lightning rods, they concentrate the diffusive fluxes ahead
of them and therefore grow out more rapidly than a flat surface. The key to under-
standing pattern formation in such situations is understanding the nature of these
instabilities.
Today’s prevailing theory of free dendrites is generally known as the “solvability
theory’’ because it relates the determination of dendritic behavior to the question of
whether there exists a sensible solution for a certain diffusion-related equation that
contains a singular perturbation. The term “singular’’ means that the perturbation,
in this case the surface tension at the solidification front, completely changes the
mathematical nature of the problem whenever it appears, no matter how infinites-
imally weak it might be.
This theory has been worked out in detail for many relevant situations, such as
the xenon dendrite shown here (Figure 4.2.1). It predicts how pattern selection is
determined, not just by the surface tension (itself a very small correction in the
diffusion equations), but by the crystalline anisotropy of the surface tension—an
even weaker perturbation in this case. It further predicts that the sidebranches are
produced by secondary instabilities near the tip that are triggered by thermal noise
and amplified in special ways as they grow out along the sides of the primary
dendrite. The latter prediction is especially remarkable because it relates macro-
scopic features—sidebranches with spacings on the order of tens of microns—to
molecular fluctuations whose characteristic sizes are on the order of nanometers.
Each of those predictions has been tested in the xenon experiment, quantita-
tively and with no adjustable fitting parameters. They have also been checked in
less detail in experiments using other metallurgical analog materials. In addition,
and theoretical investigation of mushy-zone dynamics in relatively simple situa-

tions would yield useful new information.
Yet here is another example of today’s widening gap between fundamental
research and applied technology in the United States. Few if any materials
manufacturing companies in this country continue to support research in this
area, and most no longer even maintain technical staffs that could take advantage
of new developments. Some serious efforts are being made at government-
supported laboratories to remedy this situation, but the university-industry-
government consortia that exist in Europe and Asia do not exist here at present.
PROCESSING AND PERFORMANCE OF STRUCTURAL

MATERIALS: SOLID MECHANICS
Solid mechanics, by necessity, has been a very well studied part of engineer-
ing and the applied sciences. We depend on experts in this field to design

the theory has been checked in numerical studies that have probed its nontrivial
mathematical aspects. As a result, although we know that there must be other
cases (competing thermal and chemical effects, for example, or cases where the
anisotropy is large enough that it induces faceting), we now have reason to feel
confident that we understand at least some of the basic principles correctly.
FIGURE 4.2.1 Xenon dendrite (Courtesy of ETH, Switzerland.)
structures—buildings, automobiles, airplanes, connections in electronic devices,

and so on—that will be strong, safe, and reliable.
Although some of the basic principles of modern solid mechanics were
established by physicists (for example, the dislocation theory of plastic deforma-
tion in crystals), the field has developed largely outside of mainstream physics
throughout the last half of the twentieth century. The experts in solid mechanics
have been engineers, applied mathematicians, materials scientists, geologists,
and so on, but seldom physicists.
That situation is changing. In just the last few years, there has been a healthy
revival of interest in this area within the physics community, and interdiscipli-
nary activities have been expanding. Perhaps the most important reason for this
change is that many of the most challenging modern problems in solid mechanics
involve nonequilibrium phenomena and therefore pose novel fundamental ques-
tions. Another important reason is that, for the first time in history, we have the
experimental and computational tools needed to answer those questions.

Brittle and Ductile Solids

As an introduction to some of these issues, consider the distinction between
brittle and ductile solids. A brittle solid breaks when enough stress is applied to it,
whereas a ductile material deforms plastically. Remarkably, we do not yet have a
truly fundamental understanding of the distinctions between these two behaviors;
we do not even have a sharp definition of “brittleness” and “ductility.” The con-
ventional theory says that dislocations form and move more easily through ductile
materials than brittle ones, thus allowing deformations to occur in one case and
fracture in the other. But this picture is incomplete and far too simple.
One difficulty in the standard picture emerges when we realize that all solids
deform plastically under very high stresses, such as those in the neighborhood of
a crack tip. Those stresses, by definition, must be high enough to break the bonds
between neighboring molecules; thus they ought to be high enough to rearrange
the molecules and thus cause plastic deformations that blunt the tip or limit the
stresses in its neighborhood. How, then, can cracks propagate through any mate-
rial? Do some materials spontaneously harden in regions of concentrated stress?
If so, why? Or might they sometimes fail to deform plastically if the stresses
change too rapidly? These are fundamental nonequilibrium questions that lie at
the very heart of solid mechanics.
Another equally fundamental difficulty is that the concept of “dislocation” is
meaningful only for crystalline solids; but noncrystalline materials such as glasses
and amorphous metals can also be brittle or ductile. What is happening in such
systems? Materials scientists have speculated for many years about an amor-
phous analog of dislocation motion, but we do not yet have a clear idea of what
that might be, and we are very far from being able to describe such mechanisms
quantitatively.
In fact, we still have no satisfactory understanding of the equilibrium proper-
ties of the glassy state; we do not even know whether it makes sense to use the
term “thermodynamic equilibrium” for such systems (see Box 4.3). Perhaps
glassy materials exist only as long-lived metastable or unstable states. If so,
where do they fit into our classification of solid-like materials? What language
do we use to describe their properties? Questions of this kind will become even
more urgent and difficult when, later in this chapter, we talk about granular
materials, biomaterials, materials in constrained geometries, or a variety of other
states of matter whose unconventional mechanical properties have yet to be ex-
plored and understood.
Instabilities in Dynamic Fracture

The field of fracture mechanics is among the most elegant and important in
all of the engineering sciences. In the last several decades, its practitioners have
developed powerful mathematical theorems and numerical algorithms that permit

BOX 4.3 Glassy States of Matter
It is quite remarkable that, despite literally centuries of scientific study, we still

do not have a fundamental understanding of glassy states of matter. This gap in
our knowledge looks even more remarkable when we realize that the category of
glassy materials—i.e., amorphous, noncrystalline solids, includes a very large frac-
tion of the substances that we encounter in everyday life. It includes window glass,
of course, and metallic glasses; and it includes many polymeric materials. Indeed,
very many simple substances—even ice—can exist with great stability in glassy
states. Condensed-matter physicists accurately use the term “glass” to describe
yet other strongly disordered systems. For example, “spin glasses” are magnetic
systems in which the interactions between the atomic spins are randomly distribut-
ed in sign, thus frustrating any tendency toward long-range order. The term “vor-
tex glass” refers to the tangle of field-carrying vortices that occurs in certain kinds
of superconductors.
For ordinary practical purposes, glassy materials become solids when cooled
below their so-called “glass temperatures.” They acquire immeasurably large vis-
cosities and they support shear stresses. The uncertainties are whether these
materials might continue to behave like liquids if only we could measure their prop-
erties over sufficiently long times or whether, on the other hand, this solid-like
behavior is characteristic of some new, intrinsically nonliquid state. This is not an
academic question. If we need to predict the structural or thermal properties of
amorphous materials, then we need to know what fundamental concepts are
relevant.
A great deal of progress has been made in the study of glassy materials during
the last decade or so. That progress has consisted of many new phenomenolog-
ical insights about a wide variety of different kinds of glasses and also some care-
ful new experiments that seem to point to the need for unconventional descriptions
of the ways in which molecules move and interact in glassy systems. In addition to
new understanding of the behavior of glasses themselves, the concepts that have
emerged in these investigations have generated novel ideas in fields as far from
condensed-matter physics as numerical mathematics and psychology. “Simulated
annealing,” for example, is a powerful numerical strategy for solving optimization
problems. It is based on a model of how a glass-forming material finds its state of
(near) equilibrium when it is cooled at a controlled rate through its glass tempera-
ture. “Neural network” models of associative memory originally were developed in
conjunction with studies of the properties of spin glasses with different kinds of
couplings between the spins. It seems likely that this deep and subtle field of
research will continue to generate new concepts of far-reaching impact.
them to compute stress distributions and failure criteria for highly complex solid
objects. With the help of modern computers, they are now able to predict with
confidence the mechanical properties of structural materials in a wide variety of
engineering applications.
Almost all of this progress, however, pertains to static—or very nearly
static—phenomena. Roughly speaking, conventional fracture mechanics has been
concerned primarily with predicting when materials will break and much less

with understanding what happens after failure occurs. The latter topic, “fracture
dynamics,” remains largely unexplored. It is fundamentally more challenging
than its static counterpart because it involves very deep issues in nonequilibrium
physics. Some of the most important outstanding questions are, How fast do
cracks move? What mechanisms limit their growth? How is energy dissipated in
fracture? What determines the various kinds of fracture patterns that we see in
nature?
One of the most important recent developments in fracture dynamics has
been the experimental demonstration that fast brittle cracks undergo material-
specific instabilities (see Figure 4.1). Fracture surfaces frequently are rough;
they may even be fractal. We now know that this roughness often occurs because
fast cracks are unstable with respect to bending away from their directions of
propagation or dissipating energy in the form of tip-splittings or sidebranches.
High-speed fracture is frequently a complex, chaotic, pattern forming process.
But instability is not a universal phenomenon. Since our ancestors first made
stone tools and later learned how to “cut” diamonds, it has been clear that sharp,
smooth fracture surfaces can be made by producing cleavage cracks in glassy or
crystalline solids. Apparently the trajectories of those cracks are stable.
FIGURE 4.1 Unstable fracture in a polymeric glass. This figure illustrates an experiment
in which a crack was observed with high precision as it moved along the center line of a
long strip of the polymer. (a) The graph of crack speed versus crack length. We see that
the initial crack in the unstressed sample was about 2 cm long. The stress applied to
the sample was increased until the crack suddenly started moving at a speed of about 200
m/s. The crack then accelerated smoothly up to a critical speed of about 400 m/s, at
which point an instability occurred that shows up on the graph as a rapid and irregular
oscillation of the crack speed. (b) Photograph of the fracture surface left by the unstable
crack. The front face is the fracture surface itself, with visible roughness on the scale of
0.1 mm. The top and right faces show that the instability also generated sidebranching
cracks and subsurface damage as the main crack moved through the system. (Courtesy of
University of Texas, Austin.)

Despite literally thousands of years of familiarity with these phenomena, we

still do not know what mechanisms control fracture stability. There exist some
candidate ideas, a few of which have yet to be tested; but there is as yet no theory
that is sufficiently plausible and well developed that it can serve as a guide to
experiment. One hint, known for about 30 years, is that the stresses in the
neighborhood of a crack tip moving at an appreciable fraction of the speed of
sound transform in a way that might cause bending. But this observation does not
address crucial questions pertaining to the dynamics of deformation and deco-
hesion near the crack tip, which must surely be relevant. The situation is further
complicated by the lack of a good theory of ductile yielding in situations where
stresses and strains are varying rapidly in both space and time.
In some respects, the present state of the theory of dynamic fracture re-
sembles that of dendrite theory almost half a century ago, before scientists had
identified the diffusive instability that underlies pattern formation in crystal
growth. To be sure, elastodynamics, plasticity, and decohesion in solids are
much more complex phenomena than diffusion. Also, it is quite possible that
there are many qualitatively different mechanisms that cause instability in frac-
ture. Perhaps this additional complexity explains why progress has been so slow
in this field. With modern tools and interdisciplinary modes of research, we
should be able to do better in the future.
Polymers and Adhesives

As discussed elsewhere in this report, an increasing fraction of the structural
materials used in modern technological applications are polymers or polymeric
composites. Nonequilibrium phenomena are involved both in the chemical and
thermal processing of these materials and in the way they respond to stresses
during use. These materials occur both as structural elements by themselves and
as the adhesives that bind different kinds of structural components in complex
applications.
Many structural polymeric materials are alloys of two immiscible polymers,
consisting typically of micron-sized droplets of one polymer dispersed in a ma-
trix of another. The mechanical behavior of such a composite is not some simple
average of the properties of its constituents. Rather, it depends crucially on the
shapes of the droplets and the properties of the interfaces between the droplets
and the matrix. Common examples are rubber-toughened glassy polymers used
to produce materials that resist high-speed impact damage and, in recent applica-
tions, three-phase blends consisting of one rubbery, one glassy, and one semi-
crystalline phase. Control of both the particle morphology and the fracture tough-
ness of the internal interfaces depends on so-called “compatibilizers,” copolymers
usually produced in situ by reaction during a mixing flow in the molten state.
Besides promoting the breakup of particles into a fine dispersion by their action

as polymeric surfactants and inhibiting particle coarsening by preventing coales-

cence, these compatibilizers help strengthen the interfaces between the phases.
Some progress has been made in understanding how these connectors work,
in large part because we now have instrumental probes that allow us to see what
is happening on submicron length scales or smaller. Techniques for using co-
polymers to strengthen interfaces between immiscible glassy polymers are now
fairly well established. However, it is still far from clear how to ensure entangle-
ment between polymers, and thus achieve fracture toughness, at interfaces with-
out connectors. The rules for strengthening interfaces involving semicrystalline
polymers are especially important for practical purposes but as yet remain undis-
covered. Consider polyethylene, the most common semicrystalline polymer, as
an example. Outstanding questions include, How long do polyethylene connec-
tors at an interface have to be to allow a zone of plastic deformation to form ahead
of a crack tip? If parts of such connectors are incorporated into crystals, is that
sufficient to lock them into place, or do they have to be both entangled and run
through the adjacent crystals for effective anchoring? What role does crystalliza-
tion play in the strengthening or weakening of such interfaces? Such evidence as
exists suggests that the influence of crystallization is significant. Do the answers
to the above questions depend on crack growth rate?
Most adhesives are polymeric, and these play increasingly significant roles
in a wide variety of technologies. Adhesives span the range from the very rigid
materials used in structural applications to very soft solids such as the pressure-
sensitive adhesives used in adhesive tape. In all cases, the performance of the
adhesive joint is determined by a complex interplay between the bulk mechanical
properties of the participating materials, including the adhesive itself, and the
detailed microstructural features of the interface. As in the case of the polymer
alloys, these molecular-scale features are becoming accessible to physical probes
such as secondary-ion-mass spectrometry, ion-beam analysis, and neutron reflec-
tometry. Thus, while adhesives traditionally have been developed by time-
consuming, empirical approaches, the prospect now exists for rational design
based on molecular-scale information.
Friction
Another classic part of materials research that is enjoying a resurgence of
interest among physicists is the science of friction. This topic has much in
common with dynamic fracture and adhesion. Two interacting solid surfaces
sliding past each other look in many ways like a dynamic shear crack. Mecha-
nisms such as cohesion and decohesion, energy dissipation, elastic deformation,
and so on are all relevant. But friction is an even larger and more complex topic
than fracture because it occurs in such a wide variety of circumstances and,
apparently, with an equally wide variety of underlying physical mechanisms.
The conventional goal of research on this topic is to determine frictional

forces as functions of the relative state of motion of two solid surfaces and the
stress holding the surfaces in contact with each other. Real friction, however, is
far more interesting and complex than this conventional statement would make it
seem.
Much of the recent progress in this area has been based on novel techniques
for visualizing the microscopic processes that take place during friction-con-
trolled sliding. Several atomic-scale probe microscopies have been used, as well
as some relatively simple and direct methods for following the motions of larger
features such as contact points and asperities. Numerical simulations, especially
via molecular dynamics, are now beginning to provide very valuable insights;
and good use also is being made of analog systems for making accurate observa-
tions of slipping events. A recent example of the latter technique involves layers
of carefully characterized granular substances confined between sliding plates.
Friction problems fall very roughly into three different categories: friction
between molecularly flat crystalline surfaces, friction between deformable rough
surfaces, and, in a very general sense, lubricated friction—that is, friction con-
trolled by the dynamic behavior of substances constrained to move between the
surfaces that are sliding across one another. In the first of these categories, the
clean crystalline surfaces, it is possible to make plausible models that involve
only atomic-scale degrees of freedom. Although such models still must include
assumptions about irreversible behavior, they are relatively well posed and, in
some cases, they are now beginning to produce credible agreement between
theory and experiment.
The other two categories of friction problems are fundamentally more chal-
lenging because they involve two or more widely separated length scales and
timescales. They may also be of broader practical importance.
In dry friction between polycrystalline, noncrystalline, or otherwise imper-
fect surfaces, the actual area of contact is much smaller than the nominal area of
the surfaces. The behavior of the small contact regions is crucial in determining
frictional forces and dissipation rates, but there is as yet no clear understanding of
the physical mechanisms that occur there. The problem seems to have issues in
common with fracture; the behavior is governed by cohesion and decohesion at
atomic-scale contacts that are strongly coupled to larger-scale elastic and plastic
modes of deformation. One useful way of dealing with systems of this kind is to
describe them not just by the relative positions and speeds of the sliding surfaces
but also by “state variables” that might represent, for example, the density and
strength of the contacts, and that obey equations of motion of their own. Such
“rate and state dependent” friction laws have been developed especially by
seismologists.
The ostensibly most complex problems in this field are those in which a
“lubricant”—that is, some extraneous substance—is present in the space sepa-
rating the sliding surfaces and transmits the frictional forces from one surface
to the other. In some of the most interesting recent experiments, the lubricant

is confined to a very small region, just a few molecular diameters across, and
thus its properties—especially under shear—may be quite different from those
of the same substance in bulk. Now the use of state variables is absolutely
essential. The lubricant may respond to changes in the shear rate by changing
its state, perhaps from liquid-like to solid-like, and such variations may occur
on many different space scales and timescales. The challenge is to identify
the essential degrees of freedom for these complex systems and to under-
stand the interrelations between the relevant microscopic and macroscopic
phenomena.
One of the most interesting and characteristic kinds of behavior seen in
friction experiments is stick-slip motion. In many circumstances, surfaces in
contact with one another will stick together until the applied shear stress reaches
some threshold, and then will slip past each other in accord with a rate-dependent
friction law until, under the influence of external forces perhaps, they come to
rest and restick. Familiar examples include squeaky door hinges and the motion
of a violin string driven by a bow.
It is easy to imagine how stick-slip motion can occur at a localized asperity,
that is, at a point where irregularities on opposite surfaces are attached to each
other via contact forces or molecular bonds. Slipping begins when the bond
breaks and stops when a new bond is established. On macroscopic scales, friction-
limited slipping may be the average of very many uncorrelated microscopic stick-
slip events. Macroscopic motions also may have a stick-slip character, as in the
case of the squeaky hinge. Such behavior occurs when the combined action
of dynamic friction and external loading induces some kind of mechanical
instability.
One interdisciplinary research topic that combines many of these ingredi-
ents—stick-slip friction plus fracture—is earthquake dynamics. Earthquakes, by
definition, are stick-slip events. They are triggered when some piece of a fault is
brought to its slipping threshold by the tectonic forces in the Earth’s crust. They
have the additional features that they occur on large length scales and have an
extremely broad range of sizes, even on single fault segments. Both physicists
and seismologists have been interested recently in the discovery that models of
earthquake faults consisting simply of elastically coupled stick-slip slider blocks
are deterministically chaotic systems that exhibit some of the characteristic be-
havior of real faults. Of course, these models do not account for the geometric
complexity of real seismic phenomena; but the qualitative picture that they pro-
vide, in which large events occur intermittently as cascades of small events, is at
the least an intriguing caricature of many kinds of self-organized phenomena. It
might even prove to be useful in seismology.

Granular Materials
Granular substances such as sand provide an especially clear example of a
familiar class of materials whose properties have yet to be understood from a
fundamental scientific point of view. These materials have been studied empiri-
cally for centuries in civil engineering, geology, soil mechanics, etc., because
they are essential ingredients in a wide variety of natural phenomena and have
many practical applications. But we do not know how to answer some of the
most basic questions about their behavior.
There are several clear distinctions between granular materials and the other,
superficially comparable, many-body systems that are more familiar to physi-
cists. Because they have huge numbers of degrees of freedom, they clearly need
to be understood in statistical terms. However, individual grains of sand are
enormously more massive than atoms or even macromolecules; thus thermal
kinetic energy is irrelevant to them. On the other hand, these grains also have
infinitely many internal degrees of freedom; thus they may—or may not—be
highly inelastic in their interactions with each other or with other objects. They
also may—or may not—have irregular shapes; arrays of many grains may achieve
mechanical equilibrium in a wide variety of configurations and packings. It
seems, therefore, that the concept of entropy must be relevant. We shall need
some way of deciding which are the statistically most probable states under
various constraints. But is there any analog of temperature or internal energy?
What other quantities might be necessary for describing the states of these
substances?
The questions become even more interesting when we consider the analogs
of nonequilibrium properties for granular materials. What happens to sand when
it is made to vibrate? Or when it is exposed to shear stresses? In some circum-
stances it behaves like a solid; close-packed sand can support limited shear
stresses. In other circumstances—strong shaking in an earthquake, for example—
it flows like a liquid. In yet other circumstances, granular materials behave in
ways that we do not yet know how to characterize (see Figure 4.2). Their free
surfaces spontaneously form regular patterns when shaken in special ways; their
internal stresses organize themselves into chain-like structures under certain kinds
of loading; flow patterns sometimes look roughly like localized shear bands.
Granular materials are only the simplest examples of states of matter that are
unfamiliar and relatively unexplored from a fundamental point of view, yet ap-
pear in many ordinary circumstances. To change the granular system just a little,
we might consider cases in which the grains cohere to each other. If the coher-
ence is weak, such substances may behave like viscous fluids—wet sand or clay,
for example. If it is strong, then we have materials like concrete or sandstone
which, for the most part, behave like ordinary solids. They support shear stresses,
and they can be brittle or ductile in their failure modes. In both cases, however,

FIGURE 4.2 Localized standing wave in a vertically vibrated layer of 0.2 mm diameter
bronze balls. (Courtesy of Center for Nonlinear Dynamics, University of Texas, Austin.)
when we try to understand the nonequilibrium properties of these materials, we

find ourselves in uncharted territory.
We find ourselves even further afield when we consider the nonequilibrium
physics of yet more dynamically complex materials such as foams, or the colloi-
dal suspensions, gels, and so on discussed in Chapter 5. Foams, for example, are
close-packed collections of bubbles separated by fluid films. They may be simi-

lar in some respects to granular materials; their fluid-like properties may be

controlled by local rearrangements of the bubbles.
Such considerations lead us inevitably to think about the nonequilibrium
behavior of biological materials. Cellular membranes, for example, are double
layers of large phospholipid molecules (see Chapter 5). These membranes obvi-
ously have a high degree of structural integrity; they do not pull apart easily and
they resist bending. Yet the molecules rearrange themselves easily within the
layers, which behave in many ways like two-dimensional fluids. There has been
substantial progress in the last decade in understanding the properties of these
basic biological materials. But it is only very recently, with the advent of new
experimental techniques, that the outstanding questions in this immense field are
beginning to become well-posed problems in nonequilibrium materials physics.
Length Scales, Complexity, and Predictability

There is a growing consensus among seismologists that it is impossible, even
in principle, to predict earthquakes. By this, they mean that they may never be
able to tell us, say a month or a year in advance, that an earthquake will occur at
a certain time and place. They have good reasons to be optimistic that, with new
scientific techniques, they will be able to make increasingly accurate estimates of
seismic hazards; and they may even be able to identify some precursory phenom-
ena that, in special circumstances, are warnings of imminent seismic events. But
earthquake faults are extremely complex, unstable, dynamical systems. When
near their slipping thresholds, they are highly sensitive to everything from large-
scale motions of the Earth’s crust down to the detailed friction laws governing the
motions of rocks at the points where failure might occur. Even if we had an
arbitrarily large computer and a complete understanding of the physics at each of
the relevant length scales and timescales, it seems highly unlikely that we could
ever determine the state of such an immensely complex system with enough
accuracy to be able to make event-specific predictions.
Are there similar in-principle limitations in other areas of solid mechanics?
In the foreseeable future, we ought to be able to determine from first principles
the elastic-plastic response and fracture toughness for single-crystal copper or
silicon, or perhaps even for some amorphous materials. As we have seen, these
are challenging but potentially solvable problems. Is there any hope, however, of
being able to make such determinations for multicomponent, polycrystalline,
structural alloys, or for multiphase polymeric composites, and then go on to
predict how those materials will perform in service over extended periods of
time? Or are such predictions as difficult as predicting earthquakes?
As seen from the perspective of the last decade of the twentieth century, it
appears that the next decades of research in nonequilibrium solid mechanics
should be characterized by a diversity of goals and modes of inquiry. It seems
clear that we must continue to move in certain well-established and productive

directions—ab initio calculations of dislocation dynamics in crystals, for ex-

ample, or experimental tests of such theories using synchrotron radiation. The
results of those investigations should provide data and new insights that will be
essential for a wide range of related research and applications, and they should
point the way to new research in directions that we cannot now anticipate.
In pursuing these investigations, however, we must recognize that making
the transition from atomistic theories of single-crystal plasticity to engineering
design of large-scale, complex, structural materials is not just a matter of building
bigger computers. We are almost certain to find new physics problems that need
to be solved at each of the many stages of this process. If the analogy of
earthquake prediction is accurate, then many of these problems will have to be
solved in ways that are not now familiar to us.
FURTHER PROSPECTS FOR THE FUTURE
Nonequilibrium Phenomena in the Quantum Domain

Modern technological advances in mesoscopic and atomic systems, described
elsewhere in this report, have made it imperative that we extend the study of
nonequilibrium phenomena to the quantum domain. The inclusion of quantum
mechanics makes an already difficult task even more difficult. In addition to
having to understand which microscopic details are relevant to observed macro-
scopic effects, quantum mechanics forces us to consider the idea of “coherence,”
that is, the degree to which quantum mechanical wavefunctions preserve not just
their amplitudes, but also their phases during dynamical processes. We have to
think carefully about the physical meanings of both classical statistical fluctua-
tions and quantum uncertainties. Not only do we have only partial information
about the relative probabilities of various atomic or electronic configurations, but
now we must take into account that we have only partial information about the
quantum phases.
Such considerations become yet more challenging when we consider the
problem of “quantum chaos”—the quantum mechanics of systems whose classi-
cal behavior is chaotic. In classically chaotic systems, we lose predictability as
the system evolves in time. What happens to such systems in the quantum
domain? Until just a few years ago, such a question seemed to be more impor-
tant philosophically than practically; but that situation has changed dramatically
with recent developments in mesoscopic physics. The electronic orbits in artifi-
cally structured nanosystems are often chaotic, and the control of these systems is
now so precise that the electronic states can remain coherent long enough for the
chaotic behavior to be relevant. Thus, what had previously been an abstract
problem in quantum measurement theory is now becoming a practical problem in
the design of advanced electronic devices.
An even more advanced example of the growing importance of quantum

dynamics in nonequilibrium phenomena is the current effort to develop quantum

computers. Here, as in the mesoscopic devices, we are dealing with systems far
from equilibrium coupled to an external environment and a “classical” measure-
ment apparatus. But, in this case, the whole concept depends on the possibility of
maintaining systems with many degrees of freedom in quantum mechanically
coherent states for times long enough actually to perform useful computations.
Related questions have been raised by the production of Bose-Einstein conden-
sates by evaporative cooling in atom traps. We are only beginning to understand
how to describe the dynamics of the formation of a coherent condensate in a
quasi-isolated system driven out of equilibrium by evaporative cooling.
Yet another example of the importance of dissipation and decoherence can
be found in the study of quantum critical phenomena such as the metal-insulator
transition. The dynamics of critical phenomena are often best studied using both
linear and nonlinear response to applied external probe fields. It is often the case
that “external” dissipation (due to phonons, for example) is irrelevant to the
equilibrium-critical behavior because the effective electron-phonon coupling
vanishes at low temperatures. However, this coupling can be “dangerously ir-
relevant” to the nonlinear transport because the external dissipation is the only
mechanism available to carry away the Joule heat. Hence, the less relevant the
phonons are to the equilibrium properties, the larger the bottleneck they represent
for energy dissipation in the nonequilibrium case. This can lead in some cases to
a singular temperature rise that obscures the underlying singular response of the
quantum critical fluctuations.
In short, there continues to be a host of deep and largely unresolved philo-
sophical questions in quantum measurement theory, forced on us by the devel-
opment of systems at the interface between the quantum and classical domains.
These questions may well be of growing practical importance in the next
decade.
Nonequilibrium Phenomena in Biology

Living systems are, by definition, in states that are far from thermodynamic
equilibrium. They are very different from any of the examples that we have
discussed so far, however. The most obvious difference is that they are highly
complex in their basic ingredients. Even the simplest biological materials are
composed of large multicomponent molecules that, individually, perform spe-
cific chemical and mechanical functions. More important, the selection of these
molecular constituents, and the ways in which they are assembled to make living
organisms, has taken place not according to some global optimizing principle of
the kind cherished by physicists, but rather according to the incremental and
perhaps chaotic processes of evolution. In dealing with systems of this kind,
physicists are learning to make basic changes in their research strategies.
Biology always has been a far more empirical and phenomenological science

than physics. Until very recently, there has been little room in biology for what
physicists call “theory.” The complex phenomena being observed and inter-
preted by biologists are taking place in systems whose fundamental properties are
not understood in the way we understand, for example, the physics of solid xenon
or the mechanical properties of grains of sand. Physicists usually have not had
the information they need for developing quantitative theories of biological phe-
nomena or the tools they need for testing those theories.
As described in more detail elsewhere in this report, that situation is now
beginning to change. Laser tweezers, atomic-force microscopes, and the like are
permitting us to see what individual molecules are actually doing during biologi-
cal processes. It is now possible, for example, to measure forces between cellular
membranes, to watch those membranes change their shapes in response to vari-
ous kinds of stimuli, or to see how proteins are formed and transported from one
place to another within cells. From the wealth of information just now becoming
available, we are beginning to understand that large biological molecules often
function as machines, absorbing energy from their chemical environments, dissi-
pating energy, and doing biologically useful work—all in accord with the basic
principles of nonequilibrium physics.
There seems little doubt that, so far, we are seeing only a very small part of
the huge world of biological materials and biophysical phenomena. The near-
term challenges for physicists working in these areas will be to identify those
biological systems that are ripe for quantitative investigation, to develop the
instruments and techniques for data analysis that will be needed to characterize
those systems, and to induce quantitative and predictive theories that can serve as
guides for further experimentation. Ultimately, the goal is to acquire a deep,
detailed understanding of the most extraordinary of all nonequilibrium phenom-
ena: life itself.

In summary, the committee draws the following conclusions regarding re-
cent developments and future directions for research in the nonequilibrium phys-
ics of condensed matter and materials.
1. Fluid dynamics, in addition to being relevant to a wide range of topics in

science and technology, remains a uniquely valuable laboratory for the study of
complex, nonequilibrium phenomena that emerge in relatively simple, easily
characterized systems.
2. Very significant progress has been made in the last decade in understand-
ing dendritic pattern formation in crystal growth. That progress, however, has yet
to have a major impact on efforts to predict and control solidification microstruc-
tures in industrially important materials. In part, the difficulty is that there
remain some challenging scientific problems to be solved, such as the problem of

the “mushy zone.” Another part of the difficulty is that there is relatively little
effort in this area in the United States, especially in industrial laboratories.
3. Recent developments in scientific instrumentation, especially atomic-
scale resolution in probe microscopy, plus extraordinary advances in computing
power, mean that long-standing problems in solid mechanics should now be
solvable. These are fundamentally challenging problems that involve non-
equilibrium statistical physics, nonlinear dynamics, and the like. They are also,
essentially without exception, directly relevant to modern technology. Among
those problems are the following:
a. The origin of dynamic instabilities in brittle fracture;
b. The fundamental distinction between brittleness and ductility in both
crystalline and amorphous solids;
c. The relation between molecular and mesoscopic structure and mechani-
cal properties, especially fracture toughness, in composite materials containing,
for example, varieties of polymeric constituents;
d. The relation between molecular and mesoscopic structure and the dy-
namics of friction in an extremely wide variety of situations, ranging from atomi-
cally flat surfaces interacting across molecularly thin layers of lubricants, to
tectonic plates interacting across earthquake faults; and
e. The relation between elementary interactions between grains and the
macroscopic mechanical behavior of granular materials.
4. In all probability, the next major frontier for research in nonequilibrium
physics will be in the area of biological materials and phenomena.
5. The same recent advances in scientific instrumentation and computing
power that portend both major advances and major surprises in nonequilibrium
materials research also force us to face fundamental issues in the physics of
complex systems. The problem of understanding the limits of predictability in
these systems must be addressed with every bit as much skill and objectivity as
the more familiar problems of understanding specific properties of specific sys-
tems. These issues lie, not just at the interface between different scientific disci-
plines, but also at the interface between science and public affairs.

5
Soft Condensed Matter:
Complex Fluids, Macromolecular Systems,
and Biological Systems
The vast territory of “soft” materials extends to paints, surfactants, porous

media, plastics, pharmaceuticals, coatings, ceramic precursors, minerals in sus-
pension, foodstuffs, textiles, proteins, fats, blood, and guitar strings. These mate-
rials are composed of colloids, gels, emulsions, micelles, foams, liquid crystals,
polymer melts, and other regimes of organization.
Biological physics, widely regarded as a major growth area for physics in the
next decades, is already closely allied with the study of macromolecules and
complex fluids—both active subfields of physics today. Labeling these as sepa-
rate fields is already arbitrary, and with good luck, separation will become impos-
sible. Chemical synthesis using biological methods will create huge classes of
materials amenable to physical experiments. Physical techniques and principles
will come to be applied to biological materials in unexpected ways.
This new domain of physics includes phenomena ranging from the precise
agility of liquid crystals to the lurches and shudders of sandpiles, from the resil-
ience of rubber to the self-organizing structure of soft surfaces, and from neuro-
muscular twitch to single-molecule mechanics.
A major difficulty in preparing this report was how to organize it into topics.
The word “interdisciplinary” inadequately denotes the new paths of learning,
distinct from those identified in earlier surveys and in university curricula. This
chapter discusses the following:
• The necessary combination of traditionally distinct fields of physics,

chemistry, and biology;
• The relentlessly increasing complexity of the materials examined;
194

SOFT CONDENSED MATTER 195
• The imaginative and exciting use of these materials; and

• The birth of new physics based on the theme of softness, malleability, and
fragility.
It is only through basic research, rather than goal-driven manipulations of

materials, that the essential connections between structure and function will
emerge. Practical applications, whose development is often easier to support,
will flow more easily once basic connections between structure and function have
been elaborated. This chapter argues for research that, at its best, celebrates the
complexities of the source material while taxing scientists’ ingenuity to knead
those complexities into tractable and relevant form.
There are abundant new industrial and medical products based on the soft-
ness and fluidity of materials. In fact, there have been uses from ancient times.
The softness of rubber was enjoyed in pre-Columbian American ballgames.
Emulsions and foams such as mousse and hollandaise sauce have long been used
in food preparation. Today’s new products are often discovered by ingenious
trial and error rather than by systematic theory and physical understanding (see
Box 5.1). The experience of practical innovation becomes a source of informa-
tion to learn the general features of these soft materials.
Understanding inevitably leads to practical use, but it can take decades to
progress from initial scientific query and curiosity to practical application. From
the invention of the transistor to the first useful integrated circuits took about 20
years. From the realization that DNA stores the genetic code to the beginnings of
a viable biotechnology industry took even longer.
With soft materials there are several unusual challenges to be recognized.
Our effort to see what is common and mutually constructive in working with
diverse soft materials immediately encounters cultural differences between physi-
cists, engineers, and biologists. Particularly at the intersection between biology
and physics, barriers to learning from each other are daunting. More than in any
other chapter of this report, the primary emphasis here is on educational needs
and opportunities for students and professionals. Following are a few examples
of learning opportunities that would cost little compared to the large potential
rewards:
• Summer schools,
• “Bilingual” survey texts and tutorials,
• Continuing education,
• Industry-academic visitation and collaboration,
• Grant programs to encourage truly basic research, and
• Graduate training in chemistry, physics, and biology.
Education must be deep as well as broad; it must obviate departmental bound-

aries. Nothing is more challenging than the creation of optimal modes of training

BOX 5.1 The Use of Milk Proteins
The world produces 5 × 1011 (500,000,000,000) liters of milk each day. Some
of this is directly consumed. A major part is processed or used to supply industrial
components. The milk protein casein, for example, 170 million pounds of it per
year in the United States, is put into bakery products, medicines, adhesives, pa-
per, low-fat coffee whiteners, and synthetic whipped dessert toppings.
Milk is a fragile mixture of fat and proteins in water. The structure and compo-
sition of fat globules, casein micelles, globular proteins, and lipoprotein particles
have the malleability to allow them to be made into hundreds of butter, cream,
yogurt, and cheese products. Their natural “complex fluid” properties are the kinds
that physicists are now beginning to recognize.
In the dairy industry, processing is often guided by ingenious trial and error.
The condensed-matter physics of soft matter can now have a chance to contribute
here. The gelation of fat globules and proteins, the distribution of gel networks,
and the size of nano-droplets of dispersions—which change the texture, taste,
and feel of food—are in fact physical properties amenable to systematic physical
investigation.
in fields that traditionally disdain each other. The complexities of materials are
themselves challenging enough to require no elaboration. New materials and
properties are now studied in physics departments; at the same time there is
increasing need for good physics in biology and engineering departments.
It is said that one of Isaac Newton’s greatest achievements was to extract
from Johannes Kepler’s notebooks the two Kepler Laws that showed Newton the
way to the discovery of gravity and the explanation of planetary motion. The
notebooks and their calculations were themselves inspired by Tycho Brahe’s
astronomical observations. There is an analogy here to modern soft-materials
research.
Biological systems present a set of successful molecular mechanisms that
create the living state. The path of trial and error to industrial success leaves a
valuable though diffuse trail of information. To pick out tractable essentials from
these data is a challenge that might lead to the discovery of what makes a system
live, today’s equivalent of Newton’s realization of gravity. The very mass of new
data creates its own challenges. Entire genomes of species, including our own,
are being mapped. Already one hears biologists speak of a “post-genomic era”
when new thinking will be needed to work with the new information and new
materials. Much of that thinking is expected to come from physicists.
Condensed-matter and materials physicists are used to thinking in terms of
emergent phenomena in large complex systems (see Chapter 3) and understand
that the simple paradigm that “structure determines function” can easily fail
because of collective phenomena. However, much of our experience is in rela-

tively simple systems with a great deal of symmetry (translation symmetry in

a ferromagnet, for example). We need to be looking for new deep concepts
in biology. These will necessarily require thorough knowledge of the details
of structure, but will, we hope, capture fundamental and general principles of
function.
The committee foresees possibilities for a shift to biologically based indus-
try, for advances in medicine, for insight to understand and simulate the thinking
process itself. The study of soft materials—such as complex fluids, macro-
molecules, colloidal suspensions, and biological preparations—is already
creating materials and processes with useful medical, industrial, and domestic
applications. So successful has physics been in medicine that the view of physics
is distorted by its success. Virtually all the sophisticated hardware used in medi-
cine is based on physical techniques and innovation of the kind described in this
report. Physical gadgets are saving so many lives that nonphysicists often believe
that gadgetry is the right place for physics in biology and medicine. Practical by-
products should not deflect attention from the central message that basic research
will ultimately bring much greater rewards.
COMPLEX FLUIDS
As though condensed fluids were not already sufficiently complex (see Box
5.2), condensed-matter physics has defined “complex fluids” in an effort to in-
vestigate the suspensions and solutions of large molecules. Here “large” begins
with the nanometer size of proteins and high polymers and extends to the micron-
plus dimensions of colloids, liquid crystals, and grains of sand. Particles of this
size organize themselves by steric collisions that create unexpected symmetries
and sensitivity to boundary surfaces. Their interactions are governed by electro-
static and solvation forces in forms not seen between smaller particles.
Liquid Crystals and Microemulsions

Most large asymmetric molecules, viruses, and lipids assemble spontane-
ously into ordered structures whose dimensions and macroscopic properties vary
dramatically with small changes in the conditions under which they are formed.
The statistical mechanics of these assemblies challenges the best theorists, and
measurements of macroscopic behavior and microscopic structure are a primary
activity in materials research. Since the early 1960s it has been known that what
underlies the phase diagrams of lipid-water mixtures is a set of lamellar, hexago-
nal, cubic lattices whose dimensions and symmetry change with temperature,
concentration, and the salts dissolved in the water phase.
Force measurements on lamellar stacks of sheet-like membranes reveal steric
repulsion resulting from the loss of thermal motion. The collisions between these
sheets can be hard bumps or soft encounters through spatially varying electro-

static, van der Waals, and hydration forces. The stability of a lamellar array
reflects the interplay of all these factors, together with the layer flexibility that
allows thermal undulation in the first place.
Similar reasoning holds for the packing of rod-like particles such as slightly
flexible linear polymers and some viral particles.
Pursuing a sudden opportunity to examine the huge number of new liquid-
crystal phases with natural and artificial materials in solution, theorists are
BOX 5.2 An Enduring Challenge: The Structure of Liquids
Formulation of a paradigm for the structure and transport properties of liquids

that is as compelling as periodicity is for crystals or “sparseness” is for gases
remains one of the grand challenges of science. The periodicity of the crystal
allows precise definitions of lattice excitations (phonons) and crystal defects (va-
cancies, dislocations), which let us understand in detail its thermodynamic proper-
ties, atomic transport, and deformation. Kinetic theory plays a similar role for
gases.
The complexity of the liquid structure arises from liquids being almost as dense
as crystals without the organizing principle of periodicity. The phase space of a
liquid contains many closely spaced energy levels with low barriers between them.
Computer simulations have produced many models of liquids, in excellent agree-
ment with the data from diffraction experiments. Nevertheless, a simple, unifying
picture of what gives rise to these structures and their associated transport behav-
ior is still missing.
One approach to achieving such a picture is the introduction of large numbers
of defects into a crystalline lattice. These models fail to make a specific link to the
experimental and computational features of the liquid structure and are thermody-
namically unsatisfactory. The alternative approach starts from the gas and gradu-
ally densifies it. Keeping track of the atoms, however, is a difficult task, and the
formalism required to account for the thermodynamic and transport properties be-
comes quite complex.
The closest we have come to formulating a simple paradigm for the liquid is the
“polytetrahedrality” of monatomic liquids, which goes back to a suggestion by F.C.
Frank. The densest local configuration of equal spheres is a tetrahedron. Close
packing of these tetrahedra around a common center leads to the formation of
(imperfect) icosahedra, which, through their fivefold symmetry, explain the lack of
periodicity. Although it is not possible to fill three-dimensional (3D) Euclidean
space with perfect tetrahedra, it is possible to make a perfect packing of tetrahedra
as the curved 3D surface of a four-dimensional polytope (see Figure 5.2.1). This
surface can be mapped onto 3D Euclidean space by the introduction of line de-
fects (disclinations), and the pair distribution function of the resulting structure is in
good agreement with experiment.
Although this approach comes closer than any to defining a structural para-
digm, more work is clearly needed, such as an extension to larger clusters and the
detailed study of the defect lines—their identification in computer models, their
systematic enumeration and statistical mechanics, and a demonstration of their
role in atomic diffusion and viscous flow.

The study of glasses is particularly useful here because they allow us to narrow
the energy range and hence the number of configurations of the liquid that need to
be considered. Metallic glasses are the prime experimental systems to test the
above paradigm because, unlike network-forming or organic glasses, the building
blocks of metallic glasses are single, spherically symmetrical atoms. All glasses
are intrinsically unstable; they are formed when the liquid goes out of equilibrium
when cooled below the glass transition temperature. As a result they can contin-
uously lower their free energy by a process of structural relaxation. Study of these
relaxation phenomena yields unique additional information about the structure and
defects of these glasses.
FIGURE 5.2.1 Two-dimensional projection of the 120 vertices of 720 nearest-

neighbor bonds of a four-dimensional polytetrahedral polytope. The perfect tetra-
hedral packing in this structure is the organizing principle of the structure of
simple liquids.
creating a new language of structure and symmetry. From the observed struc-
ture of these phases, experimentalists construct materials of controlled micro-
scopic structure, symmetry, density, and thermal conductivity. For example,
the fragile cubic lattice of a lipid-water microemulsion can be perfused by
water-soluble monomers that are then polymerized to create a hardened tortu-

ous network. These materials have extraordinarily high surface areas for their
volume and can be engineered to host chemical reactions that must progress on
surfaces.
Polymeric microemulsions—i.e., polymer equivalents of microemul-
sions—have been identified. Thus it may now be possible to make inexpensive
blends out of immiscible polymers and create particles whose sizes are tens
of nanometers. To control particle size precisely, we must understand the kinet-
ics of formation of these microemulsions out of their highly viscous polymer
components.
Liquid crystals of lipid and water can hold DNA or drugs to deliver them
through the lipids of the membranes that protect biological cells. Strategies are
being developed to transfect cells by delivering alien DNA across this protective
barrier, while protecting the DNA so as to allow it to become part of the target
cell’s genome.
Specialized domains in cell membranes that surround cells confine proteins
to force them into two-dimensional order. Physical theory and measurement of
lateral organization is already an important part of the search to explain the origin
and function of these functional regions.
Colloidal and Macromolecular Interactions

During the past 10 years there has been a burst of measurements of the forces
between colloids and macromolecules: polystyrene lattices, membrane bilayers,
and biological macromolecules such as DNA and collagen in solution. Optical
tweezers (see Figure 5.1), atomic-force microscopes, osmotic stress, electric and
magnetic fields, and immobilizing surfaces have been used to position nanom-
eter- to micrometer-size particles and measure the forces between them. At more
than nanometer separations, there are clearly defined electrostatic double layer
interactions; at smaller distances, solvation and the properties of the restructured
solvent often dominate intermolecular forces. Taken together, this body of mea-
surements introduces us to a new physics of the forces that act to organize
biological macromolecules and colloidal suspensions.
Having entered the realm of solvation forces, one is immediately confronted
by the embarrassing realization that many of them would not have been predicted
beforehand. Measured forces frequently look nothing like those predicted by the
computer simulations of biomolecules generated by programs used to predict
structure and design drugs. Double-layer electrostatic forces have been known
for decades and behave much as expected, even though qualitative discrepancies
between observation and expectation occasionally occur. Short-range, exponen-
tially varying forces at the nanometer range, usually dubbed “hydration forces,”
are still only formally described. A rigorous theory needs to recognize not only
the restructuring of the solvent in the face of the intrusive interface, but also the
way that the macromolecular surface has been engineered by nature to work into

(a) focused laser beam

r trapped sphere
water
glass slide
objective lens
(b) r(t)
FIGURE 5.1 The laser grip of optical tweezers makes it possible to position two micron-
sized spheres at a specified separation. When the laser is turned off, the spherical colloids
begin to diffuse. This diffusion is followed through computerized image analysis of the
spheres’ motions as seen through a light microscope. From the paths of the two colloids
after release, it is possible to infer the forces between the spheres. If they repel, the
spheres drift apart. Micron-sized spheres can be positioned at various locations to test the
consequence of proximity to surfaces. (Courtesy of the University of Chicago.)
the structure of the solvent. All the usual difficulties that impede understanding
of highly structured liquids are amplified by the minute details of macromolecu-
lar structure.
Still, the empirical facts speak for themselves, telling us how to think more
logically about molecular organization. New forms of colloidal crystals and
suspensions can be designed using measured forces. Computer algorithms can be

reconstructed to incorporate observed forces. Phase diagrams of assembling

molecules and colloids can goad far more careful thinking about the statistical
mechanics of liquids and liquid crystals.
For colloids, practical applications will probably come sooner than funda-
mental theories. New ways to position materials to effect force measurements are
also new ways to organize those materials for practical use. Colloidal systems
are particularly promising, in that there is already extensive experience in their
synthesis and commerce. The peculiarities of unexpected forces in response to
manipulation become new ways to make industrial materials such as paints,
slurries, and hitherto unimagined suspensions or colloidal gels.
We can expect that basic research will be increasingly able to point the way
to practical design. For example, it has been known for years that polymers
attached to colloidal particles can act as “bumpers” to prevent aggregation by
steric repulsion. Now we have measurements of forces between polymer layers
attached to solid surfaces or to bilayer membranes. Theories of polymer steric
repulsion can be critically tested. Application of polymers to surfaces can be
designed for desired properties.
Conversely, polymers that are in solution but unable to associate with col-
loids can act to create depletion forces that act to drive the colloids together.
These forces can be created, measured, and controlled by connecting known
properties of polymers to observations of how those polymers change colloidal
forces. Micron-size colloids can be concentrated into lattices of such good order
that they are beginning to be used to create optical devices that work by diffrac-
tion and absorption of light.
Polyelectrolytes
Polymers whose properties are dominated by their electrostatic charge are
instructive because of their solution properties, their ability to control ion activi-
ties, and their propensity to form liquid crystals. Among biopolymers, DNA has
been the most intensely studied from the viewpoints of liquid-crystal physics as
well as its “solution” properties in the cell. Intermolecular forces have been
measured in detail, both for molecules in simple salt solution and for those
organized by natural condensing agents. There has been extensive work aimed at
modeling the electrostatic potential around DNA.
Among artificial materials, there are several electrically charged or polariz-
able polymers, both natural and synthetic, that form networks controlled by
applied electric fields. Some of these materials are block copolymers, neutral as
well as charged, whose long-range order can be seen to emerge from mesogenic
organizing centers in the molecules themselves. Enhanced stiffness in polyelec-
trolytes can be achieved by neutralization with oppositely charged aliphatic
surfactant molecules. Modest electric fields can be particularly effective in
creating organization in liquid-crystalline polymers. Large-scale organization

can also be induced by shear processing these materials because, like most
mesomorphic materials, they readily align in shear flow.
The interplay between the various degrees of flexibility and freedom and the
electrostatic forces within and between molecules creates many modes of packing
and stimulates theories of molecular organization. The need is for complete theo-
ries that include real force potentials rather than analytically convenient approxima-
tions. Precise determination of phase structure from x-ray and neutron diffraction,
combined with direct measurement of the work of assembly, will be essential.
At the moment, DNA is probably the friendliest polyelectrolyte, natural or
synthetic, used to create well-defined liquid crystals in water. Soon there should
be other made-to-order polymers in practically any single length. Polydispersity,
a major nuisance when testing theories of polymer assembly, is not an impedi-
ment with uniformly engineered DNA. It may even be that the size regulation so
useful for fundamental studies will also make DNA and other precisely prepared
synthetic model compounds similarly useful for practical applications. Because
they are highly soluble in water, polyelectrolytes might come to replace organic
polymers, which must be dissolved in environmentally unsuitable solvents.
Polysaccharides
Although the substance of enormous industries (see Box 5.3), polysaccha-
rides have been relatively unappreciated by most polymer chemists and physi-
cists. Cellulose, whose biomass exceeds that of any other natural polymer, was
not even mentioned in the National Research Council’s 1994 survey of polymers.1
At present, modifications in chemistry and physical processing are creating new
research questions and many practical applications, from the design of new paper
currencies to the creation of industrial fibers to cosmetics to artificial food and
blood thickeners.
It has recently become possible to measure equations of state of several
polysaccharide systems, a development that should demand better theories of
polymer assembly. Considering the mass of polysaccharides in the world, their
economic and practical importance, and the excellent chemical and biochemi-
cal work already done, it is surprising that physical research has been so lim-
ited. Because polysaccharides are often polymers of repeating units, they would
seem to be an ideal material for physicists to study. There is a splendid oppor-
tunity here for instructive physics on materials far less complicated than the
more popular proteins. Their swelling properties, their viscous and elastic
capabilities, and their stability over a wide range of solution conditions and
temperatures are theoretically intriguing and technically enticing. There is
already the expectation of creating bacterial polyesters and biodegradable ther-
1Polymer Science and Engineering: The Shifting Research Frontiers, National Academy Press,
Washington, D.C. (1994).

BOX 5.3 Growth of the Use of Polysaccharides:

Xanthan, Guar, and Cellulose
The label on a bottle of salad dressing, a box of ice cream, a coffee whitener
reminds us of the various polysaccharides that we consume. Among these many
polymers of sugar are guar from seeds, carrageenan from seaweed, pectin from
fruits, and xanthan from the coats of microbes. These compounds are used as
thickeners and preservatives, often playing a role parallel to that played in natural
circumstances. Xanthan is so versatile, so stable in its physical properties in the
face of heating and mixing with salts that it is pumped into the ground to stimulate
the recovery of oil wells and into your stomach after giving food the right “mouth
feel.” The animal polysaccharide hyaluronic acid is a significant component in
cartilage and connective tissue; commercially extracted from animals, it is increas-
ingly used medically for the repair of joints and cartilage.
It is no surprise then that natural polymers, or slightly modified natural poly-
mers, are industrially popular. Several billion pounds of starches from plants are
used in the United States alone for processing paper and in sizing, binding, and
adhesive applications. Hundreds of millions of pounds of modified cellulose find
their way into foods as well as paper and construction materials.
Viscous and elastic properties make these polymers industrially valuable.
These are physical properties. Yet physics has paid surprisingly little attention to
polysaccharides and related polymers. With its new capabilities, soft-matter phys-
ics can be expected to recognize and to modify the behavior of these materials that
have traditionally enjoyed the attention mainly of chemists, colloid scientists, and
chemical engineers.
moplastics. The natural polysaccharides that coat some bacteria are able to
direct the precipitation of minerals dissolved in the surrounding solutions;
heroic hopes for deep-sea mining might be coupled to learning how tiny bacte-
ria collect minerals.
Taken in the context of polymer studies in general, there is the possibility to
study materials that have already been selected by nature for their physical prop-
erties. Most industrial use has been guided by trial and error rather than by
combination with systematic physical theory and experiment. In the food indus-
try particularly there are huge potential benefits.
MACROMOLECULES AND MACROMOLECULAR FILMS
Phase Separation and Ordering in Thin Polymer Films

Because diffusion is so slow in molten polymer systems, physicists have
been able to observe the very early stages of phase separation—stages in which
change is so slight that simplified, linear theories can be applied. It is possible to
see the importance of polymer chain length on the kinetics and evolution of chain

morphologies, the different classes of behavior approaching critical points, and

the effects of surfaces and interfaces on phase separation. Phenomena that can
only be observed in atomic or molecular films when they are, at most, 5-nm thick
can be seen in 500 nm thick polymer films. Because of this extra range, it has
been possible to see phase separations as a function of time and position from an
organizing surface. Patterned surfaces can be templates to create three-dimen-
sionally patterned films (see Box 5.4).
Structured films of synthetic and of natural polymers can be used as sub-
strates to host and guide the growth of biological tissues. New processing treat-
ments of surfaces for medical implants might follow from fundamental discover-
ies on thin polymer films.
New Macromolecular Materials

Dendritic and hyperbranched polymers have quite dense structures but nearly
monodisperse size distributions (from 2 to 50 nm). These macromolecules can be
tethered to surfaces to act as “bumps” to prevent the “stiction” of hard-disk drive
heads; they can also be used to separate active ions such as erbium in optical
amplifiers. The nature of the surface of these dense macromolecules, their be-
havior in solutions and melts, and their internal structure all have physical conse-
quences. Their compact, well-defined shape stops mutual interpenetration or
strong entanglement, which creates low-viscosity melts and solutions. Potential
applications include their use as highly reactive, low-viscosity components for
construction of thermosetting polymer networks. Spherical and wedge-shaped
“monodendrons” can be produced (see Box 5.5). Attached hydrophobic groups
create a variety of cylindrical crystal structures with ion-conducting channels.
The possibilities of design are so encouraging that we have begun to speak of
biomimetic polymers. The scale of the opportunities afforded can perhaps be
gauged by the degree to which planar macromolecular assemblies (i.e., self-
assembled monolayers) are currently being investigated by polymer physicists.
Flexible polymerized or “tethered” membranes are natural generalizations
of linear polymers. Examples include graphite oxide sheets, the “rag” structure
of MoS, and the spectrin skeleton of red blood cells. Theory predicts a remark-
able flat phase, with anomalous roughness and singular elastic constants, caused
by a delicate interplay between thermal fluctuations and the Gaussian curvature.
The behavior of defects such as dislocations in unpolymerized flexible mem-
branes (such as lipid bilayers) with local crystalline order is also remarkable.
Unlike crystalline films forced to be flat by a surface tension, it is energetically
favorable for these defects to buckle into the third dimension (see Figure 5.2).
The macroscopic result is a “hexatic” membrane with a finite dislocation density
at any low, but nonzero temperature, i.e., a membrane with zero shear modulus
but with extended bond orientational order and a continuously variable fractal
dimension.

BOX 5.4 Control of Phase Morphology
Films of phase-separated polymers can be forced to take on a microscopic

lamellar structure when the film is “capped” by stiff coating.
A mixture of the immiscible polymers polystyrene (PS) and polymethylmetha-
crylate (PMMA) in a bulk melt forms a disordered arrangement of large
(>1 µm), almost pure PS and PMMA phase domains. Remarkably, if a thin film of
a mixture of PS and PMMA on a silicon oxide (SiOx) substrate is quenched so that
phase separation is prevented, then capped with an additional layer of SiOx, and
finally heated to allow demixing to occur, a very regular pattern of the PS and
PMMA domains can result. A schematic of the domain structure through the film
thickness is shown (Figure 5.4.1).
The figure shows that there are many long, parallel phase-separated domains
with a well-defined periodicity within the plane of the film, necessarily accompa-
nied by a periodic deformation of the upper film surface. The periodicity scales
with the thickness of the polymer film and disappears if the SiOx capping layer is
very thick; in this case the film consists of a uniform, five-layer sandwich, SIOx/
PMMA/PS/PMMA/SiOx. The structure comes from a balance between the free
energy associated with forming the interfaces between PS- and PMMA-rich do-
mains and the free energy increase associated with the elastic bending of the
silicon oxide capping layer. These factors create both the lateral morphology ob-
served for small capping layer thickness and the transition to only five layers (SiOx/
PMMA/PS/PMMA/SiOx) as the capping layer thickness is increased.
A notable feature of many liquid crystals and macromolecular films is their ex-
traordinary sensitivity to their bounding surfaces. A change in surface tension or
surface stiffness can be felt even millimeters away from the surface. This kind of
sensitivity to outside influence is an unexpected tool for arranging molecules into
desired microscopic form.
SiOx
PMMA
PS P
S
PMMA
SiOx
PS
SiOx
PMMA
SiOx
FIGURE 5.4.1 Schematic of PS and PMMA domain structures. (Courtesy of the

University of Guelph.)

BOX 5.5 Dendrimers, Strictly Spherical Polymers
We usually think of polymers as a string of flexibly linked beads. It is possible,

though, to link together Y-shaped units. The pattern of regular branching creates
spherical dendrimers, whose precisely determined diameters are ~100 Å (Figure
5.5.1). These spheres can be coated with a variety of chemical groups so that
their microscopic surfaces can have different qualities. Surface chemistry con-
trols the way these tiny spheres move and pack under concentrated-solution
conditions.
The viscosity of such dendrimer fluids is much lower than that of normal poly-
mers, leading to novel applications. In dilute suspensions, chemically labeled den-
drimers can be directed to react specifically with desired sites. One possibility is
that single dendrimers, loaded with drugs, will release those drugs at the places to
which dendrimers have been directed to bind (Figure 5.5.2). Another is that partial
dendrimers, dendrons, with liquid-crystal elements will self-assemble into arrays of
cylinders with precisely tailored inner and outer surfaces. These cylinders may
find uses as engineered channels through cell membranes.
Because they can be engineered so reliably and because of their rigidly simple
spherical shape, dendrimers are a powerful research tool. The idealized models
used in many physical theories resemble the well-defined spherical structure of
dendrimers. In addition the structures of dendrimers can be systematically modi-
fied to test predictions of physical theories.
FIGURE 5.5.1 Single dendrimer. (Courtesy of the National Institute of Standards

and Technology.)

BOX 5.5 Continued
FIGURE 5.5.2 Single dendrimers (top) “packed” with drugs and (bottom) releas-
ing the drugs at specified binding sites. (Courtesy of the National Institute of
Standards and Technology.)

FIGURE 5.2 The crumpling of a membrane sheet. Perspective and side view of an
instantaneous configuration of a large tethered membrane composed of 4219 monomers.
[Reprinted with permission from F.F. Abraham and D.R. Nelson, “Diffraction from
polymerized membranes,” Science 249, 394 (1990). Copyright © 1990 American Asso-
ciation for the Advancement of Science.]
Associating polymers are molecules with hydrophilic backbones and two or

more associating hydrophobic groups (“stickers”) per chain. These polymers
have very unusual rheological properties because of the tendency of the associat-
ing groups to cluster and form transient networks at sufficiently high polymer
concentrations. Their dramatically altered solution elasticity and viscosity al-
lows applications as thickening agents and rheology modifiers.
Unfortunately, most systems have stickers that are randomly placed along
the chain; such associating polymers are poorly understood. New synthetic meth-
ods now allow us to prepare systematically varied molecules with specified num-
ber and location of stickers. Polyelectrolytes and polyampholytes, with similarly
daunting structural heterogeneity can now be more systematically produced. The
possibility of learning from the properties of these molecules leads naturally to
related phenomena, such as protein folding and the organization of polymer
systems of increasing but controlled “randomness.”
Polymers associated into gels will hold drugs whose diffusive release into the
body can be controlled by gel compactness. These gels can be placed in a particular

part of the body for local, directed, sustained drug release. Stable substrates of
synthetic and natural polymers create substrates for directed cell culture.
Structural Polymers: Controlling Properties of

New Polymers from Old Monomers
Polyolefins, so-called “commodity polymers” such as polyethylene and poly-
propylene, are produced in huge quantities by the petrochemical industry. Poly-
mer production for U.S. consumption alone is about 1011 pounds per year. This
is roughly equal to steel production in weight, but it is about seven times steel
production in volume. Polyolefins are nearly 60 percent of the total. These
polyolefins are cheap. Their chain architecture can be manipulated by relatively
crude methods that offer some control over branching and stereoregularity of the
chain. In the early 1990s, polymer chemists developed new transition metal
catalysts. These catalysts offered unprecedented freedom to copolymerize the
olefins with other monomers; they also allowed much tighter control over branch
content and stereoregularity. It is now possible to achieve properties for ethylene-
containing polymers that range from those of good elastomers (soft, with only a
very small fraction of tiny crystals to act as crosslinks) to highly crystalline (hard)
polymers. This wide range of properties can be achieved using a very cheap
monomer to make up most of the polymer. Great commercial and scientific
opportunities exist for polymer physicists to develop the relation between chain
architecture and the properties of these new materials.
For example, high-density (unbranched) polyethylene of high molecular
weight is used routinely for the socket of artificial hip joints. For this use it has
an elastic modulus of 103 GPa and a failure stress of only 50 MPa. The same
polyethylene, processed with solvent into a dilute gel, dried, and then drawn into
fibers, has an elastic modulus of 170 GPa and a failure stress of 3000 MPa along
the fiber direction. Processing methods such as fiber spinning, blow molding,
injection molding, extrusion, film blowing, solution casting (for adhesives and
coatings), and reactive blending subject the molten polymer or polymer solution
to a flow field that strongly distorts or aligns the molecular conformations. Such
processing is able to effect the final material properties after cooling, cross-
linking, or evaporation of solvent. Trial-and-error improvement in commercial
processing will be more efficient with better theories of polymer organization.
The most serious lack of knowledge concerns what determines the mechani-
cal properties of semicrystalline polymers and how they depend on flow history
and polymer architecture. Because ease of processing and final properties are
equally important attributes of a polymer, both melt rheology and final properties
need basic study. Studies in the 1970s did not emphasize the strong effects of
flow, which can reorganize the orientation of crystals and change crystallization
rates by orders of magnitude. Modern physical probes (e.g., small-angle neutron

and synchrotron x-ray scattering, infrared dichroism, and Raman spectroscopy)

could provide the tools to understand the transient effects of flow on the molecu-
lar conformation, crystallization, plastic deformation, and fracture.
Biological Connections
In contrast to synthetic polymers, which are composed of at most three
monomer types, normally arranged in random order, proteins are synthesized
according to a programmed sequence involving 20 kinds of monomer. They are
also produced to a precise length. Other classes of biopolymers, such as saccha-
rides and nucleic acids, are also very precisely specified compared with artificial
synthetics; even heterogeneity appears to be intentionally created. Polymer chem-
ists and molecular biologists have begun to collaborate to synthesize copolymers
with the same precise control of monomer sequence and chain length. The
challenge for polymer physicists, as precision-architecture polymers become
available, is to understand the link between architecture and polymer system
properties. Lured by the wide range of properties conveyed by biological macro-
molecules, from spider silk to the elastin of blood vessel walls, we expect to see
polymers with similarly remarkable properties emerge from these new syntheses.
Given the vast range of possibilities and the small initial quantities of each
polymer, it will be necessary to develop methods for rapid screening. Scanning-
probe microscopies have begun to be used to determine mechanical properties.
The aim is to be able to screen polymers for desired properties with the same
efficiency that is achieved for developing and producing biological polymers by
the natural checks of evolution and growth.
BIOLOGICAL SYSTEMS
Biological molecules are substances that have evolved to do highly specific
jobs on highly specific timescales. Physicists have had impressive success study-
ing the dynamics of macromolecules, particularly proteins. The mechanics of
single molecules can be measured and used to test theories of molecular confor-
mation. The measured energies of packing biopolymers inform us of the work
needed to package them into cells and viruses and challenge us to explain and
manipulate macroscopic properties.
It helps to distinguish incidental and essential physical properties of
biomolecules. For some materials, such as DNA, the cell works with physical
properties because it must. For others, such as RNAs, proteins, lipids, and
polysaccharides, molecular physical properties are themselves useful to the or-
ganism. There are bulk materials that provide structural stability to the cell or
organism. Happily, the language and concepts of lyotropic liquid-crystal physics
often meet the need to examine biological materials.

Two Traditions of Learning Must Merge to Allow Systematic Progress

For there to be the necessary crossover between biology and physics, there
will have to be a significant change in the way we teach ourselves and our
students to handle new materials and to respect the natural ways designed by
patient evolution. In the ideal scenario, physics students will learn the facts and
methods of biochemistry and molecular biology, and biology students will lose
their fear of and skepticism about talking with physicists (and perhaps even learn
some physics). In this area more than in any other addressed by this report,
progress will have to follow education. It will be built on a developed respect for
the very different thinking and experimental methods used by the two “sides.”
This point is far more pertinent than any review of particular systems or predic-
tion of future events. A 1996 study on self-assembling biological materials2
nicely summarizes the current state of learning about molecular organization and
provides many examples of doing physics with biomaterials, including:
• New paths for synthesis of peptide (proteinaceous) chains with practical

properties as well as properties that will be available to test physical models of
assembly;
• Spontaneously assembled surfactants, both natural and synthetic, with
their possibilities for structuring surfaces, hosting proteins or DNA or molecular
sensors, binding stabilizing polymers, and (again) creating structures amenable to
systematically developed theories of lipid assembly;
• Layered polymer systems that can act as sieves, scaffolds for growth and
hardening of nonorganic materials, and mechanically stabilizing films; and
• Gene therapy, in which physical methods might be used to design the
delivery and incorporation of new genes to be reproduced within the genome of
target cells.
The committee enthusiastically agrees with that study and will not repeat its
advice here. Rather, this section will provide more examples for both basic and
applied research. It will suggest possibilities for a physics of biological materials
in which physical thinking will be essential to the understanding of how biologi-
cal substances are designed to work in their native habitat. There are many
biological phenomena that traditionally or currently have been studied produc-
tively through physical thinking. Some examples are as follows:
• Protein-DNA and protein-protein interactions;

• Molecular motors and locomotion;
• Protein interaction, folding, and dynamics;
2National Research Council, Biomolecular Self-Assembling Materials: Scientific and Technologi-

cal Frontiers, National Academy Press, Washington, D.C. (1996).

• Photosynthesis and energy transfer; and

• Nerve action.
Physics and Structural Biology

If allotted text were in proportion to progress, the discussion of molecular
structure determination and structural biology would nearly fill this chapter.
Because of advances in physics, we now expect to know the structure of large
functional biological molecules in crystals and in solution to angstrom resolution.
Any thinking about functional mechanisms is expected to build on known struc-
tures. Although structure determination of proteins in solution is usually by
nuclear magnetic resonance (NMR) and is considered the province of chemists,
most structures are delineated by x-ray diffraction, whose procedures are pre-
dominantly the work of physicists. New sources—synchrotrons, free-electron
lasers, and high-power x-ray laboratory generators—together with better lenses
(e.g., optical fibers, multilayer optics, and single-capillary microbeams) and a
new generation of fluorescence and charge-coupled device detectors, offer the
possibility not only to determine structure but to observe several classes of mo-
lecular motion (see Figure 5.3).
Synchrotrons, neutron sources, laboratory x-ray generators, and NMR ma-
chines, with their ancillary detectors and computation algorithms, are practical
microscopes whose success can be measured in the number of publications in-
volving their use, number of students studying and using them, and numbers of
dollars expended on them. Increasingly precise molecular structures, frequently
with better than 1 Å resolution, are the product of strong light sources as well as
better handling of delicate materials. Bright synchrotron sources are especially
useful for time-resolved studies, in which snapshots of the structure can be taken
in small time increments to make it possible to study intermediate states during
kinetic processes such as protein folding, allosteric changes, and association or
dissociation. Observable time resolution can be as short as nanoseconds, with
about 0.1 ns expected soon. Here, as elsewhere in this report, we note the need to
nurture these facilities, improve them, and expand them so that they can continue
to meet and encourage the growing demand for revealing molecular structure,
assembly, and dynamics.
More urgent is that, while the world grows x-ray and NMR rich, it remains
neutron poor. Neutron and x-ray scattering, as well as NMR, allow us to study
the solution structure and dynamics of proteins and lipids and, perhaps, devise
industrial applications. Neutrons are sensitive to the positions of biologically
abundant light elements such as hydrogen, carbon, nitrogen, and oxygen. Be-
cause of this, with hydrogen-deuterium isotope substitution for contrast, small-
angle neutron scattering can provide unique information about the structure and
function of biological macromolecules, protein-nucleic acid or protein-lipid com-
plexes, and multi-subunit proteins. Neutron reflectivity has come to reveal fea-

FIGURE 5.3 Quick clicks. High-power x-ray sources provide successive pictures of
a protein process. [Reprinted with permission from W.A. Eaton, E.R. Henry, and
J. Hofrichter, “Nanosecond crystallographic snapshots of protein structural changes,”
Science 274, 1631 (1996). Copyright © 1996 American Association for the Advance-
ment of Science.]

tures of lipid monolayer and bilayer systems in aqueous environments, especially

for preparations that are difficult to crystallize. Reflectivity could similarly be
used to aid the biosensor industry by measuring the interactions between biologi-
cal components and organic or inorganic surfaces and to assist in the understand-
ing of nonspecific binding of proteins to surfaces. Dynamic processes in macro-
molecules can also be probed directly by neutron scattering because scattering
cross sections relate directly to oscillation frequencies and amplitudes of motion.
Optical microscopic techniques like fluorescent energy transfer are very useful
for obtaining information about proteins in vivo.
The need for good physics goes beyond mere observation. Today, about 35
years after the first hemoglobin structure, we still do not understand how that
protein changes its binding affinity for oxygen by assuming distinct allosteric
forms. Energy storage and energy flow through this nanometer-sized machine
still deserve the attention of molecular biologists and biophysicists, who still
have difficulty conversing.
Molecular Conformation and Protein Folding

The protein-folding problem attracts some of the best minds in biological
physics and statistical mechanics, but it will require much more effort to reach
satisfactory results. The question of how a linearly synthesized protein curls up
to its three-dimensional functional form continues to challenge and excite theo-
rists. The committee concurs with the eloquent review found in a recent National
Science Foundation study.3 Decades of witty measurements and imaginative
theories suggest that there can be some progress on this vexing problem, though
success in prediction is still elusive.
At this stage, it is clear that physicists have defined the language in which
folding is being examined. Cellular chaperone proteins, which wrap a protein
during its transformation from a linear chain to a three-dimensional structure, are
now believed to act by reversing random errors in folding. Their action is discussed
by biologists and physicists alike in terms of their kicking the protein out of snarls
that might otherwise trap it on its way to correct conformation. In this way, cellular
activity is thought to facilitate what is essentially a statistical physical process. The
tools to follow folding are increasingly based on physical techniques, particularly
high-power, high-speed x-ray scattering and spectroscopy.
Single-Molecule Motions and Mechanics

Laser tweezers allow one to hold the ends of linear molecules, particularly
double-helical DNA, to measure the force of extension in different solutions and
3Ken Dill, NSF Workshop on Interdisciplinary Macromolecular Science and Engineering (unpub-
lished), chaired by S.I. Stupp, University of Illinois at Urbana-Champaign, May 1997.

with association with other molecules. Suddenly it is possible to think about

single molecules as mechanical objects, on which physics can be performed
analogous to that done on macroscopic materials. Pipette aspiration allows
equivalent mechanical manipulations of membranes and bilayer vesicles (see
Box 5.6). The various moduli and deformabilities are just beginning to be codi-
fied and connected with the language of mechanics. The actual values of these
material properties still often surprise us and require new thinking.
Force microscopes can be used to break bonds, stretch molecules, or observe
spontaneous changes in macromolecular conformation. The breaking strengths
of important bonds, such as those between an antigen and an antibody, have been
observed using labeled polystyrene lattices. It has been found that the force
needed to break a bond is a monotonically decreasing function of the time that the
BOX 5.6 The “Spring” of a Bubble to

Tug Apart Large Molecules
Many biological processes depend on associations that require no chemical

bonds between molecules. Important examples are the association between anti-
gens and antibodies that allow cells to recognize alien matter or between integrins
that hold cells together. Even without being pulled apart, these molecules will
spontaneously come apart with time.
In a functioning cell, the precisely controlled duration of molecular association
can be more important than the strength of association. Cells create characteristic
times for many processes by controlling association times. The measurements
illustrated here show how times of association between a single pair of large mol-
ecules can be measured and instructively varied.
The trick is to pull on the molecules with a spring whose rate of tugging (force/
time) can be varied by 100,000,000 times (see Figure 5.6.1). Springs are made
from lipid bilayer vesicles or from red cells—effectively bubbles or microscopic
bags—to which associating molecules can be strongly attached. The bubble is
held by being gently sucked into a pipette whose suction pressure can be varied to
change tension in the vesicles.
To set up the measurement, a molecule on one bubble is brought near to an-
other bubble that contains the mating molecule; the bubbles stick at the point of
molecular contact. Then, by sucking on the pipette, stretching tension can be
transmitted to the two molecules. The time to breakage of the antigen/antibody
bond varies with varied rates of applied tension. From this measured time-
to-breakage, it is possible to infer the kind of contact that the molecules made and,
more important, to learn how the molecules create their important times of associ-
ation.
In this particular example, binding is observed between biotin and avidin. Dis-
sociation time ranges from 0.01 seconds to 100 seconds after the onset of a
ramped force. These gentle-tug measurements show how association lifetimes
can be exquisitely sensitive to small changes in applied structural forces. Physical
forces can regulate cellular events.

FIGURE 5.6.1 Using a bubble to tug apart large molecules. (Courtesy of Boston
University and the University of British Columbia.)
force is applied. This connection between time and strength, understandable in

terms of diffusion in the presence of a distance-dependent bonding potential,
reveals the dynamics of molecular association in the context of biological con-
trol. One can expect many single-molecule systems to be observed and analyzed
by probe microscopies to create a nanomechanics of molecular force and assem-
bly. There is already a small literature on the spectroscopy of single proteins
trapped in small spaces and illuminated by narrowly focused laser light.
Through the combined efforts of structural biologists, muscle biophysicists,
and statistical physicists, force generation in muscle and in transport within cells
is being seen as the combination of stochastic events and directed response. The
conversion of chemical reaction to directed physical action has posed a funda-

mental problem because of the different symmetries of biochemical cause and

physical effect. The puzzle is being solved through molecular tracking and
stochastic models. We can now expect the design of new mechanical transduc-
tion systems.
Single ionic channels show electrically detectable transitions between “open”
and “closed” configurations, whose probabilities are a function of solution condi-
tions as well as the applied transmembrane electric fields. There is now a possi-
bility of studying the dynamics of the channel molecules, as well as the solution
components that affect them, simply by watching singular molecular events over
very long times (see Figure 5.4). With channels, as with other proteins, it has
been recognized for almost 30 years that occupation of the different conductance
states follows simple Boltzmann statistics that allow us to relate the probabilities
of different states with the changes in energy needed to achieve them. In fact, for
a channel or other responsive molecule to sense changes in condition, it is neces-
sary that there be small differences, comparable to the thermal energy kT, in the
energies of differently functioning states.
FIGURE 5.4 A molecular Coulter counter. A bilayer membrane between two chambers
contains a single ionic channel of ~1 nm diameter. If a small molecule moves into an
open channel, the event is seen as a reduction in electric current. The duration of this
reduced current measures the residence time of the molecule diffusing into and out of the
channel. [Reprinted with permission from S.M. Bezrukov et al., “Counting polymers
moving through a single ion channel,” Nature 370, 279 (1994). Copyright © 1994 Nature.]

As a next step in time-resolved, small-current detection, it is possible to see

changes in the “open” state when single molecules enter and exit the chan-
nel. In this way it is possible to measure the statistics and dynamics of flexible
polymers as they move within the confines of a precisely defined single-
molecule structure.
What does it mean to watch the changes in a single molecule? Can one use
rigorous physics to describe these changes? Can this physics give us the ener-
gies and entropies that drive the system to different states? The answer seems
to be yes. Statistics, statistical mechanics, and functional control present a
perfect chance for physicists to bring their methods to help biologists. There
can be ready extrapolation to create practical devices, such as detectors and
computers, informed by biological designs, while single-molecule thinking in-
spires a new statistical mechanics of strongly coupled systems with enormous
fluctuations.
It is known now that many biological systems, from single ionic channels to
entire sensory systems, practice a kind of stochastic resonance. Physicists in the
1920s realized that adding some noise to a weak radio signal could improve
signal detection. Today’s physicists and biophysicists have succeeded in gener-
alizing those ideas, raising the hope that they might be applied to helping the
hearing-impaired.
Protein dynamics are a subject of intense interest. Binding of small mol-
ecules (see Figure 5.5) and changes in protein shape are essential properties that
physicists are in an excellent position to explain. Timescales are especially worth
recognizing here. Nerve signals, for example, occur on timescales of millisec-
onds, and different nerve channel proteins act at slightly different rates. Single
molecules remain “open” or “closed” for milliseconds. These millisecond-char-
acteristic times reveal the limits of computer simulation. Considering that these
simulations can cover only nanoseconds, there is still a factor of 106 to cover to
connect molecular dynamics computations with functionally interesting molecu-
lar times. The wit of physical theorists is the most promising way to compensate
for this daunting factor in computation.
Molecular Association
There is justified pride in modern polymer synthesis, by which stretches of
one or another kind of monomer allow polymers to associate in parts to multimo-
lecular arrays of specific symmetry, packing, and material properties. Yet this
kind of packing is rough compared to that of proteins or DNA, whose every
monomer has functional consequence. One mutation in one amino acid of an
antibody will qualitatively weaken its antigen-antibody binding strength and
specificity. One change out of six nucleic acids will spoil that sequence for
recognition by a protein that controls gene expression. Strength and specificity
are what count when an antigen or a hormone binds to a cell-surface receptor at

FIGURE 5.5 The right details: precision fit in the binding of an antigen to an antibody.
The antigen, a lysozyme protein nestles into an antibody. A groove in the antibody
matches itself tightly against a ridge in the lysozyme antigen. This ridge is formed by two
arginines, at positions 45 and 68. Such is the precision of the match that mutation of
Arg68 to a chemically similar Lysine reduces binding strength by a factor of 1000.
[Reprinted by permission from S. Chacko, E. Silverton, L. Kam-Morgan, S. Smith-Gill,
G.H. Cohen, and D.R. Davies, “Structure of an antibody-lysozome complex. Unexpected
effects of a conservative mutation,” Journal of Molecular Biology 245, 261-274 (1995).
Copyright © 1995 Academic Press.]
the end of a molecule that reaches through the cell membrane into the cell itself,
where it can organize internal machinery just from the tension created by external
binding. Even as x-ray diffraction reveals the intricacies of the essential contacts,
we have no more than cartoon ideas of how energies are transmitted and applied.
Physical opportunities abound.
Between the chemists’ syntheses and nature’s precise machining, there is the
possibility to work both ways: to use new tricks in synthesis to create molecules
with preferred properties, and to make changes in nature’s design—intentional
mutations of natural structures—to modify properties.
Great possibilities will be realized here when physicists trained to think
about molecular organization are also trained in the much easier crafts of synthe-
sis, mutation, modification, and manipulation. For example, biosensors are being
designed with biological materials for contact with the species to be detected and
electrodes with integrated circuitry for amplified response.

Consequences of the Human Genome Project and

Other Genome Determinations
Probably the most difficult question to speculate about is the consequence to
materials physics that will result from mapping of the human genome. It is hard
even to describe the magnitude of the information being collected. It will be
possible to synthesize and to mutate virtually every protein in our bodies or in the
body of any known organism. There are about 100,000 identifiable human genes.
The number of possible mutations is burdensome to behold. Given the 3 billion
base pairs that compose our genome and the possibility of putting 4 different
letter pairs at each of these 3 billion positions, the number of mutations easily
exceeds anything one would try to change systematically and exhaustively.
In the context of this chapter and this survey, it is to the learning opportuni-
ties for materials research that these numbers direct our attention. Physicists can
learn to produce any protein in desired quantities and to process and package it
with increasing skill. Excellent demonstration of this comes from the synthesis
of polypeptides of relatively simple sequence. The lure to create new industrial
and medical materials compels us to think how these gene products can be de-
signed and manipulated.
Simply knowing the amino acid sequence of a protein is yet not enough to
predict its properties. Similar to the exasperation we suffer in studying collective
quantum behavior (Chapter 3), difficulties in understanding proteins come from
their ability to achieve the unpredictable properties that emerge because of their
physical size.
As suggested at the beginning of this chapter, the nub of the matter is educa-
tion. Ideally, physics students will soon be as comfortable with gene-processing
procedures as they are with other ways to manipulate materials. New substances
whose properties differ qualitatively from those usually considered by physicists,
even in these advanced and exciting times, will also confront them.
It is probably pointless even to speculate about what we will be able to do
with all these new techniques and manipulations. There is already a National
Research Council study on new technology based in molecular biology.4 Natural
polymers such as silk and collagen will sooner or later be produced synthetically.
It is possible to imagine using elastin, the animal’s equivalent of rubber, as an
industrial product. Talk of DNA computers and molecular motors is no longer
strictly speculation or science fiction. Administration of gene therapy will come
to be guided by the principles of organization learned from preparing condensed
arrays of genetic material. Physicists who know how to make these materials will
be in an excellent position to think about how they work and how to work with
them using physical intuition.
4Biomolecular Self-Assembling Materials: Scientific and Technological Frontiers, National Acad-

emy Press, Washington, D.C. (1996).

Biological materials present a large opportunity for condensed-matter and

materials physics research and application. At the same time, they present a large
uncertainty in the time needed for that opportunity to be realized. It is difficult to
predict the seminal moments in an untried marriage of new physics and new
biology.
DIRECTIONS AND PRIORITIES

Despite the many different kinds of research described in this chapter, a few
general themes emerge. From these themes we can identify needs and priorities
for the support of research on soft materials.
Physicists have lost their pessimism about doing good physics on complex
materials. Whether in physics departments or in other departments, they are
studying biological materials for practical as well as fundamental research.
Among many physicists there is huge optimism over the learning opportuni-
ties provided by biological systems, in spite of conflicting traditions of learn-
ing and reasoning. Although the necessary development of physics in biology
can be expected to proceed naturally, the course and pace of this merger are
uncertain.
The deformability and other macroscopic features of soft condensed matter
are now routinely examined in terms of their microscopic structures and their
large thermal fluctuations. We already think of the various forms of soft matter
in terms of molecular arrangements, rather than their macroscopic properties.
Biological processes are coming to be routinely discussed in atomic detail. With
adequate support, structure determination and structural thinking can be expected
to grow rapidly for at least another 10 years.
The ability to observe, to manipulate, and to characterize single molecules
and to measure forces that create functional groupings of molecules is new and
exciting. Mechanical properties and biological functions such as information
transmission are increasingly discussed in terms of molecular structure. A sci-
ence of single molecules or similarly small objects—as mechanical objects, as
functioning machines, as interacting bodies—can be expected to have a large
impact on biological science and on the development of artificial materials.
New tools of synthesis create new polymers and reproduce or modify natural
biological polymers. These tools will become increasingly useful in the design of
practical materials, medical, industrial, and domestic, and will enable systematic
basic research to relate molecular cause and macroscopic effect.
Because of the complexity of the materials being examined, physicists are
learning to manipulate a much larger range of material properties than had been
thought possible before. Flow, deformability, microscopic patterning, strength,
and durability are being evoked from substances previously not considered to
have such possibilities. From better ways to design for particular properties, we
may hope that industrial progress will grow less empirical and more logical.

Research on soft materials creates vast amounts of information. Whether in

the possibilities built into the genetic code, the molecular details of protein struc-
ture, the many microscopic structures of liquid crystals, the nuances of medical
scanning, the chemical possibilities of polymer synthesis, or the scrap heap of
trial-and-error industrial innovation, the numbers that go into description are
huge. The growing size, number, and kinds of data banks are teaching us new
ways to organize and use information. We may expect physicists to grow in-
creasingly comfortable working with such “rich” systems.
Priorities
Education
When physicists work with materials that were once the province of other
fields, and when scientists in those fields use what physicists have learned, they
discover that there are different ways of learning, thinking, and even speaking in
the different fields. It is easy to say that education in physics, chemistry, and
biology must be broad as well as deep. It is easy to argue that tomorrow’s
condensed-matter physicists should not fear to synthesize polymers or handle
proteins or express genes. Although such skills are easily learned, there are many
obstacles to such broad learning. Even if there were time in school, subject
matter changes too fast to rely only on what is learned in school.
Several strategies can be tried:
• Interdisciplinary workshops;
• Summer schools with laboratories, for scientists at all career stages;
• New courses for biologists in elementary physics and for physicists in wet
chemistry, biochemistry, and molecular biology;
• Introductory physics instruction that emphasizes soft systems; and
• Bilingual texts—e.g., in biology and physics—that teach the vocabulary
and basic phenomena of particular systems. (This may be a good time for another
review for physicists modeled on the landmark 1959 series in Reviews of Modern
Physics.5)
Basic Research
Industrial and medical results will follow naturally, as they have inevitably
followed basic research in the past. Grant mechanisms can be established to
encourage the necessary interdisciplinary work.
5Raymond E. Zirkle, “Biophysical science. A study program: General features of radiobiological

actions,” Reviews of Modern Physics 31, 269 (1959).

• Special grant programs to compensate for the double jeopardy that goes
with the present system when research is judged both as biology and as physics;
• Fellowships developed and expanded for physicists to work in biological
laboratories—the NSF-NIH one-year visit program is one example; and
• Contact between university researchers and industrial scientists and be-
tween physicists, chemists, and biologists to foster collaborations, particularly
with the chemical, medical, and pharmaceutical industries.
The residue from trial and error in industrial research is an abundant source
of information for new physics. Biological systems are an inspiring source of
solved problems for doing physics in a new place. We can work to create
comfortable common ground for collaboration.
Undersupported research areas should be identified in which results will be
needed. For example, polyelectrolytes and biological polymers will be increas-
ingly used for products to displace environmentally unfriendly organic materials.
Research Facilities
For structure determination, neutron sources in particular are urgently needed.
Synchrotron x-ray, ion beam, transmission electron microscope, and surface probe
facilities are high on the list. Data processing is needed for the large amounts of
information being generated and the large computations that will be undertaken.
Overall
Intellectually, industrially, and medically, soft-material research has a poten-
tial that justifies funding increases like those being given to research in biology
and medicine.

NEW TOOLS FOR RESEARCH 225
New Tools for Research
Scientific progress is predicated on the observation of new phenomena, and

there are two basic paradigms for making scientific observations. The first is the
Galilean paradigm, which calls for building a better tool, such as a telescope, to
investigate a familiar object, which in Galileo’s case was Jupiter. The second
could be called the Columbian paradigm, which calls for using existing tech-
nology, such as a small fleet of ships with the best available equipment, to
investigate previously uncharted waters. Most of this report is dedicated to the
Columbian paradigm and its technological consequences. This chapter summa-
rizes where the Galilean paradigm has led us in the last 10 years and where
building better tools might lead in the coming decade.
What we are really dealing with are new ways of seeing what has been there
all along. The suite of small-to-large scale facilities that have enabled con-
densed-matter physicists to image atoms and electrons is as essential to the con-
densed-matter enterprise as the network of telescopes and detectors probing opti-
cal and cosmic ray spectra are fundamental to astronomy and cosmology. For
more than a century, the condensed-matter suite has included small apparatus
such as magnetometers and calorimeters. During the last few decades the suite
has expanded to include synchrotrons and free-electron lasers, which produce
highly coherent light of wavelengths from the far infrared to hard x-rays; nuclear
reactors optimized for neutron yields; proton accelerators with targets for neutron
and meson production; electron microscopes; and scanning-probe microscopes
sensitive to everything from electron densities to magnetization at surfaces. Other
exploratory tools include machines for subjecting matter to extreme conditions
such as high magnetic and electric fields and pressures or ultralow temperatures.
225

Finally, in the past decade, direct computation or simulation has become an

increasingly routine and reliable method for seeing and understanding condensed
matter.
This chapter consists of sections devoted to each of the tools noted. Each
section describes specific accomplishments these tools made possible in the last
decade as well as opportunities and challenges for the future. Even though the
sections deal with quite distinct facilities and techniques, there are certain
overarching themes. An excellent example of an important scientific contribu-
tion over the last 10 years has been the effort to unravel the astonishing properties
of the high-Tc cuprates and their siblings. It would be very difficult to imagine
where our knowledge of the cuprates would be without the atomic coordinates
given by neutron diffraction carried out at proton accelerators, the electronic
bands given by photoemission at synchrotron sources, the defects found by elec-
tron microscopy, the magnetic order and fluctuations discovered using both reac-
tor- and accelerator-based neutron sources, the charge transport measured in
extreme pressures or magnetic fields, and the computer calculations of electronic
energy levels. The experience with the cuprates shows that each of the facilities
used is both unique and indispensable, and that their power is vastly amplified by
combining data from the entire suite.
In addition to addressing specific scientific problems, another overarching
theme includes the invigorating effects of new facilities, be they large national
resources such as the Advanced Photon Source, the new hard x-ray synchrotron
at Argonne National Laboratory; medium-scale installations such as the newly
formed National High Field Magnet Laboratory operated in Florida and New
Mexico; or electron microscopes and surface characterization equipment in cen-
tral materials research facilities. The commercial availability of increasingly
powerful workstations, electron microscopes, piezoelectric scanning-probe tools,
and superconducting magnets have played an equally important but different
role—namely, that of democratizing access to atomic resolution and high mag-
netic fields by giving individual investigators with small laboratories extraordi-
nary capabilities formerly limited to those with access to large facilities.
A final thread linking the tools is a direct product of the information revolu-
tion seeded by condensed-matter physics and discussed at length elsewhere in the
report—specifically, the proliferation of information the tools provide and the
increasingly quantitative nature of the information. The most obvious manifesta-
tion is the trend away from simple black-and-white x-y plots and toward digital
color images as experimental outcomes. Such images were exotic and labori-
ously produced 10 years ago. (The original scanning-tunneling microscopy im-
ages of silicon surfaces by Binnig and Rorer were actually photographs of card-
board models constructed from chart-recorder traces.) Today, color images are a
routine feature of output from all of the techniques and facilities described below.
The future holds many opportunities and challenges including raising probe
particle brilliance, improving instrumental resolution, extending spectral ranges,

and diagnosing increasingly complex phenomena in areas from ceramic process-

ing to biology. Less obvious but equally important is the need to continue to
collect and take full advantage of the large and quantitative data sets that the tools
of today and tomorrow promise. This implies a broad program including ele-
ments such as quoting results that had hitherto been considered qualitative in
absolute units, modeling strong probe-sample interactions, and taking advantage
of the most advanced data collection and display technologies available.
ATOMIC VISUALIZATION THROUGH MICROSCOPY

A quick glance at the illustrations in this report confirms that atomic visual-
ization underpins much of condensed-matter and materials physics. Knowledge
of the arrangements of atoms is a prerequisite for understanding and controlling
the physical properties of solids. The techniques needed to visualize atoms in
solids themselves challenge our scientific and engineering capabilities. Research
in atomic visualization techniques has often lead to improved manufacturing
technologies, for example, in semiconductor fabrication and quality control.
Tools used for atomic visualization are small enough to fit into an average-
sized laboratory and are inexpensive enough to fit into the budget of a small-
instrumentation grant, but cooperative usage (as facilities) and especially coop-
erative instrumental development can be invaluable.
Our ability to see atomic arrangements and identify local electronic structure
has progressed dramatically in the last decades. The Nobel Prize in Physics of
1986 recognized the development of the two most important techniques for this
purpose—scanning-tunneling microscopy and transmission-electron microscopy
(TEM) (see Table O.1). Since then there has been astounding progress. The
tunneling microscope has given birth to a burgeoning industry of versatile “scan-
ning-probe” microscopes that, while sharing many characteristics with the scan-
ning-tunneling microscope, do not rely on vacuum tunneling for image forma-
tion. Whereas the tunneling microscope is sensitive to local electronic states,
probe microscopies can examine chemical reactivity, magnetism, optical absorp-
tion, mechanical response, and a host of other properties of surfaces on a near-
atomic scale. The United States is a leader in research with probe microscopes,
and this is the only microscopy area in which we dominate commercially.
Probe microscopy is undoubtedly powerful, but it is to a large extent limited
to surface imaging. There are interesting exceptions, such as ballistic emission
electron microscopy (BEEM) in which fast electrons are injected into a layer and
their propagation is influenced by interfacial structure. Other complementary
surface microscopy techniques that have grown in the last decade include low-
energy electron microscopy (LEEM) and near-field scanning optical microscopy
(NSOM). TEM, however, remains the dominant tool used for the microstructural
characterization of thin films and bulk materials because its images are not con-
fined to the surface. In the transmission-electron microscope, a high-energy

electron beam, guided by magnetic lenses, is scattered by a thin specimen. Dif-

fraction makes it possible to study atomic structures inside solids and examine
microstructure on scales from 0.1 nm to 100 µm. One example of the innovations
achieved in the last decade with TEM is the discovery and structural solution of
carbon nanotubes and nanoparticles. There has been significant progress in the
last decade in the TEM field as well, for example, improved resolution (now at
about 1 Å). Resolution is likely to be improved even further, using innovative
aberration-correction techniques. Concomitant with improved spatial resolution
in microscopy has been an improvement in efficiency and resolution in spectros-
copy with electrons, which has enabled atomic-scale characterization of elec-
tronic structure. These techniques are complementary to, and synergistic with,
improved neutron and x-ray tools described elsewhere.
Despite the undoubted value of improved resolution, a more important fron-
tier in electron microscopy involves the ability to extract reliable quantitative
information from images. An example is the use of fluctuation microscopy to go
beyond the limits of diffraction in studying disordered materials. We anticipate
much progress in the quantitative arena in the next decade. Although the proverb
holds that a picture is worth a thousand words (no doubt true aesthetically), in
science a few well-chosen words are sometimes worth a thousand pictures. This
is because scientific questions involve precise answers, and pictures are by their
nature imprecise. However, the theory of high-energy electron scattering is well
developed, and continuing improvements in electron image detection and image
analysis permit quantitative interpretation of images at the atomic level. We can
expect that this capability will eventually reach a level at which nonexperts can
use TEM as a quantitative structure analysis tool.
Similar progress can be expected in electron spectroscopy. Local spectros-
copy allows not only atomic visualization, but also characterization of the
electronic and chemical states of individual atoms or groups of atoms. Spec-
troscopy of surface atoms is the natural result of scanning-tunneling micros-
copy and can also be obtained (on groups of atoms) using TEM and surface-
electron microscopy by electron energy-loss spectroscopy. Near-edge structure
observed at characteristic x-ray energies can be used to determine band struc-
ture at buried interfaces, for example. Recent work has directly revealed the
importance of metal-induced gap states in metal-ceramic bonding. One expects
improvements both in the sensitivity of these techniques and in the quantitative
modeling and data analysis needed to interpret their results. Ultimately, we
need to obtain both atomic positional and chemical information for full struc-
tural characterization.
Although probe microscopes and some electron microscopes can flourish in
the individual-investigator or small-facility setting, some instruments required
for the future growth of atomic visualization will be of a scale such that they will
need to be located in regional, if not national, centers. With computer network

access, remote control of the instruments is likely to become widespread. So

even though instruments may be located in only a few institutions, accessibility
will be universal. It remains desirable to maintain centers of excellence where
experts in the appropriate techniques can be available for consultation and col-
laboration. Also, instrument and technique development could be facilitated on
the regional-center scale and should be encouraged because although it has his-
torically been underemphasized, it is critical to scientific and technological suc-
cess. In addition, centers facilitate education in instrumentation, so critical for
industrial competitiveness.
Atomic Structure
Scanning-probe microscopes have made atomic resolution imaging of sur-
faces almost routine, with tremendous impact on surface science. We are finally
beginning to understand the important subject of thin-film growth, one atom at a
time, and can observe how atomic steps can prevent atom migration in one
direction compared with another, leading to undesirable roughness in deposited
films. Here, there is close interaction between experimental visualization and
computer modeling. A particularly exciting development in scanning-probe mi-
croscopy has been the imaging of chemical and biochemical molecules and the
possibility of monitoring chemical reactions. By choosing one molecule as the
tip of the atomic-force microscope (AFM), the forces between molecules can be
directly measured and chemical reactions sensed with unprecedented molecular
sensitivity. This has already led to new insights into the rheology of macromol-
ecules (see Chapter 5), and we can expect great advances in the near future,
especially in the biological sciences. For example, the use of “smart” tips would
allow recognition of molecules using specific receptors adhered to the tip.
The scanning-tunneling microscope (STM) views the local electronic struc-
ture, so careful image simulations must be made to deduce atomic structure. In
general, for structural studies on surfaces, the best results have been obtained by
a combination of direct STM imaging with diffraction—for example, by x-rays
or electrons. The highest directly interpretable spatial resolution for atomic
structure has been obtained with TEM (see Box 6.1); instruments capable of
resolving 1 Å have recently been demonstrated. The committee notes that, partly
because of the ~$50 million price tag for these instruments and partly because of
the damage accompanying the high accelerating voltages required, no such
instrument can be found in the United States. Researchers’ hopes are pinned on
lower accelerating voltage approaches to improved TEM resolution, such as
holographic reconstruction, focus variation, incoherent Z-contrast, and aberration
correction. However, it is troubling that work in these areas is predominantly
located in Europe and Japan; a notable exception is work on incoherent Z-contrast
imaging (see Box 6.1). A relatively recent study of trends in atomic resolution

BOX 6.1 Being Certain About Atom Positions at Interfaces
Identification of atomic structure at interfaces has been one of the important

applications of high-resolution transmission electron microscopy. Interfaces con-
trol mechanical strength in ceramics, electrical transport in transistors, corrosion
problems in aircraft, tunneling currents in superconductor junctions, and a myriad
of other practical materials behavior. Yet, with rare exceptions, interfaces are not
amenable to diffraction analysis because they are very thin and not usually uni-
form. Figure 6.1.1 shows an example of a high-resolution transmission-electron
microscope image, using “z-contrast” of a grain boundary in MgO (courtesy of Oak
Ridge National Laboratory), in which atomic columns at the boundary are revealed.
Images like this are beginning to be analyzed in a quantitative manner, using accu-
rate measurements of intensity, simulations of electron propagation, and computa-
tional modeling of atomic structure, to achieve unprecedented reliability in analysis
of interfaces.
FIGURE 6.1.1 High-resolution transmission electron micrograph, using z-contrast,

in MgO.
microscopy was published by the National Science Foundation.1 Advances in

electron microscopy enable advances in related industrial technologies, espe-
cially semiconductors; so the value of U.S. investment in this area extends far
beyond atomic visualization.
A clear example of the value of improved resolution in TEM is tomography.
Tomography has been widely used in biology to reconstruct objects at about
1-nm resolution. Only with a resolution of about 0.5 Å will it be possible to
1National Science Foundation Panel Report on Atomic Resolution Microscopy: Atomic Imaging
and Manipulation (AIM) for Advanced Materials, U.S. Government Printing Office, Washington,
D.C. (1993).

reconstruct objects in three dimensions at the atomic scale. This would be par-
ticularly exciting for amorphous and disordered materials; knowledge of their
atomic structure is limited to statistical averages from diffraction. Instruments to
enable this will require ~0.5 Å resolution combined with high specimen-tilt
capability (>45°). Such will be possible either with very high voltages or with
aberration correction.
Electronic Structure
For many research problems in condensed-matter and materials physics, it is
important to visualize the electronic structure on a near-atomic scale. STM
provides direct information about electronic states at surfaces but is often used
for purely structural analysis and has had tremendous impact on surface science.
Examples in the report include the germanium “huts” in Figure 2.13. In general,
probe microscopy combined with electron microscopy has revolutionized our
understanding of thin-film growth and epitaxy (see Chapter 2).
STM has been profitably used to examine surface electronic states and chemi-
cal reactions on the atomic level. Although detailed electronic structure calcula-
tions are needed to interpret STM images in terms of atomic positions, often the
electronic structure information is directly useful. For example, Box 6.2 gives an
example of direct STM imaging of the electronic states associated with individual
dopant atoms in semiconductors.
Electron energy-loss spectroscopy in TEM provides an important method to
obtain electronic structure from the interior of samples on a near-atomic level.
Improvements in the sensitivity of detection, using more monochromatic field-
emission electron sources and parallel detection, have led to important advances
in the last decade. For example, dopant segregation at semiconductor grain
boundaries has been identified.
Nanoproperties of Materials
One of the most significant developments of the last decade is the prolif-
eration of scanning-probe techniques for measuring the nanoproperties of ma-
terials. Figure 6.1 shows a large variety of signals that are now detectable.
Nanomechanical (force) measurements can be used to watch the behavior of
individual dislocations; optical measurements can visualize single lumines-
cent states; piezoelectric measurements can identify the effect of defects on
ferroelectrics, which have potential for high-density nonvolatile memory;
magnetic measurements can show the effect of single atoms on spin alignment
in atomic layers; ballistic electron transport can identify the electronic states
associated with isolated defects inside a film. We can expect these capabilities
to revolutionize our ability to characterize the physical properties of nanoscale
materials.

BOX 6.2 Single Impurity Atoms Imaged

in Semiconductor Layers
One critical issue, as semiconductor devices are scaled down in size for higher
density and speed, is the stochastic nature of the location of dopant atoms. These
atoms, which lend electronic carriers to the active semiconductor layers, are typi-
cally present in densities of only about 1 in a million. Until recent years, it was an
impossible dream to identify the exact location of these dopant atoms, but this has
recently proved possible with scanning-tunneling microscopy. Figure 6.2.1 shows
detection of the local electronic state generated by the impurity. When a semicon-
ductor structure is cleaved in vacuum, the individual impurity atoms near the sur-
face are clearly visible. The image (courtesy of Lawrence Berkeley Laboratory)
shows the position of Si dopants in GaAs as bright spots. Also present in the
image are Ga vacancies, which appear as dark spots.
FIGURE 6.2.1 Local electronic states in GaAs generated by Si impurities.
Tunneling
Current
Light, Sound
Force
(electrostatic,
magnetic)
Electron
Transport
FIGURE 6.1 Schematic drawing of the signals detected in scanning-probe microscopy.

(Courtesy of the University of Illinois at Urbana-Champaign.)

Similar developments have occurred in other imaging systems. A beautiful

example of a technique known as “scanning electron microscopy with polariza-
tion analysis,” which allows imaging of magnetic monolayers at surfaces in a
modified scanning-electron microscope, is discussed in Chapter 1.
Atomic Manipulation
Whether intended or not, our atomic-scale characterization tools can change
the structures they are examining. This can be used to our advantage in manipu-
lating atoms on the atomic scale for making nanostructures. Figure 6.2 shows the
classic example of a ring of iron atoms assembled by the tip of a scanning-
tunneling microscope. The circular atomic corral shows the resonant quantum
states expected from simple theory. The imagination boggles at the possibilities
with related techniques. In principle, we can assemble arbitrary structures to test
our understanding of the physics of nanostructures and perhaps make useful
devices at unprecedented density. Two major issues will need to be addressed
before these methods can reach their full potential. First, even when we place
atoms where we choose, with few exceptions (such as the Fe atoms in Figure 6.2
at ultralow temperatures), they will not stay there. So, to assemble structures that
FIGURE 6.2 Atomic manipulation. The image shows the atomic scale capability for
patterning that is possible with the scanning-probe microscope. Atoms of Fe (high peaks)
were arranged in a circle on the surface of Cu and caused resonant electron states (the
ripples) to appear in the Cu surface. The structure is dubbed the “quantum corral.”
Related structures might one day be useful for electronic devices, where as many devices
as there are humans in the world could be assembled on an area the size of a pinhead
(1 mm2). (Courtesy IBM Research.)

retain their integrity, we need to understand the stability of materials on this

scale. Second, the speed with which we can pattern structures with a single
scanning probe is far too slow to allow practical device fabrication on the scale of
modern semiconductor technology. Alternate methods involving massive arrays
of tips, projection electron lithography, or other short-exposure techniques must
be developed.
Conclusions
Atomic visualization is a crucial part of condensed-matter and materials
physics. It is a thriving area in which advances usually driven by physics and
engineering have wide impact on science and technology. Many manufacturing
technologies depend on innovations enabled by atomic visualization equipment,
so research in the field has important economic value. We expect continued
developments, but attention must be paid to nurturing the development of appro-
priate instrumentation in close connection with scientific experiments. Depend-
ing on the nature of the visualization tool, the funding scope ranges from indi-
vidual investigator to small groups, to national centers of excellence in
instrumentation. From our success in probe microscopy, it appears we are stron-
ger at the individual-investgator level but weaker at the medium- and larger-scale
instrumentation development levels. A concern is that many new students are
attracted by computer visualization rather than experimental visualization. The
two methods are obviously complementary, and we are not yet near the point
where we can rely only on computer experiments. Thus funding must be main-
tained at a level sufficient to create opportunities that will attract high-quality
students into this field.
NEUTRON SCATTERING
The neutron is a particle with the mass of the proton, a magnetic moment
because of its spin-1/2, and no electrical charge. It probes solids through the
magnetic dipolar interaction with the electron spins and via the strong interaction
with the atomic nuclei. These interactions are weak compared to those associated
with light or electrons. They are also extremely well known, which makes it
possible to use neutrons to identify spin and mass densities in solids with an
accuracy that in many cases is greater than with any other particle or electromag-
netic probe. The wavelengths of neutrons produced at their traditional source,
nuclear research reactors with moderator blankets of light or heavy water held near
room temperature, are on the order of inter-atomic spacings in ordinary solids. In
addition, their energies are on the order of the energies of many of the most
common collective excitations—such as lattice vibrations—in solids. To image
spin and mass densities, condensed-matter physicists usually aim neutrons moving
at a single velocity and in a single direction, that is, with well-specified momentum

and energy, at a sample and then measure the energy and momentum distribution of
the neutrons emerging from the sample. Such neutron-scattering experiments have
been important for the development of condensed-matter physics over the last half
century. Indeed, the impact of the technique has been such that C. Shull (Massa-
chusetts Institute of Technology) and B. Brockhouse (McMaster University) were
awarded the 1994 Nobel Prize in Physics for its development (see Table O.1). In
previous decades, neutron scattering provided key evidence for many important
phenomena ranging from antiferromagnetism, as originally posited by Neel, to
unique quantum oscillations (called rotons) in superfluid helium. But what has
happened in the last decade in the area of neutron scattering from solids and liquids,
and what is its potential for the coming decade?
The Past Decade
Overview
Three major developments of the last decade are (1) the emergence of neu-
tron scattering as an important probe for “soft” as well as “hard” condensed
matter, (2) the coming of age of accelerator-based pulsed neutron sources, and
(3) the revival of neutron reflectometry. The first development has expanded the
user base for neutron scattering far beyond solid-state physicists and chemists,
who had been essentially the only users of neutrons. The second development is
associated with a method for producing neutrons not from a self-sustaining fis-
sion reaction, but from the spallation—or evaporation—that occurs when ener-
getic protons strike a fixed target. As depicted in Figure 6.3, a spallation source
consists of a proton accelerator that produces short bursts of protons with ener-
gies generally higher than 0.5 GeV, a target station containing a heavy metal
target that emits neutrons in response to proton bombardment, and surrounding
moderators that slow the neutrons to the velocities appropriate for experiments.
Until the mid-1980s, the leading facility of this type was the Intense Pulsed
Neutron Source (IPNS) at the Argonne National Laboratory. In the last decade,
the clear leader by a very wide margin has been the ISIS facility in the United
Kingdom. Successful developments, especially at ISIS, have given the neutron-
scattering field growth prospects that it has not had since the original high-flux
nuclear reactor core designs of the 1960s. This follows because pulsed sources
are more naturally capable of taking advantage of the information and electronics
revolutions and because the unit of cooling power required per unit of neutron
flux is almost one order of magnitude less than for nuclear reactors.
The revival of neutron reflectometry seems at first glance less momentous
than the emergence of neutron scattering as a soft condensed-matter probe or the
emergence of accelerator-based pulsed neutron sources. However, as so much of
modern condensed-matter physics and materials science revolves about surfaces
and interfaces, neutron scattering could hardly be considered a vital technique

FIGURE 6.3 Drawing of the planned Spallation Neutron Source at Oak Ridge National
Laboratory. The basic design features are similar to those for the Los Alamos Neutron
Scattering Center (LANSCE) and the planned European Spallation Source (ESS). The
linear accelerator takes protons to 1.33 GeV, while the accumulator ring groups them into
1 µsec bursts, occurring at a repetition rate of 60 Hz, which then impinge onto a liquid
mercury target. The neutrons emanate in corresponding bursts from the target and feed
scattering instruments with flight paths with lengths from 2 to 100 m. (Courtesy of Oak
Ridge National Laboratory.)
without some clearly defined contribution in these areas. The revival of

reflectometry has enabled neutrons, in spite of their weak coupling nature, to
become a legitimate probe of surfaces and interfaces. Here we use long wave-
lengths and incident and reflected beams that nearly graze the sample, so that we
are in the surface-sensitive regime near the condition of total external reflection.
Locating the Atoms

The major contributions of neutrons to condensed-matter and materials phys-
ics in the last decades come from using neutrons to answer the most fundamental
question that always arises when new materials are discovered—“Where are the
atoms?” Although this question is generally answered using x-ray diffraction, the
unique properties of neutrons offer significant advantages in many important
cases. However, since neutrons couple via the nuclear interaction to the atomic

cores rather than via the electromagnetic interaction to the atomic electrons,
neutrons can be equally sensitive to light (low-Z) and heavy (high-Z) atoms,
whereas x-rays always couple much more strongly to the heavy elements. Neu-
trons are especially sensitive to the lightest and arguably most important element
of all, hydrogen, and quite sensitive to its rival in importance, oxygen. In addi-
tion, it is possible to change atoms’ visibility to neutrons, without appreciably
changing the bonding or chemistry of a particular atom, by changing the isotope.
Thus, particular sites in a material can be labeled for investigation of their micro-
scopic coordinates and motion. Finally, the combination of various neutron
sources, as well the ability to tailor wavelength distributions even at a single
source, permits the examination of structures with characteristic length scales
from angstroms to microns. The weak coupling nature of the probe means that
even as the wavelengths of the neutrons used experimentally change over three
orders of magnitude, the scattering cross sections do not and absorption and
resolution corrections remain simply calculable.
One of the most lively areas in condensed-matter science over the last decade
has been that of transition metal oxides, a field dramatically revived by the
discovery of high-temperature superconductivity in oxides of copper. The
materials are generally combinations of relatively heavy lanthanides, medium-
weight transition metals, and light oxygen atoms. With this set of constituents,
neutron scattering was ideally positioned to make an important contribution to
the structure determination. The technique did not disappoint. First it has been
demonstrated that the key structural elements common to all of the cuprate super-
conductors are nearly square planar arrays of copper and oxygen. The signifi-
cance of this simple finding is impossible to overstate. That copper oxygen
planes are the key feature of the high-temperature superconductors has been the
starting point for essentially all of our thinking about high-temperature supercon-
ductivity as well as searches for materials with better superconducting properties.
Beyond revealing the ubiquity of the copper oxygen planes, neutron diffraction
has revealed how the planes appear singly, in pairs, or even as triplets, sometimes
with and sometimes without copper oxide chains in intervening layers. The
picture of the intervening layers as reservoirs that provide charges for the copper
oxygen planes is largely the result of a combination of neutron diffraction and
classical measurements of bulk electrical properties such as resistivity.
Extensive work has shown close correlations between structural details and
superconducting properties. For example, in a mercury-based compound exhib-
iting an extraordinarily high Tc, which itself is very sensitive to pressure, neutron
diffraction showed dramatic changes in the atomic coordinates with applied pres-
sure (see Figure 6.4).
Even after 10 years of indispensable contributions to the understanding of
high-Tc superconductivity, neutron diffraction retains its unique, driving role in
this field. A recent illustration of this is the excitement generated by the discov-
ery that certain materials very closely related to the high-temperature supercon-

Cu2-O3
FIGURE 6.4 Mercury-based cuprates exhibit not only the highest transition tempera-
tures Tc for superconductivity, but also extraordinarily pressure-dependent Tc’s. High-
resolution neutron diffraction at pulsed spallation sources has revealed the complex struc-
tures (at right) of these compounds. In addition, the penetrating power of the technique
has been exploited to examine the pressure dependence of the structure. There is an
astonishing 0.25 Å contraction of the marked copper-to-oxygen distance as pressure is
applied to raise Tc from 138 to 160 K.
ductors undergo phase transitions to states with large-scale superstructures. Neu-

tron scattering has provided atomic-scale information not only about the high-
temperature superconductors, but also about many other transition metal oxides.
Notable examples are the perovskite manganites whose “colossal” magnetoresis-
tance—large changes in the electrical resistivity when external magnetic fields
are imposed—has recently been rediscovered. Neutron diffraction has been
used to identify the structural parameters most strongly correlated with the
magnetoresistance.
Seeing the Spins

Once they know the locations of atoms in a particular solid or fluid, con-
densed-matter physicists generally would like to know what the electrons are

doing. The electrons of particular interest are the outer electrons because they
account for the chemical bonding and electrical and magnetic properties of a
solid. The neutron couples to these electrons through the magnetic dipole inter-
action; because its energy is typically much too small to excite the electrons from
the core where they form a closed shell with zero net orbital and spin-angular
momenta, the cores are invisible. The outer electrons are easiest to see with
neutrons when they live on a regular lattice and their spin orientations repeat
periodically. In this case, they produce diffraction spots entirely analogous to
those associated with atomic nuclei. As Shull showed in the 1950s, it is then
possible to do magnetic crystallography to image the spin arrangements in virtu-
ally any magnet. In the last decade, magnetic crystallography with neutrons has
continued to be among the most essential tools in condensed-matter physics.
Again, high-temperature superconductivity has been an area of accomplishment.
The important experiment was that which showed, shortly after the super-
conductivity’s discovery, that the insulating and undoped parent compounds of
the superconductors are actually very simple antiferromagnets. In the decade
since this experiment, the superconductivity and magnetism of the cuprates have
been inextricably intertwined. As for the neutron diffraction experiments that
revealed the microscopic structures of the high-Tc compounds, the last decade’s
progress in high-temperature superconductivity would be unimaginable without
the early magnetic diffraction data on the parent compounds.
Magnetic diffraction has played a similar role in other subfields that have
been active in the last decade. For example, it established a definite link between
the magnetism and exotic superconductivity of certain actinide and rare-earth
intermetallics, also known as heavy fermion compounds. Also, a particularly
important and elegant set of experiments explored the coupling between mag-
netic layers through intervening nonmagnetic layers in thin-film multilayer struc-
tures grown by molecular-beam epitaxy. The structures show great promise as
“spin valves” for application to computer disk drive read heads. The optimiza-
tion of their performance requires complete knowledge of the atomic and spin
densities responsible for the desirable giant magnetoresisant behavior. Using
polarized-neutron reflectivity, one can obtain a depth profile of the direction and
magnitude of the magnetic moment in these materials with 2- to 3-Å resolution.
Early polarized-neutron reflectivity studies confirmed that maximum giant mag-
netoresistance is correlated with an antiparallel alignment of the magnetic layers
across the nonmagnetic interlayers. More recent experiments revealed the com-
plex interplay between the magnetic structure and the physical characteristics.
Imaging Vortices in Superconductors

A seemingly different type of magnetic structure is that of mesoscopic field
inhomogeneities. Mesoscopic inhomogeneities are seen by the neutrons in the
same way in which they see the microscopic field inhomogeneities associated

with the electron spins—namely, through the magnetic dipole coupling between
the neutron spin and the magnetic fields. The relevant wave numbers and corre-
sponding apparatus are different, but the concepts remain the same. The most
famous mesoscopic field inhomogeneities in condensed-matter physics are those
associated with type-II superconductors. Here, the superconductor accommo-
dates an external field by admitting quantized vortices containing normal (metal-
lic) state cores embedded in a superconducting matrix. The vortices typically
arrange themselves to form a lattice with inter-vortex separations of order 100 to
1000 Å. One of the triumphs of neutron scattering in the 1960s was the verifica-
tion of the vortex lattice picture for conventional, low-temperature type-II super-
conductors. Given this early success, it should come as no surprise that as
unconventional superconductors such as actinide intermetallics and cuprates were
discovered in the 1980s and 1990s, neutrons were used to image their vortex
lattices. They provided key evidence for two of the most important new ideas
about superconductivity. The first idea is that real solids could actually display
superconductivity more akin to the superfluidity of helium-3 than to the super-
conductivity of ordinary solids like aluminum; the second is that collections of
vortices can have intricate phase diagrams much like those of complicated or-
ganic molecules in solution.
Pictures of Soft Matter

The committee has focused so far on neutron scattering from intermetallic
compounds and their oxides, which, although they are complex, are solids of
long-standing interest to condensed-matter physicists. Indeed, manganites were
among the first materials to be investigated by neutron diffraction shortly after
the invention of the technique in the 1950s. The last decade has witnessed a huge
growth in the use of neutrons to image structures formed at surfaces and inter-
faces, as well as the large-scale structures that emerge in materials with genuinely
large molecular units, such as polymers and water-based biomolecules. The
universe of such structures is actually much larger than that of traditional con-
densed-matter and materials physics and contains most of the matter essential for
our lives. One particularly successful application of the neutron technique has
been to diblock coploymers, which show a huge variety of disordered and
mesoscopically ordered states. As in classic condensed-matter physics, the goal
of the investigations is to relate the structures to properties, such as elasticity,
which determine functionality. Neutron scattering has also measured the sizes
and shapes of micelles that appear in microemulsions. Model systems mainly of
interest to statistical physicists, as well as biologically interesting micelles such
as ribosomes, have been examined. Another development of the last decade has
been the application of neutron scattering to surfaces, interfaces, and membranes
involving polymers and other large organic molecules. Knowledge of local
structural features as well as interface profiles feeds into a vast array of scientific

and technical fields from biology to integrated circuit packaging. Figure 6.5
shows the shape change undergone by diblock copolymers adsorbed on a glass
substrate. As the conditions are changed, the copolymers undergo a transition
from a mushroom- to a brush-like shape, which correlates with a change in the
adhesive properties of the coated surface.
Dynamics
Nuclear and magnetic structure determinations represent the most common
and widely understood application of neutron scattering. However, since the
work of Brockhouse in the 1950s, the study of lattice vibrations and magnetic
fluctuations has also had an impact on condensed-matter physics and materials
science. As have neutron determinations of magnetic and nuclear structure,
(a) Polymer "Mushrooms" 4
(a) Polymer “Mushrooms”

Reflectivity *Qz
10-9
φ (x)
.01 .02 .03 .04 .05
(b) Polymer "Brushes" -1
Q z (Å )
(b) Polymer “Brushes”
4
Reflectivity *Qz
10-9
.01 .02 .03 .04 .05

φ (x) -1
Q z (Å )
FIGURE 6.5 One of the most important developments of the 1990s has been the revival
of neutron reflectometry. Formerly used as a tool for establishing absolute neutron-
scattering cross sections, it has become a major technique for surface and interface sci-
ence, with particularly significant accomplishments in the fields of soft matter and mag-
netoresistive films. The figure shows data for the “mushroom” to “brush” transition for
polymers attached to a substrate. Raw data are at right, the directly deduced density
profiles are in the middle, and the inferred morphology is shown at left. The radically
different reflectivity profiles at right attest to the ability of the technique to discriminate
between the different arrangements of the polymers at the surface. (Courtesy of Los
Alamos National Laboratory.)

neutron scattering from excitations in solids has strongly influenced our thinking
about transition metal oxides. For example, work on the cuprate superconductors
includes measurements of the phonon density of states, which can be used as
inputs into traditional calculations of the superconducting transition temperature.
The apparent failure of such calculations remains an important motivation to
search for a new theory for the superconductivity of the cuprates. Much more
recent experiments provide similarly complete magnetic excitation spectra, which
can now be used in analogous tests of “conventional” magnetic theories of high-
temperature superconductivity.
An interesting development has been the use of neutrons to probe the elec-
tronic gap function and pair-breaking excitations in the superconducting
state. Neutrons are unique for this application because they allow the only
superconducting spectroscopy that is a true bulk probe capable of examining
short-wavelength phenomena with high energy resolution.
The continuing work on the dynamics of ordered solids has coexisted with
a rapidly growing enterprise concerned with the dynamics of fluids and soft
matter. Important experiments include those that have verified one of the key
concepts in polymer science—that polymers in a melt move in snake-like fash-
ion within tubular structures formed by their neighbors. The experiments are
noteworthy not only for their scientific impact, but also because they required
the use of an instrument—the neutron spin echo spectrometer—that operates on
a principle unknown to the founders of inelastic neutron scattering, Fermi and
Brockhouse.
The Next Decade

Because of unique properties associated with their mass, charge, and spin,
neutrons have a scientific future as bright as their past. Most likely, key accom-
plishments with neutrons will be as unexpected as were those of the last decade,
when they were linked to a largely unexplored class of materials—the cuprates—
that happened to display an extraordinary and unexpected property, high-Tc super-
conductivity. Thus, the cuprates offer for neutron scattering, as they do for con-
densed-matter physics as a whole, a lesson in humility to all who wish to plan future
accomplishments. At the same time, the success of neutrons in meeting the chal-
lenges of high-temperature superconductivity was not entirely serendipitous. In-
deed, the discovery and subsequent intensive study of the cuprates coincided with
other developments:
1. The rapid development of accelerator-based pulsed neutron sources and

instrumentation, whose operating paradigms are entirely different from those
invented by Shull and Brockhouse for nuclear reactors;
2. Progress in electronics, data visualization, and computation driven by the
microelectronics revolution;

3. Extension of the routinely examinable spectral range from its traditional

0.5- to 50-meV domain to its current 1-µeV to 1-eV band;
4. Development of increasingly efficient beam optics and scattered-neutron
analysis and detection schemes; and
5. Extension of sample environment capabilities to lower temperatures,
higher magnetic fields, and higher pressures.
These other developments not only coexisted with the great materials dis-
coveries of the last decade, but were actually a prerequisite for the significant
contributions ultimately made by neutron scattering to the elucidation of these
discoveries. It is our judgment that further improvements in all five of the listed
categories are inevitable in the next decade. The inevitability follows from the
continued effects of accelerator-based pulsed neutron sources and instrumenta-
tion, and of advances driven by the microelectronics revolution on the entire
field, that has been hampered by the limits imposed by the modest incident fluxes
that even modern research reactors can provide. Advances in both accelerator-
based pulsed neutron research and microelectronics have made it possible to
multiplex many experiments on an enormous scale, for example, simultaneously
collecting 106 usable pixels of information where the old reactor-based methods
would yield a single pixel. Thus, the field of neutron scattering has changed
qualitatively over the last decade, even though only one major new source (ISIS
in the United Kingdom) has been completed. The figure of merit for many
important experiments has been transformed from the reactor power to the infor-
mation rate. In the coming decade, we expect the useable information rates as
measured by the product of incident flux delivered by the beam optics and the
number of independent pixels to grow in tandem with the microelectronics revo-
lution (Figure 6.6). Beam optics are also on a growth curve driven by improve-
ments in thin film-technology and x-ray and light optics, and so are also likely to
improve. The continued growth in capabilities will make many new experiments
possible, as well as allow old measurements to be performed with greater preci-
sion. The new experiments might include measurements of vortex lattice dynam-
ics in type-II superconductors, investigations of the magnetic aspects of the quan-
tum Hall effects, characterization of fluid flow in small capillaries, and studies of
electromigration at silicon-metal interfaces. Of course, the most exciting experi-
ments will be those dealing with phenomena we are unaware of today.
Neutron experiments have continued to be popular even in the absence of a
new neutron source because of the neutron’s uniqueness as a probe of condensed
matter and because neutron experiments are so readily improved by ongoing
advances in microelectronics and thin-film technology. However, merely trans-
ferring technology developed for other uses to its antiquated neutron-scattering
centers will not allow the United States to recapture its lead in neutron science.
There is no substitute for constructing a new high-power spallation source with
many high-flux beam lines. In recognition of this, the government is supporting

10 7
ESS
Pixel Power (MW)
106
SNS
5
10 MAPS/ISIS
reactors
104 spallation sources
HET/ISIS
Brockhouse
103
HFIR MARI/ISIS
102 ILL
HFBR HET/ISIS
1970 1990 2000 2020

Year
FIGURE 6.6 The information acquisition rate (left) for single-crystal inelastic experi-
ments is the product of the flux at the sample (expressed in nuclear reactor equivalent
MW units) and the number of useable pixels within which the scattered and incident
neutrons fall. Brockhouse was co-recipient of the 1994 Nobel Prize for developing the
single-pixel triple-axis spectometer (see Table O.1), which dominated inelastic neutron
scattering until around a decade ago. The development of pulsed spallation sources and
fast rotor chopper spectrometers has moved inelastic neutron scattering onto a growth
curve (Moore’s Law) driven largely by the electronic data-processing industry. The
neutron sources identified are the HFBR (High Flux Beam Reactor, Brookhaven National
Laboratory), HFIR (High Flux Isotope Reactor, Oak Ridge National Laboratory), and ILL
(Institut Laue-Langevin, France) reactors and the ISIS (Rutherford-Appleton Laboratory,
United Kingdom), SNS (proposed Spallation Neutron Source, Oak Ridge National Labo-
ratory), and ESS (European Spallation Source, currently unsited) accelerator-based facil-
ities. MAPS, HET, and MARI correspond to ISIS instruments at different stages of
development. [Physics World, 33 (December 1997).]
the construction of precisely such a source, the Oak Ridge Spallation Neutron
Source, whose completion will be the big event of the next decade for neutron
science.
SYNCHROTRON RADIATION
In the past 30 years, the use of infrared, ultraviolet, and x-ray synchrotron
radiation (SR) for condensed-matter and materials physics research, as well as
research in the other natural sciences, engineering, and technology, has blos-
somed. The pace and scientific range of SR utilization has increased even more
rapidly during the past decade because of source improvements, advanced instru-

mentation, and more beam time than was possible a decade ago. Further impetus
was provided by the construction of new facilities with extreme performance. As
a consequence of these developments, approximately 4,000 scientists from
academia, industry, and government laboratories now use U.S. SR facilities.
In the 1960s and 1970s, research was initiated using SR produced by the
bending magnets at storage rings designed for high-energy physics. As shown in
Figure 6.7, such rings provided about four orders of magnitude greater brightness
than the best in-laboratory sources. In addition, the radiation covered a very
broad spectrum, in contrast to the line source x-ray tubes then available. These
features made a number of previously unfeasible experiments possible.
FIGURE 6.7 History of (8 keV) x-ray sources. Brilliance (or brightness) is defined as
source intensity per illuminated solid angle. (Courtesy of Argonne National Laboratory.)

Because of the science and the large user communities resulting from the
first-generation sources, they were joined by second-generation, high-brilliance
rings designed specifically for SR research in the mid-1980s. The increased
brightness and the greater availability of these sources, as well as the increased
flux achieved by insertion devices at all sources, further expanded both the science
and the user community. (Insertion devices, known as wigglers and undulators,
are magnetic arrays that cause the charged particles to undergo quasi-sinusoidal
paths, producing far brighter radiation than can be achieved with bending mag-
nets at the same storage ring.)
During the past decade, third-generation rings [the Advanced Light Source
(ALS) and Advanced Photon Source (APS; shown in Figure 6.8) in the United
States, SPRING-8 in Japan, and the European Synchrotron Radiation Facility in
France], with still higher brightness (by 4 to 5 orders) and many straight sections
for insertion devices, have been constructed. At the same time, the first- and
second-generation rings have been modified so that their performances have
increased markedly. Such increases form the basis of revolutions in the research
that utilizes SR—a process that is likely to continue well into the next century
with new sources.
FIGURE 6.8 Overview of the recently completed Advanced Photon Source (APS) at
Argonne National Laboratory. Electrons circulate in the storage ring and emit brilliant x-
ray beams that are used to probe the structure of condensed matter at scales ranging from
the atomic to the macroscopic. (Courtesy of Argonne National Laboratory.)

The Past Decade
Protein Crystallography
The goal of understanding life has evolved into a large interdisciplinary
effort that integrates information extending from experimental results at the
atomic and molecular levels to studies of organelle, cellular, and tissue organiza-
tion and function. Atomic-level information will increasingly provide the means
through which biological function, and malfunction that leads to disease, will be
understood. Macromolecular crystallography has provided the vast majority of
information about three-dimensional biological structure and will play an even
greater role in the future. Information relating structure to function has also led to
the development and successes of new approaches to drug discovery (often called
structure-based drug design).
The unique properties of SR—namely, its tunability and high brilliance—
have allowed it to play a seminal role in these advances. So important is SR to
protein crystallography that 73 percent of new structures published in Nature
and 60 percent of those published in Science in 1995 used synchrotron-based
data, and this percentage continues to grow. Some of the most important results
include the structure of the myosin head, which has led to a molecular-level
interpretation of muscle contraction; the structure of cytochrome oxidase, which
is the enzyme that carries out the final step in mammalian respiration; the struc-
ture of the enzyme nitrogenase responsible for production of most of the assimi-
lable (fixed) nitrogen in our biosphere; the structure of the ribozyme, which is a
catalytic form of RNA; numerous plant and animal virus structures (for an impor-
tant example, see Figure 6.9), as well as studies of their interaction with potential
antiviral drugs; and structures of a variety of enzymes, like topoisomerases,
involved in DNA transformations and regulation.
Kinetic Studies of Structure

The five order of magnitude increase in photon flux provided by the first x-
ray SR sources immediately enabled time-resolved diffraction studies. Structural
biologists addressed the changes in muscle tissue as it contracts and expands and
have come to a detailed understanding of the mechanism of force generation.
Subsequently, time-resolved scattering and x-ray absorption spectroscopy (XAS)
studies, as well as the related studies of systems in excited states, have blos-
somed, providing kinetic understanding of reactions and processes that cannot be
obtained in other ways. Following are examples of other types of studies that
have benefited from time-resolved scattering and XAS:
1. In situ studies of thin film growth by sputtering, organometallic vapor

phase epitaxy, and molecular-beam epitaxy;

2. Both protein crystallographic and depolarization studies of atomic reorga-

nization in photosensitive biological molecules subjected to light pulses (see
Figure 5.3);
3. In situ small-angle x-ray scattering studies of the refinement of heavy
crude oils; and
4. Structural studies of phases formed during various stages of welding.
The examples illustrate a portion of the range of time-resolved studies that

have been performed thus far. With third-generation sources completed and
fourth-generation sources being planned, applications to faster processes, shorter-
lived states and more weakly scattering systems can be anticipated as we seek to
understand aspects of reactions at the atomic and molecular levels.
Surfaces and Interfaces

Both fundamental and applied x-ray scattering studies of surfaces and inter-
faces have flourished over the past decade at all of the x-ray facilities. Among the
FIGURE 6.9 Structural information is central to the development of models and cures for
disease, and today is largely established using methods and large facilities originally
developed for the condensed-matter and materials physics community. The figure shows
the exterior envelope protein (upper right) of the AIDS (acquired immunodeficiency syn-
drome) virus together with a neutralizing antibody (left) and the human CD4 receptor
(lower right). The structures are deduced from x-ray diffraction data collected at the
National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory.

most exciting of the fundamental studies have been those of continuous phase
transformations. SR studies of transformations between the different phases of
monolayers absorbed on flat, well-ordered substrates, as well as reconstructed
surfaces, have enabled significant tests of exact results from the theory of two-
dimensional physics. Similarly, the step-bunching transition on single crystal
surfaces, originally predicted theoretically, has been studied experimentally with
SR. The surface-scattering methods have also been used for studies of liquid-
surface and amorphous thin-film structures. A particularly interesting result is
that near the surface of liquid metals, there is metal atom layering.
Surface sensitive SR techniques have been applied increasingly to signifi-
cant technological problems. Several major projects have been aimed at under-
standing thin-film formation via vapor deposition and sputtering. Because the
normal surface-sensitive techniques cannot be used in these “high-pressure” situ-
ations, synchrotron-based surface-scattering studies now account for a large por-
tion of the existing in situ characterization of these processes. An important
extension of the surface-scattering technique is grazing incidence fluorescence
now being applied by several semiconductor manufacturing companies to micro-
contamination analysis of Si wafers.
Also of technological importance are the surface-sensitive electron-yield
techniques in the vacuum ultraviolet (VUV)/soft x-ray region, which measure
bond lengths of adsorbate/surface bonds and orientations of molecules adsorbed
on surfaces. These are now being used for practical applications such as deter-
mining the mechanisms governing the orientation of molecules of importance to
liquid-crystal displays. In addition, x-ray magnetic circular dichroism is having a
significant impact on the science of magnetic recording.
The number of applied problems involving surfaces, surface layers, and
interfaces is enormous. We anticipate enormous growth in experiments related to
corrosion, electrochemistry, tribology, environmental interfaces, and the like as
more beam lines are commissioned around the world. Electrochemistry deserves
special mention because already SR together with probe microscopies has trans-
formed this field from one primarily dependent on electrochemical measure-
ments and related modeling to the study of electrode processes at the molecular
level.
Microspectroscopy
The availability of the third-generation sources has made possible higher
resolution microspectroscopies. The higher brightness at ALS has enabled con-
struction of an improved scanning transmission x-ray microscope (STXM) as
well as a scanning photoelectron microscope (SPEM). The STXM is especially
useful for micro-composition and orientation measurements in multicomponent
polymers and organic systems. Spatially resolved x-ray photoelectron spectros-
copy is now being applied to a range of materials issues, such as examining

chemical structure of Ti-Al alloys reacted with graphite and chemical speciation
on bond pads of integrated circuits in order to correlate chemical state with
phenomena like adhesion and chemical residues in vias.
At APS, an x-ray microprobe with a FWHM focal spot size of 0.33 µm with
a flux density exceeding 5 × 1010 photons/m2 s (0.01 percent bandwidth) has been
developed. Using a root specimen in its natural hydrated state, elemental sensi-
tivity significantly better than 10 ppb and minimum elemental detection limit of
0.3 fg have been demonstrated. The x-ray microprobe is being used in variety of
environmental and biological research projects. Figure 6.10 shows that it is also
15
5 µm beam
InP(004)
0
Intensity (log(cts))
-1 +1
10 modulator
0
-1 +1
-2
laser
0
-4 -2 0 2
∆q/q 0 (%)
x-ray microbeam
1 µm
EM modulator
DFB laser
Electro-absorption
Modulator/Laser
FIGURE 6.10 X-ray microbeam diffraction study at the NSLS on an electro-absorption

modulator/laser device (lower figure). The upper figure shows the change in the strain
distribution on going from the modulator region to the laser region of the device. (Courte-
sy of Bell Laboratories, Lucent Technologies.)

extremely useful for the characterization of technologically important man-made

microstructures.
Insertion devices provide brilliance adequate for performing high-resolu-
tion inelastic scattering measurements of excitations in solids and liquids. X-
rays have the special advantage that they are not subject to the kinematic
restrictions that prevent neutrons from probing medium-energy excitations at
long wavelengths. In addition, their coherence as they emerge from modern
undulators is such that photon correlation spectroscopies, hitherto limited to
visible wavelengths emitted by ordinary lasers, can be extended to examine
slow dynamic processes at shorter distances than previously possible. Given
these twin advantages, it should come as no surprise that x-rays have yielded
some of the most exciting results in the physics of fluids and glasses, where
they have been able to examine portions of phase space inaccessible to both
neutron- and light-scattering techniques. Other progress has occurred in lower-
resolution measurements to examine excitations in various simple metals as
well as more complex oxides.
Photoemission Spectroscopy
Angle-resolved photoemission spectroscopy (ARPES) at SR sources has
proven to be a unique tool when addressing the question of the electronic struc-
ture of solids, most notably the variation of the band energies with respect to
momentum.
Over the last decade, such experiments have played an important role in
advancing our understanding of high-temperature superconductors. The signifi-
cant improvements in beam intensity and energy resolution obtained from
undulators and new spectrometers have facilitated the discovery of a number of
fascinating features in the electronic structure of the high-Tc superconductors.
The most notable consequence is the beginning of a detailed view of how conven-
tional band theory breaks down for these materials. In addition, ARPES has
provided images of the unconventional superconducting gap functions of the
cuprates.
Magnetic Scattering
Although the coupling of x-rays to magnetic moments is considerably smaller
than that of neutrons or electrons, the extremely high-SR intensities have enabled
qualitatively new kinds of experiments complementary to those performed with
neutrons. In particular, the availability of radiation of tunable energy and polar-
ization has led to spectroscopies that promise the separation of the orbital and
spin magnetization densities in solids. SR has made very precise characteriza-
tions of the magnetic behavior of a variety of rare-earth, transition-metal, and
actinide systems possible. The naturally high resolution not only allows the

determination of the magnetic periodicities with unprecedented accuracy, but

also allows magnetic correlations to be explored on micron length scales.
Infrared Investigations
One development that was not foreseen a decade ago was the rise of infrared
techniques using SR. For example, the vacuum ultraviolet ring at the National
Synchrotron Light Source (NSLS) at Brookhaven provides infrared light that is
103 times brighter than typical thermal sources and highly stable. Similarly, it
produces more power than thermal sources in the far infrared and is also a pulse
source suitable for time-resolved spectroscopy with subnanosecond resolution.
This source has enabled infrared spectroscopy to be applied to problems such as
the dynamics of adsorbates on metals and semiconductors, and photoconductivity.
X-Ray Absorption Spectroscopy

This is a very simple and powerful technique with applications too numerous
to list. To give an idea of what is possible, the committee considers briefly its use
in environmental science, a field driven by the tremendous need for new remedia-
tion and prevention technologies. Environmental science is therefore a growth
area for the application of methods from condensed-matter and materials physics.
The application of SR techniques, particularly XAS, to problems in environmen-
tal science has grown rapidly during the past decade. XAS is particularly useful
because easily interpretable data on chemical states can be collected in environ-
mentally relevant conditions (e.g., in the presence of water, at ambient pressures
and temperatures, at dilute metal ion concentrations greater than 10 ppm). The
resulting information is critically important for determining the toxicities, bio-
availabilities, transport properties, and environmental fate of metal ions in soils
and aquifers and for subsequently designing cost-effective and reliable
remediation.
The Next Decade

The main focus of U.S. efforts will be to fully develop the third-generation
sources that have only just come online. This means building functioning beam
lines capable of what is currently routine at the European Synchrotron Radiation
Facility (ESRF) in Grenoble (e.g., high-resolution inelastic scattering and photon
correlation spectroscopies, high-pressure diffraction). However, past experience
indicates that many of the new experimental techniques that will be developed at
the third-generation SR sources have not yet emerged. It seems likely that the
history of first- and second-generation sources, where some of the most fruitful
techniques were advanced only after experience with the source and instrumenta-
tion had been obtained, will be repeated.

Nevertheless, SR scientists are already planning fourth-generation sources

that will provide still greater brightness (about two orders of magnitude) and
subpicosecond pulses at successively shorter wavelengths using single-pass free-
electron lasers. The plans include a deep-ultraviolet source at Brookhaven Na-
tional Laboratory, a soft x-ray source at Argonne National Laboratory, and an x-
ray source providing radiation at wavelengths down to approximately 1.5 Å at the
Stanford Linear Accelerator Center. The ultimate facility will be based on a
superconducting linac of some 20-30 GeV feeding a farm of 50 or more 100-m-
long undulators with radiation from the ultraviolet to the hard x-ray.
As indicated in Figure 6.7, the FELs promise about eight-orders-of-
magnitude increases in peak brightness. They will provide diffraction-limited
radiation at their operating wavelengths with sufficient numbers of photons so
that data will generally be acquired with a single pulse. Thus, they are likely to
usher in a new era of short wavelength coherent imaging and subpicosecond
studies of electronic and atomic structure. Moreover the development of these
sources will enhance the impact of SR on biology, soil science, agriculture,
archeology, and other fields.
THE REINVENTION OF TRADITIONAL

CONDENSED-MATTER EXPERIMENTS
At the same time that the capabilities of large-scale facilities have been
dramatically expanding, there has been a quiet revolution in small-scale instru-
mentation. This revolution has had an enormous impact on both the efficiency
and capabilities of single investigators and groups working on small-scale mate-
rials experiments in traditional laboratory settings. From spectrum analyzers, to
top-loading dilution refrigerators, to personal computer (PC)-controlled param-
eter analyzers, the tools of the trade have evolved to the point where measure-
ments that once took from weeks to entire graduate student careers, can now be
routinely done in days, hours, or less. Laboratory instruments, computers, and
software to enable quick and easy automation of most laboratory measurements
are now available. Almost all commercial instruments come with IEEE GPIB
interfaces. Inexpensive PCs are pervasive, and commercial software packages
have been designed specifically for laboratory automation. The ongoing ad-
vances in microelectronics technology have spawned new generations of inex-
pensive yet extremely high-performance digital oscilloscopes, voltmeters, and all
sorts of parameter analyzers. In parallel there have been continuous improve-
ments in performance and reductions in the cost of systems such as dilution
refrigerators, pulsed lasers, and superconducting magnets. There are also new
types of commercial instruments that act as platforms for performing a number of
complex experiments on a sample, all under computer control. For example,
such probes had a huge impact on the development of the field of high-Tc super-

conductivity and are playing a very important role in the development and explo-
ration of new magnetic materials.
Another very exciting area of “small-scale” instrumentation involves lever-
aging microfabrication technology, as driven by the microelectronics industry, to
do or enable physics experiments. There are several different aspects of this. The
first relates to the custom design of electronic circuitry specifically configured for
some special laboratory instrumentation function. What used to require the effort
of numerous people hand-wiring large numbers of components together to even-
tually produce a rack full of instrumentation can now frequently be reduced to an
application-specific integrated circuit (ASIC) designed to the need, along with a
few other high-function, but standard, integrated circuits.
A second aspect of leveraging microfabrication involves special-purpose
technology developed to fulfill some engineering need, but using it for physics
applications as well. A good example of this is low-Tc superconducting electron-
ics. For the past several years high-quality foundry service has been available for
producing prototype superconducting digital circuitry. This same foundry ser-
vice has been used to fabricate on-chip experiments to study the physics of
Josephson junctions, the behavior of arrays of superconducting devices, the per-
formance of high-frequency mixers and antennae for radio astronomy, and so on.
In addition, this technology can be used to fabricate all manner of integrated
SQUIDs including, for example, magnetometers with small pickup-loop struc-
tures to be used in scanning SQUID microscopy applications. This is a fabrica-
tion service available to everyone at a very modest cost.
A third aspect of leveraging is related to microelectromechanical systems
(MEMS). MEMS is a rapidly growing engineering field, closely linked to the
microelectronics industry, that has developed a wide variety of devices such as
micromotors, microactuators, and microflow-controllers. MEMS in the form of
microcantilever structures are at the heart of many scanning-probe implementa-
tions. MEMS technology is beginning to provide some exciting opportunities to
do physics in unconventional ways on very small quantities of matter. At present,
cantilever structures in one form or another are the basis for many such experi-
ments, but it is clear that MEMS can provide an ideal platform for a wide variety
of physics experimentation. We can expect to see a rapid expansion of “labora-
tory-on-a-chip” concepts and implementations in the near future.
In their pursuit to gain control of entities of the very smallest dimensions,
scientists are developing extremely sensitive sensors to detect and analyze very
weak physical and chemical effects involving minute amounts of material. The
basic sensing element used in one such study is a silicon microcantilever like that
used in an atomic-force microscope. This microcantilever bends in reaction to
the forces imposed on it by various phenomena under investigation. Several
methods can be applied to detect the motion and deformation of the cantilever
including optical and electrical techniques, the latter using piezoresistors.

Because of their very small size, such microcantilevers—if properly designed—

feature high sensitivity and short response times.
There are two obvious prerequisites for experiments in condensed-matter
and materials physics. The first is measuring equipment, the second is interesting
specimens. As regards small laboratories, the key development is that interesting
specimens are becoming more and more indistinguishable from the measuring
equipment, in the shape of “experiments on chips.” Certainly examples exist of
outstanding physics being done with 20-year-old equipment on samples made in
a great variety of traditional ways. However, the overall efficiency and produc-
tivity of the research will be significantly enhanced through ongoing upgrades of
instrumentation and automation, both for measurement and fabrication. Incor-
porating upgrades in all the physics laboratories in the nation represents a sub-
stantial ongoing investment required to keep small-scale laboratory operations
competitive.
The scientific and technological future of nanofabrication and nanoscale
processing, which enables modern “experiments on chips,” is bright and exciting.
If, however, the momentum of this nanoscale revolution is to continue to grow
and its full promise to be realized, steps must be taken to ensure that the broad
research community has appropriate and effective access to the full arsenal of
capabilities in this area, capabilities that must be at the very forefront of
nanofabrication and nanoprocessing technology. Because of the complex and
multifaceted nature of this technology, an essential component of this access
must be via national user facilities, such as the current National Nanofabrication
Users Network (NNUN) supported by the National Science Foundation. It is
essential that each facility of this sort be adequately supported so that it can
broadly provide world-class research capabilities to academic, industrial, and
government researchers and thus continue to push the state of the art. It is also
essential that each encompass a broad range of nanofabrication and processing
capabilities so that users can take a nanoscale science or technology research
project from concept through to a working device or functional structure. Fur-
ther, it is essential that each facility be adequately staffed with highly competent
professionals oriented toward introducing new users to the technology, educating
the research community about nanofabrication, and facilitating users in success-
fully exploiting exciting new research opportunities.
MAN-MADE EXTREME CONDITIONS

The urge to discover new states of matter has been one of the deepest moti-
vations in condensed-matter and materials physics. An important route to dis-
covery has been the fabrication of new materials—new compounds, alloys, and
combinations of metals, ceramics, and organic matter. Frequently it has been
possible to design new materials for specifically desired properties. It seems
likely that modern fabrication techniques will permit us to make a host of new

objects and devices that are beyond our current imagination. Numerous advances
in the fabrication of new materials are discussed in this report.
Another path to the discovery of new phenomena has been through subject-
ing matter to unusual or extreme conditions of low temperature, pressure, and
magnetic field. Measurements under such unusual conditions have sometimes
led to dramatic surprises, with important results that could not have been antici-
pated in advance. Here, the committee looks at a few of the results and describes
the present state of the technology and future prospects. There are common
themes for research under extreme conditions: (1) The limit in the equilibrium or
static value of minimum temperature, maximum pressure, or maximum magnetic
field is 10 or more times less than transient values that can be achieved. (2) The
instrumentation required for preparing specimens and performing measurements
has become increasingly sophisticated and frequently requires facilities available
only at large laboratories. (3) The miniaturization of specimens and apparatus is
becoming increasingly beneficial to each technology.
Matter at Very Low Temperatures

The classic unexpected result in condensed-matter physics was the discovery
of superconductivity in 1911, just a few years after helium was first liquefied.
The electric resistance of superconductors becomes zero. The low temperatures
were critical for producing the phenomenon because thermal energy at higher
temperatures disrupts the delicate interactions between electrons. At low-enough
temperatures, the electrons form the paired state responsible for superconductiv-
ity. It took another 50 years before the underlying phenomenon was really
understood. The discovery was made primarily because the experimenter wanted
to see how the nature of conductors changed as they were cooled. Similarly, the
superfluid states of the helium isotopes, 4He and 3He, were discovered because of
developments in low-temperature technology and curiosity about how matter
behaved at lower temperatures. When the thermal motion is reduced, delicate
new phenomena appear.
The minimum temperature achieved under static conditions with the ther-
mometer, coolant, and specimen under investigation is 1 mK. Temperatures
down to 10 mK can be produced routinely with commercially available appara-
tus in which pumped 3He is circulated through heat exchangers. Lower tem-
peratures require a different principle: magnetic cooling. Nuclei of a metal
(usually copper) are polarized at millikelvin temperatures in a magnetic field of
10 T. The copper and specimens attached to it are then thermally isolated and
the magnetic field is removed. The polarized nuclear magnetic moments be-
come very cold. Electrons in the copper transfer heat between the specimen
and the cold nuclei.
An important challenge that has attracted quite a number of experimentalists
in this field has been the attempt to cool dilute mixtures of 3He in liquid 4He to

very low temperatures. The goal has been to discover a superfluid pairing transi-
tion similar to that which occurs in pure liquid 3He. The paired state might be
quite different from that in the pure liquid. No one has succeeded in cooling the
dilute mixtures to temperatures less than 200 µK. Heat transfer between the
metal coolant and the dilute mixture is quite difficult.
Significantly lower temperatures have been achieved for isolated systems
not in thermal equilibrium with surrounding matter. One class of experiments
has been the study of spontaneous nuclear magnetism in metals such as copper,
silver, and platinum. At the end of the magnetic cooling process, after the large
magnetic field used to polarize the nuclei is removed, the magnetic moments are
quite cold. The thermal equilibrium times are quite long, sometimes more than
108 seconds. Through clever determinations of the spin-entropy, temperatures as
low as a tens of picokelvin have been deduced. The method has been used to
examine a variety of unusual states of magnetic order. As Figure 6.11 illustrates,
some of the experiments have even been conducted in connection with neutron
diffraction at reactor facilities. The neutrons were used to image the nuclear
magnetic moments in the ordered state.
A spectacular example of the cooling of a metastable isolated system of
matter has been the studies of Bose-Einstein condensation in gases of sodium,
rubidium, and lithium. Modern optical techniques in conjunction with magnetic
traps and radio frequency fields have been used to cool dilute gases of these
atoms to sub-microkelvin temperatures. The hot atoms are kicked out of the
magnetic trap by the radio frequency electromagnetic fields. At the very low
temperatures, the atoms obeying Bose statistics can simultaneously occupy the
same state—the condition for Bose-Einstein condensation. Quantum interfer-
ence between clusters of atoms has been demonstrated. The effect is analogous
to interference between two sources of coherent light.
Matter at Very High Pressures

For most of this century, progress in achieving high pressure in matter was
achieved by building ever larger series of cascaded metal pistons to compress
material. By 1980 a dead end had apparently been reached. Even with the
strongest steel alloys, the limiting static pressure that could be produced on
samples of milliliter volumes was in the range of several hundred kilobars. The
invention of the diamond anvil pressure cell led to a major advance in high-
pressure science. Small diamond crystals are formed into narrow tips to be
pressed against each other. Typical contact regions have a diameter less than
10 µm. Forces of order of only a few Newtons can produce megabar pressures
over such small areas. To achieve high pressures, the region around the narrow
tips must be defect free. The smaller the region, the higher the probability that
there are no defects.
The maximum static pressure achieved by the diamond anvil method is a

FIGURE 6.11 Photograph of nuclear demagnetization apparatus installed on a cold-

neutron guide emanating from a nuclear reactor. The apparatus was used to discover the
ordering of the nuclear spins in elemental copper at less than 58 × 10−9 K. (Courtesy
RISØ National Laboratory, Roskilde, Denmark.)

little more than 1 Mbar. Quite a number of new dense phases of matter have been
discovered. Of particular interest has been the transition of normally completely
insulating materials such as solid xenon and sulfur in conducting metallic states.
As the atoms are squeezed closer together, the outer electrons become free.
The small size of the specimens presents a special challenge in instrumenta-
tion. The entire experiment has to be built in micron-sized volumes. Neverthe-
less, nanotechnology has been used to apply electrical leads and even magnetic
resonance coils to diamond anvil devices. The crystal structure of new high-
pressure phases of matter has been determined with x-rays from synchrotron
sources. The measurement of the pressure is also a difficult matter. Calculation
of the force per unit area is frequently insufficient because the stresses are not
uniformly distributed. Instead, a combination of calculated pressures and ex-
trapolation of material properties such as fluorescence frequencies must be care-
fully compared in many experiments to establish a reliable pressure scale.
A special goal in high-pressure research in recent years has been the search
to find the elusive metallic state of solid hydrogen. It would be an especially
interesting discovery because hydrogen should be one of the easiest materials for
which to calculate an equation of state with fundamental theory. The pressure
predicted for the metallic transition in hydrogen is very close to the values cur-
rently being produced.
Beyond providing information about systems of fundamental interest to
condensed-matter physicists, high-pressure research is essential for understand-
ing the composition and properties of Earth’s interior. Recent experiments have
led to significant new findings on phase transformations associated with deep
earthquakes, for example.
Further progress in achieving higher pressures will probably be achieved
through use of stronger materials. For example, studies of tungsten and iron
suggest that they become even stronger at megabar pressures.
Transient pressures greater than 2 Mbars have been obtained in shock waves.
The maximum pressure lasts only a few nanoseconds. Nevertheless, most of the
existing high-pressure and high-temperature data have been obtained with the use
of gas guns, high explosives, and even nuclear detonations. The development of
high-intensity lasers provides a potentially attractive complement to these meth-
ods, particularly for equation of state studies at high energy densities. By focus-
ing a short-pulse, intense laser beam on a sample, a rapidly expanding plasma is
created, which, in turn, drives a shock wave into the sample; laser-induced shock-
wave experiments to obtain high-pressure data (in excess of a megabar) have
been carried out for more than a decade. However, concerns have existed regard-
ing the accuracy of the data owing to the lack of planarity of the shock front,
preheating of the material ahead of the shock front, difficulty in determining the
steadiness of the wave front because of the small sample size, and the absence of
absolute pressure and volume data. Recent improvements in beam smoothing

and other experimental developments have improved the quality of the propagat-
ing shock wave.
Matter in Large Magnetic Fields

Large magnetic fields represent yet another extreme condition to impose on
matter. Frequently the large fields are imposed in conjunction with low tempera-
tures. A large magnetic field can orient material, confine electrons in conductors
to particular energy states and locations, and produce specially selected spin
states of nuclei and electrons. Figure 6.12 illustrates how the range of accessible
phenomena grows with the magnetic field strength, while Figure 6.13 shows the
steady growth in man-made fields over the last century. Examples of dramatic
discoveries in recent years are the integer and fractional quantum Hall effects.
Both were discovered by accident—again—because the technology was avail-
able to produce the required extreme condition and experimentalists were inter-
ested in how matter changed under the new conditions. Both are discussed in
other sections of this report.
FIGURE 6.12 Higher fields are associated with higher energies, smaller length scales,
and more extreme technologies and environments. (Courtesy of Bell Laboratories, Lu-
cent Technologies.)

FIGURE 6.13 Magnet technology, as expressed in the maximum field reached in nonde-
structive experiments, has grown exponentially over the last century. We anticipate that
the incorporation of high-Tc superconductors will assure continued growth. (Courtesy of
Bell Laboratories, Lucent Technologies.)
The highest static magnetic field achieved is 37 T (80,000 times Earth’s

magnetic field strength). The large field is achieved with a combination of two
concentric magnets—a water-cooled copper solenoid carrying a large current on
the outside and a superconducting solenoid on the inside. Today’s superconduc-
tors alone cannot carry enough current to produce a magnetic field greater than
about 15 T. The outer copper (resistive) magnet produces the additional 22 T.
The ultimate design limit on the maximum strength of steady magnetic field
is determined by the strength of the material that carries the current. The field
produces a radial outward force proportional to the current passing through the
solenoid wire. Using the strongest materials that exist, the maximum field is
approximately 50 T.
Much larger fields can be achieved for shorter times. Large current pulses
through wire coils have been used to produce fields greater than 75 T for tens of
microseconds. These magnets can be repeatedly cycled with current pulses to
obtain masses of data. The maximum fields, those in excess of 100 T, are
produced by explosive technology. Typically, current-carrying cylinders are
rapidly imploded and a very large magnetic field is produced as the tube col-
lapses. The transient-field experiments share a challenge with the transient-
pressure experiments—the data must be obtained in nanoseconds or less. The

transient experiments have been important in gaining information about the high-
field behavior of high-temperature superconductors, the optical properties of
matter, and the conducting properties of unusual metallic compounds.
The Next Decade

Matter under extreme conditions is as obvious a frontier of science as high-
energy physics or astronomy. It is also equally easy to state simply the future
program for this field—to subject matter to ever higher pressures, lower tempera-
tures, and higher magnetic fields and to use every conceivable visualization tool
to see what happens. Spectacular opportunities will arise because of new infra-
structure, such as the National Ignition Facility, actually designed for fusion
research at the Lawrence Livermore Laboratory, and the 100 T pulsed magnet
foreseen at Los Alamos. Other significant advances will arise from improved
visualization capabilities, which will follow from installation of high-pressure
cells and high-field magnets at advanced light and neutron sources.
The scientific problems addressable by experiments with samples in extreme
environments will span the range of condensed-matter physics. Past performance
suggests that such experiments will make important contributions to resolving
the problems posed by the high-temperature superconductors as well as many
other fascinating materials both known and unknown. We also look forward to
breakthroughs in areas much further from the traditional core of condensed-
matter physics. Recent examples include optical tweezers, whose development
was closely interwined with the quest for ultra-cold laser-cooled matter, and
magnetic resonance imaging.
COMPUTATIONAL MATERIALS PHYSICS

The modern high-speed computer is a remarkable device, made possible in
part by fundamental discoveries and continuing advances in condensed-matter
and materials physics. With clock speeds now routinely reaching as high as 500
MHz, small, mass-produced workstations have a computational power that would
have been possible only with giant supercomputers (now viewed as dinosaurs)
just a few years ago. Computers and their components are now so sophisticated
that each succeeding generation cannot be built without making full use of the
computational power of the existing generation. In addition to improving them-
selves, computers have become powerful tools in the study of a wide variety of
condensed-matter phenomena and materials. Figure 6.14 shows the remarkable
progress in high-end computing, together with its implications for one particular
problem, the computation of turbulence in fluids.
The history of computing has been one of frantic attempts to find architec-
tures and software that can deal with ever-changing hardware limitations. Less
than 20 years ago, memory was very expensive (witness today’s Year 2000

1013
Serial
ASCI ID system
Origin 2000
Vector
1011
Cray T3D, CM-5
Parallel
Intel Delta, CM-200, etc
Distribute Intel Gamma, CM-2, etc J-90 series
CM-1, etc
10 9
Easy commercial
Operations per second
parallel computers Cray Y-MP
Cray X-MP
Cray-1
10 7 10 4
CDC 7600
CDC 6600 Rλ
IBM 7030
10 5 10 2
IBM 704
MANIAC three-dimensional
3 Navier-Stokes turbulence
10 10 0
SEAC
Electro-mechanical
accounting machine
1940 1950 1960 1970 1980 1990 2000 2010

Year
FIGURE 6.14. The plot shows the growth of the number of operations per second from
1940 to 2010 for the fastest available “supercomputers.” Objects of different shapes are
used to distinguish serial, vector, and parallel architectures. All processors until Cray-1
were single-processor machines. The line marked “three-dimensional Navier-Stokes tur-
bulence” shows, in rough terms, the extent to which the increased computing power has
been harnessed to obtain turbulent solutions by solving three-dimensional Navier-Stokes
equations. Turbulence is used here as an example of one of the grand and difficult
problems needing large computing power. The computing power limits the size of the
spatial domain over which computations can be performed. The Reynolds number
(marked on the right as Rλ) is an indicator of this size. (Courtesy of Los Alamos National
Laboratory.)

problems) and microprocessors were much slower than discrete component de-
signs. Today memory density has risen enormously and prices have fallen dra-
matically. Microprocessors have risen several orders of magnitude in speed and
gone from 8- to 64-bit word lengths. After some tumultuous history involving
exploration of different parallel architectures, shared-memory parallel systems
combining many processors communicating via high-speed digital switches are
now rapidly developing and have largely replaced pure vector processors. Clock
speeds for microprocessors are now so high that memory access time is often far
and away the greatest limitation on overall speed. One of the great software
challenges now is to find algorithms that can take maximum advantage of parallel
architectures consisting of many fast processors coupled together.
In addition to hardware advances, the last decade has seen some revolution-
ary advances in algorithms for the study of materials and quantum many-body
systems. Improved algorithms are crucial to scientific computation because the
combinatorial explosion of computational cost with increasing number of de-
grees of freedom can never be tamed by raw speed alone. (Consider the daunting
fact that in a brute force diagonalization of the lowly Hubbard model, each site
added multiplies the computational cost by a factor of approximately 64.)
In the last two decades computational condensed-matter and materials sci-
ence has moved from the initial exploratory stages (in which numerical studies
were often little more than curiosities) into the main stream of activity. In some
areas today, such as the study of strongly correlated low-dimensional systems,
numerical methods are among the most prominent and successful methods of
attack. As new generations of students trained in this field have begun to
populate the community, numerical approaches have become much more common.
Nevertheless it is fair to say that computational physics is still in its infancy.
Pushing the frontiers of computational physics and materials science is im-
portant in its own right but also important because training students in this area
provides industry and business with personnel who not only have expertise on the
latest hardware architectures but also bring with them physicists’ methods and
points of view in analyzing and solving complex problems.
Progress in Algorithms
In spite of its great enthusiasm, the committee offers a warning before pro-
ceeding. Specifically, numerical methods have become more and more powerful
over time, but they are not panaceas. Vast lists of numbers, no matter how
accurate, do not necessarily lead to better or deeper understanding of the under-
lying physics. It is impossible to do computational physics without first being a
good physicist. One needs a sense of the various scales relevant to the problem at
hand, an understanding of the best available analytical and perturbative ap-
proaches to the problem, and a thorough understanding of how to formulate the
interesting questions.

Electronic Structure Algorithms

The goal of electronic structure calculations is to compute from first prin-
ciples or with approximate methods the quantum states of electrons in solids and
large molecules. This information is then used to predict the mechanical, struc-
tural, thermal, and optical properties of the materials. The outstanding problems
are ones of computational efficiency for large-scale calculations and conver-
gence to the thermodynamic limit. Indeed, the calculations are so complex and
time consuming that real-time dynamics can be followed only for pico- or
nanoseconds.
Perhaps the single most dramatic development in the last decade has been the
advent of the Car-Parrinello method, which has enormously enhanced the effi-
ciency of electronic structure calculations. This method calls for adjusting the
atomic positions and the electronic wave functions at the same time to optimize
the Hohenburg-Kohn-Sham density functional. Additional efficiencies come
from use of fast Fourier transform techniques to compute the action of the Hamil-
tonian on the wave functions without the necessity of computing the full Hamil-
tonian matrix.
Another area of intensive investigation has been the search for so-called
“Order N” methods. The idea is to find approximation schemes in which the
computational cost rises only as the first power of the number atoms or electrons,
as opposed to some higher power (~3) as is typically the case. So far, this has
been attempted only for tight-binding models involving spatially localized orbit-
als for the electrons. It is not yet clear that the problem will be solvable, but
research in this direction is important if we are going to be able to do larger and
more complex structures. Other techniques under investigation include adaptive
coordinate, wavelet, and direct grid/finite element methods that are useful in
situations in which the number of plane waves needed to represent atomic orbit-
als is very large.
The Kohn-Sham local-density functional approximates the many-body ex-
change-correlation corrections to the energy by a functional of the local density.
It has been very successful and is finally winning support within the computa-
tional chemistry community. An important area of current research involves
generalized gradient expansion corrections to the local-density approximation.
In several examples, simple local-density approximations fail to give correct
structures but appropriate gradient expansion functionals work. In general, how-
ever, it is often still difficult to obtain the chemical accuracy required.
Monte Carlo Methods

Fermion Monte Carlo techniques continue to be plagued by the “sign prob-
lem.” Because of the sign reversals that occur in quantum wave-functions when
two particles exchange places, not all time histories have positive weights in the

Feynman path integral. This means that the weights cannot be interpreted as
probabilities that can be sampled by Monte Carlo methods. The fixed-node
approximation attempts to get around this problem by specifying a particular
nodal structure of the wave function. This has yielded very useful results in some
cases in which the nodal structure is understood a priori. Some workers are now
moving beyond small atoms and molecules to simple solids and have obtained
good results for lattice constants, cohesive energies, and bulk moduli.
Fermion Monte Carlo path integral methods continue to be applied success-
fully to lattice models such as the Hubbard model, but again the sign problem is
a serious limitation. For example, it is still difficult to go to low-enough tempera-
tures to search for superconductivity, even in highly simplified models of high-Tc
materials.
Bosons, which are much easier to treat numerically, also pose interest-
ing problems. “Dirty boson” models have been used to describe helium films
adsorbed on substrates and to treat the superconductor-insulator transition. With
this model one makes the approximation that Cooper pairs are bosons and as-
sumes (not necessarily justifiably) that there are no fermionic degrees of freedom
at zero temperature.
Cluster Algorithms in Statistical Mechanics

One serious problem in the Monte Carlo simulation of statistical systems
near critical points is the divergence of the characteristic timescales. The com-
puter time needed to evolve the system to a new statistically independent state
diverges as some power of the correlation length or system size, LMCd+z where d
is the dimensionality. Cluster algorithms have been extremely successful on
certain classes of problems (such as the Ising and XY models and certain vertex
models) and are able to reduce the dynamical exponent zMC to nearly zero. This
is accomplished by constructing clusters of spins, and for each cluster, choosing
a random value of spin that is assigned to the individual spins it contains. Such a
move cannot be implemented in an ordinary Metropolis algorithm because the
Boltzmann factor would make the acceptance rate of the move essentially zero.
The trick is to have the probability that a cluster grows to a particular size
and shape be precisely the Boltzmann factor for the energy cost of flipping the
cluster. This is a very tiny probability, but it is canceled by the fact that there are
a huge number of different possible clusters that could have resulted from the
random-growth process.
This has been a very important advance. Unfortunately there are still many
cases (such as frustrated spin systems) for which cluster methods cannot (as yet) be
applied because of technical problems similar to the fermion minus-sign problem.

Density-Matrix Renormalization Group

A revolutionary development in computational techniques for quantum sys-
tems is the “density matrix renormalization group.” The essential idea is to very
efficiently determine which basis states are the most important to keep to be able
to describe the quantum ground state. The procedure is the first one ever found
that gives exponentially rapid convergence as the number of basis states is in-
creased. It applies to essentially any one-dimensional model with short-range
forces, even random systems without translation symmetry and fermion systems.
Using this technique it is now easy to compute ground state energies and correla-
tion functions to 10-digit accuracy on a desktop workstation. Ongoing work is
extending the technique to excited states and to higher dimensions.
Computational Physics in a Teraflop World

In this section we contemplate questions of the future of computation and what
can be (optimistically) done with the next factor of 1000 in computing power.
Glassy Systems, Disorder, and Slow Dynamics

At first sight, these problems do not seem well suited for more computer time.
They are too hard. Experimentally, the phenomena are spread over fifteen decades
in frequency, and even that dynamical range in the experiments is often not enough
to reach firm conclusions. Current simulations span perhaps three decades: one
might think that three more won’t make an overwhelming improvement.
There are two reasons to be optimistic. First, in numerical simulations, it is
straightforward to watch individual atoms/spins/automata relax. The last decade
has seen tremendous progress in the visualization and study of spin glasses,
charge density waves, glassy behavior in martensites, and “real” glasses. We are,
however, barely into the scaling region for many of these simulations: even if the
scaling region grows only logarithmically with the timescale, three more decades
might make the patterns clear.
Second, there is every reason to believe that we can get around these slow
timescales. There is no reason for our methods for relaxing glassy systems to be
as inefficient as nature. Until now we have mainly developed techniques to
mimic nature with as little wasted effort as possible. This was sensible for
studying systems in which nature relaxes efficiently; when you are barely able to
follow the system for a nanosecond, you study systems that relax rapidly. Now
that we are turning to problems for which nature is slow (for example, glasses and
phase transitions) we are making rapid strides in developing acceleration algo-
rithms. In particular, because we are more likely to gain the next factor of 1000
in computing power by increasing the number of processors rather than through

raw speed increases, we will naturally learn new algorithms for relaxation to
exploit the extra processors.
Quantum Chemistry and Electronic Structure of Materials

With these problems we are not confused about the physical behavior. For
these problems, the answers to the interesting questions inherently demand im-
mense precision. Quantum chemistry is difficult not because the systems are
complex and subtle, but because the standards are high. All of chemistry is con-
trolled by reaction and binding energies that are tiny compared to total energies.
Electronic-structure calculations for materials face exactly the same problem. We
can now study only relatively simple molecules and crystal structures; with the next
generations of machines and algorithms, this will change qualitatively.
Structured Systems: From Inorganic Industrial Materials to Proteins

These are systems for which there are huge ranges of length scales and
timescales, which interact in nontrivial ways. We have to understand the physics
and materials science on each scale and connect together the properties at differ-
ent scales. The algorithms appropriate to the models at different scales can be
quite different from each other.
The category of “industrial materials’’ includes ceramics, concrete, poly-
crystalline metals and alloys, and composites. Their important properties are
normally almost completely removed from the world of perfect crystals and
equilibrium systems often studied by mainstream physics. The wearing proper-
ties of steel, the resistance of concrete to cracks, the thermal and electrical prop-
erties of polycrystalline metals—all are dominated by the mesostructure, the
detailed arrangement of domain walls, pebbles, and grains.
Three issues must be confronted to make progress. First, the materials are
disordered. Second, they display history dependence; for example, the polycrys-
talline domains in metals are dependent in detail on how the metal was cast,
rolled, and stamped during its manufacture. Third, the systems have a large range
of scales. The dynamics of grain boundaries under external strain is determined
by the dynamics of the individual line dislocations that make them up. The line
dislocations interact logarithmically (in inscrutable ways), and one can only simu-
late them at the current level of knowledge. Their dynamics, in turn, is deter-
mined by atomic-scale motion; the diffusion of vacancies and the pinning to
inhomogeneities (and to other line dislocations) are crucial to understanding their
motions. It is this enormous range of scales that we can only hope to disentangle
with large-scale simulations (see Figure 6.15).
Proteins and biomolecules provide similar problems. The molecular biolo-
gists separate their structures into primary, secondary, and tertiary precisely as a
set of length scales on which the structure is organized. The functional behavior

FIGURE 6.15 Million-atom molecular dynamics simulation of ductile behavior in

nanophase silicon nitride, which is being explored for its extraordinary resistance to frac-
turing under strain: a 30 percent strain is required to completely fracture the nanophase
system, while only 3 percent is required for single-crystal silicon nitride. Shown is the
system before it fractures under an applied strain of 30 percent and a zoom-in to atomic
scale visualizing that the crack front advances along disordered interfacial regions in the
system. It is along the amorphous intercluster regions where the crack propagates by
coalescence of the primary crack with voids and secondary cracks. (Courtesy of Louisi-
ana State University.)
on the largest scales depends in detail on the dynamics and energetics not only
down to the protein level, but even down to the way in which each protein is
hydrated by its aqueous environment.
Quantum Computers
Theoretical analysis of the quantum computer, in which computation is per-
formed by the coherent manipulation of a pure quantum state, has advanced
extremely rapidly in recent years and indicates that such a device, if it could ever
be constructed, could solve some classes of computational problems now consid-
ered intractable. A quantum computer is a quantum mechanical system able to
evolve coherently in isolation from irreversible dephasing effects of the environ-
ment. The “program” is the Hamiltonian. The “input data” is the initial quantum
state into which the system is prepared. The “output result” is the final, time-
evolved state of the system. Because quantum mechanics allows a system to be
in a linear superposition of a large number of different states at the same time, a
quantum computer would be the ultimate “parallel” processor.
The basic requirement for quantum computation is the ability to isolate,
control, and measure the time evolution of an individual quantum system, such as
an atom. To achieve the goal of single-quantum sensitivity, condensed-matter
experimentalists are pursuing studies of systems ranging from few-electron quan-
tum dots to coherent squeezed photon states of lasers. When any of these reach
the desired single-quantum limit, experiments to probe the action of a quantum

gate could be immediately designed. Recent theory shows in principle how to

form different types of gates and provides error-correcting codes to enhance
robustness. At this point it is quite unclear if a practical system can be developed,
but many clever ideas are being explored. Interesting physics is sure to result
and there is at least a remote possibility of a tremendous and revolutionary
technological payoff.
Several groups have reported an experimental realization of quantum com-
putation by nuclear magnetic resonance (NMR) techniques. The race is now on
to demonstrate more complex quantum algorithms, to compute with more quan-
tum bits than the two bits of the first demonstration, and to verify error-correction
techniques.

Tools for visualizing atoms and electrons have been at the center of con-
densed-matter and materials physics since Bragg and von Laue first observed x-ray
diffraction from crystals nearly 100 years ago. These tools will remain at the center
of the field and many others, from catalysis to biochemistry. The last decade has
seen great progress in research performed using apparatus of all scales.
In the area of medium-scale infrastructure, the three important developments
have been widespread access to sophisticated electron microscopes and related
equipment, the exploitation of the Cornell nanofabrication center, and the rein-
vigoration of U.S. high-field magnet research by the founding of the National
High Field Magnet Laboratory. Access to equipment has fueled and will doubt-
less continue to fuel improved understanding and applications of bulk materials,
surfaces, and interfaces. Beyond enabling U.S. academe to participate in and
thereby greatly accelerate the development of mesoscale (between atomic and
macrosopic scales) physics, the Cornell nanofabrication center has been an ex-
traordinarily fertile training ground for the U.S. microelectronics industry. The
National High Field Magnet Laboratory will provide access to a scientific fron-
tier—a key site for discoveries and technological developments ranging from
magnetic resonance imaging to the quantum Hall effect.
Turning finally to large-scale facilities of a type that can only exist at na-
tional laboratories, the major events have been the commissioning of third-gen-
eration synchrotrons at the Argonne and Lawrence Berkeley laboratories and the
decision to recapitalize U.S. neutron science via construction of a pulsed spalla-
tion source at Oak Ridge. The synchrotrons will produce the x-rays and light
necessary for the United States to compete in emerging areas such as time-
resolved protein crystallography. Even though a U.S. scientist (Shull) shared the
1994 Nobel Prize for inventing neutron scattering in the 1950s (see Table O.1),
the Europeans have since then established a clear lead. The Oak Ridge source
will reestablish U.S. competitiveness in this area, which over the last decade has

proven so vital for imaging atoms and spins in materials ranging from high-
temperature superconductors to polymers.
In previous decades, key events in condensed-matter and materials physics
have been the exploitation of inventions and investments in large facilities. The
inventions and the facilities are devices with the special purpose of being tools
for condensed-matter and materials physics. The last decade is unique in that the
major event relating to such tools is actually not directly connected with inven-
tions and facilities. Instead, it is the same phenomenon that has profoundly
transformed nearly all other aspects of our society—namely, the information
revolution. An obvious consequence of the information revolution for condensed-
matter and materials physics is the recent progress in computational materials
science. Less obvious but equally important is the ability to collect and manipu-
late progressively larger quantitative data sets and reliably execute increasingly
complex experimental protocols. For example, in neutron scattering, data gather-
ing rates and, more crucially, the meaningful information content, have risen in
tandem with the exponential growth of information technology
What will happen in the next decade? Although we cannot predict inspired
invention, we anticipate progress with ever-shrinking and more-brilliant probe
beams and increasingly complete, sensitive, and quantitative data collection. One
result will be the imaging and manipulation of steadily smaller atomic land-
scapes. Another will be the analysis and successful modeling of complex mate-
rials with interesting properties in fields from biology to superconductivity.
The promised performance improvements with applications throughout ma-
terials science will come about only if balanced development of both large-scale
facilities and technology for small laboratories takes place. For example, deter-
mination of the crystal structures of complex ceramics and biological molecules
is likely to remain the province of neutron and synchrotron x-ray diffraction,
performed at large facilities, while defects at semiconductor surfaces will most
likely remain a topic for electron and scanning-probe microscopy, carried out in
individual investigators’ laboratories and small facilities. Thus, the cases for
large facilities and small-scale instruments are equally strong. Although the
larger items such as the neutron and photon sources appear much more expensive
than those that benefit a single investigator, recent European experience suggests
that the costs per unit of output do not depend very strongly on the scale of the
investment, provided of course that it is properly chosen, planned, and managed.
Information technology is also blurring the difference between large and small
facilities, as they all become nodes on the Internet. One important upshot will be
that the siting of large facilities as well as the large-versus-small facility debates
will largely cease to be of importance to scientists.
In addition to the construction of large facilities such as the SNS and APS,
healthy research in instrumentation science is crucial to the development of
improved tools for atomic visualization and manipulation. Although we have
impressive success stories to point at, as in the dominance of the probe micros-

copy business, we strive for similar success in other areas of instrumentation

that are important for both research and manufacturing. In the United States,
scientific research and instrumentation have traditionally had an uncomfort-
able relationship. Although it is very important that instrumentation programs
be science-driven and not isolated, sometimes long lead times and the need for
expert research in the instrumentation itself (for example, in advanced lithog-
raphy and electron, x-ray and neutron optics) require that special investment
be allocated for instrumentation. The absence of such middle-scale invest-
ment as well as a perceived lack of intellectual respectability are key reasons
why the nation is lagging in beam technology and science. A solution would
be the development of centers of excellence in instrumentation research and
education, the latter being an equally important role for this research. A model
might be the National High Field Magnet Laboratory, which has recently
revived magnet research in the United States. It is also clear that viable
centers can exist in already strong centers of materials research.
The committee’s list of priorities is designed to enable the United States to
recapture its leadership in scientific tools for condensed-matter and materials
physics and their exploitation. The goals to be achieved by the large neutron and
synchrotron facilities are obvious—namely, to duplicate and then to exceed what
the Europeans can do today. The recapitalization of the university laboratories
will serve the similarly obvious purpose of maintaining the efficiency and quality
of university research. The nanolithography investment will maintain user facili-
ties in an area of extraordinary importance in materials research as well the U.S.
economy. The medium-scale centers devoted to topics such as electron optics
and high magnetic fields will serve not only to develop new technologies in the
areas they are specifically devoted to, but also to establish a flourishing culture of
scientific instrumentation within condensed-matter and materials physics. Fi-
nally, condensed-matter and materials physics needs to take advantage of all
available information technology to continue to move toward its central goal of
seeing all the atoms and electrons all of the time.
Outstanding Scientific Questions

• Can we manipulate single atoms fast enough to make devices?
• Can we use computation to predict superconductivity in complex materials?
• Can we make inelastic scattering using x-rays, neutrons, and electrons as
important to materials science and biology as elastic scattering is today?
• Can we image and manipulate spins on the atomic scale?
• Can we develop a nondestructive subsurface probe with nanometer reso-
lution in three dimensions?

Priorities
• Build the Spallation Neutron Source and upgrade existing neutron sources.
• Fully instrument and exploit the existing synchrotron light sources and do
R&D on the x-ray laser.
• Build state-of-the-art nanofabrication facilities staffed to run user pro-
grams for the benefit of not only the host institutions but also universities, gov-
ernment laboratories, and businesses that do not have such facilities.
• Recapitalize university laboratories with state-of-the-art materials fabri-
cation and characterization equipment.
• Build medium-scale centers devoted to single issues such as high mag-
netic fields or electron microscopy.
• Exploit the continuing explosion in information technology to visualize
and simulate materials.

Changes in the R&D Landscape
Science has been a powerful agent of change throughout history. Science

expressed through technology has redefined warfare, enabled economic growth,
and extended the lifetimes and enhanced the well-being of billions of people.
Over the past half-century, condensed-matter and materials physics has pro-
foundly affected our lives, ushering in the information age and contributing to
advances in communications, computing, medicine, transportation, energy, and
defense. These advances have transformed the economy and dramatically altered
our worldview. They have also changed the environment (the R&D landscape) in
which science is performed.
FROM THE COLD WAR TO THE GLOBAL ECONOMY

Condensed-matter and materials physics is a young field. Although compo-
nents of the field existed earlier, its modern development was enabled by the new
discoveries in the 1930s of quantum mechanics and the wave nature of the elec-
tron. Its emergence as a discipline was heralded by the invention of the transistor
in 1947. In the brief 50 years since then, an impressive understanding has been
achieved of the structure and properties of materials on the atomic scale. Accom-
panying this understanding have been extraordinary technological develop-
ments, including the integrated circuit, optical fibers, solid-state lasers, and high-
temperature superconductivity.
Powerful forces have driven the development of condensed-matter and mate-
rials physics. In the beginning, the desire was to replace inconvenient and bulky
vacuum tubes with solid-state devices. Then came World War II with radar and
274

CHANGES IN THE R&D LANDSCAPE 275
defense technology. The arms race, Sputnik, the energy crisis, and the informa-
tion revolution stimulated continued growth in the field over the subsequent
decades. For most of this period, there was sustained growth in the federal
investment in science, including condensed-matter and materials physics. This
federal role in fundamental research, originally articulated by Vannevar Bush at
the end of World War II in Science: The Endless Frontier,1 was substantially
justified on the basis of national defense.
In the late 1980s, the end of the Cold War, the emergence of the global
economy, and the growing federal deficit combined to shake the foundations of
the national R&D enterprise. In the absence of a major military threat, invest-
ments in the defense establishment were reduced, including support for R&D.
Overall federal R&D investments, which peaked at $80 billion (in 1997 dollars)
in 1987, declined 20 percent in the following decade (see Figure 7.1) as priorities
shifted away from defense, and the desire to reduce the deficit applied increased
pressure to the discretionary part of the federal budget. Federally supported basic
research, performed mostly at universities, fared much better, increasing by 30
percent between 1985 and 1995 (see Table 7.1). This increase was dominated by
increased investment in the life sciences; only modest gains were recorded for
physics. At the same time, competition in the global economy (which itself was
enabled by communications advances rooted largely in condensed-matter and
materials physics) forced industry to sharpen the focus of its R&D investments.
Industrial R&D turned away from long-term physical sciences and toward projects
with more immediate economic return, reducing fundamental research invest-
ments that have been essential to the development of new technologies.
A DECADE OF CHANGE
The transition to the global economy represents a significant opportunity for
condensed-matter and materials physics. Competitiveness in a fast-moving
economy is critically dependent on advances in materials for a broad range of
applications from information technology to transportation to health care.
Condensed-matter and materials physics has responded effectively over the past
decade, supporting continued innovation in electronic and optical materials, while
developing new thrusts in complex fluids, macromolecular systems, and biologi-
cal systems (collectively known as “soft materials”), and nonequilibrium pro-
cesses. At the same time, science has become increasingly international, and
U.S. leadership in many areas of science and technology, including condensed-
matter and materials physics, is being challenged. Continued progress in con-
densed-matter and materials physics is critical to sustained economic competi-
1Vannevar Bush, Science the Endless Frontier: A Report to the President, U.S. Government Print-
ing Office, Washington, D.C. (1945), reprinted by the National Science Foundation, Washington,
D.C. (1960).

90
80
Non-Profits
Federal R & D Expenditures
70
(billions of 1997 dollars)
60
Industry
50
40
Federal Government
30
20 FFRDCs*
10
Universities
0
1970 1975 1980 1985 1990 1995
Year
*Federally Funded Research and Development Centers operated by universities, industry,
and non-profits.
Source: National Science Board, Science and Engineering Indicators—1998, National

Science Foundation (NSB98–1).
FIGURE 7.1 Federal investments for R&D by performer, 1970-1997.
TABLE 7.1 Trends in Federal Investments in Basic Research by Discipline

Expenditures (billions of 1995 dollars) % Change
Research Area 1985 1990 1995 (1985-1995)
Life Sciences 5.20 5.98 6.94 33.5
Physical Sciences 2.50 3.08 2.91 16.4
(Physics) (1.32) (1.71) (1.50) (13.6)
Environmental Sciences 0.96 1.46 1.54 60.4
Mathematical & Computer
Sciences 0.36 0.47 0.58 61.1
Social Sciences 0.19 0.17 0.21 10.5
Engineering 1.22 1.27 1.29 5.7
(Materials) (0.30) (0.30) (0.28) (–6.7)
Other 0.14 0.35 0.53 78.6
Total Basic Research 10.57 12.78 14.00 32.5
SOURCE: National Science Board, Science and Engineering Indicators—1996 (Table 4-22), National
Science Foundation, Washington, D.C.

tiveness in a broad array of current and emerging technologies. Successfully

navigating the changes in the R&D landscape while strengthening condensed-
matter and materials physics is a strategic imperative for the field and for the
nation.
Within the major industrial laboratories, investments in fundamental physi-
cal sciences have been reduced, and much of the remaining effort has been
focused on nearer-term projects. The situation has been exacerbated by the
increasing tendency to conduct manufacturing offshore to reduce costs. This
change is particularly alarming because the special environment of these labora-
tories sparked many of the important discoveries that led to the major technologi-
cal advances of the twentieth century (see Box 7.1). This environment—which
balanced enlightened management with opportunities for independent inquiry,
assembled a critical mass of researchers from a diversity of disciplines, and
encouraged “unfettered” research within a framework of strategic intent—was
unprecedented in its scientific and technological impact. It was also dependent
on monopoly or pseudomonopoly positions, since the profits associated with
many of the scientific advances accrued to other companies. There was a high
probability that scientific results would fall outside the commercial interests of
the parent company, and in many cases the technological value of the new dis-
coveries was not apparent for many years, allowing the information to diffuse
throughout the community. This system was inefficient for the parent company,
and unsustainable in the current world of global competition and corporate raid-
ing, but very productive for the economy overall. Recreating this environment
within the present R&D system represents a major challenge and opportunity.
Within the universities, there has been a steady decline during the past de-
cade in the number of new students entering the physical sciences (see Table 7.2).
In fact, undergraduate enrollment in physics (including condensed-matter and
materials physics) is at its lowest level in 30 years. This appears to be a response
to an apparent oversupply of new Ph.D. physicists in the early 1990s, in combina-
tion with a slow job market for physical scientists in fundamental research during
this period. The only scientific discipline to increase undergraduate enrollments
during the period was biology, which is consistent with the increasing federal
investment in biomedical research. The declining numbers of physical science
undergraduates raise serious questions about the availability of future human
capital in the technologies that drive large sectors of the economy. For example,
shortages in many areas of software research and semiconductor processing are
already apparent. Physicists, who often possess skills that are attractive to high-
technology industry, provide some of this human capital by pursuing careers in
industry. In addition, the economy relies heavily on foreign students who remain
in the United States to work after completing their Ph.D. Currently half of the
graduate students at U.S. universities in the physical sciences are foreign nation-
als. There is evidence that many of these students are choosing to return to their
homelands as global opportunities in science and technology improve. Unless

BOX 7.1 The Legacy of the Industrial Laboratories
For condensed-matter and materials physics related to applications, the tweni-

eth century has been the century of the large industrial laboratory. A handful of
corporate research laboratories—Bell Laboratories (see Figure 7.1.1), IBM Re-
search, DuPont, and others—have dominated the scene with developments such
as the transistor, the solid-state laser, optical fiber, synthetic polymers, high-
temperature superconductivity, scanning-tunneling microscopy, and electron dif-
fraction. These organizations operated at the frontier of science in a strategic
context, developing broad new understanding to advance both science and tech-
nology and making profound contributions with impacts far beyond their corporate
borders.
The corporate research laboratories emerged to exploit the promise of the
physical sciences for the development of revolutionary new technologies and prod-
ucts. Condensed-matter and materials physics, invigorated by the new quantum
mechanics, was on the verge of an intellectual explosion. Many corporations rec-
ognized the importance of being part of that explosion. Some became leaders by
FIGURE 7.1.1 Bell Laboratories at the time of the invention of the transistor.
(Courtesy of Bell Laboratories, Lucent Technologies.)

committing to fundamental research in condensed-matter and materials physics

as a path to new technologies.
A number of forces combined to promote the rise of the corporate laboratories.
First, the time was right. The development of quantum mechanics, advances in
the understanding of electrons in solids, and new tools such as x-ray diffraction,
electron microscopy, and neutron scattering provided fertile ground for research.
At the same time, it was apparent that advances in condensed-matter and materi-
als physics were key to the new materials and devices that would drive modern
technology. In many cases the military was willing to pay initial development costs,
and the success of the Manhattan Project generated optimism about the power of
physics and corporate-scale research. Finally, many of these laboratories enjoyed
monopoly or pseudomonopoly positions because of regulatory policy or market
dominance. As a result, these institutions took on many of the characteristics of
“national laboratories.”
The corporate research model was very successful in developing new science
and technology. Corporations brought together scientists from different disciplines,
provided freedom within the context of strategic intent, and had the resources and
vertical integration to support large-scale, long-term R&D. Technical manage-
ment, drawn from the research ranks, was empowered to make financial decisions
and to move quickly without formal peer review. The resulting research environ-
ment was extremely productive—but the economic benefits did not always accrue
to the parent corporation. The unpredictability of research results and applica-
tions, the diffusion of knowledge, and the ability to bring new technologies to mar-
ket were all factors in spreading the economic impact of corporate research. This
widespread impact was good for the economy (AT&T maintained an open license
for the transistor) and for the development of condensed-matter and materials
physics.
As we enter the twenty-first century, condensed-matter and materials physics
has become much too large to be dominated by a few corporate research labora-
tories. Furthermore, corporate research has become more focused, and the ex-
tent of corporate participation in long-term condensed-matter and materials phys-
ics research in the future cannot be predicted. In addition, many industries are
emphasizing software and systems research over hardware, and there is a trend
toward more research being done in small companies. As a result, the special
research environment that led to many of the fundamental condensed-matter and
materials physics discoveries of the twentieth century no longer exists. Today, this
special environment can best be emulated by government laboratories and univer-
sities working together with industry to create distributed, multidisciplinary networks
in condensed-matter and materials physics. Within these networks, industry must
continue to play a significant role in fundamental research in order to provide the
vision needed to connect the research to technological applications.
Computers, new synchrotrons and neutron sources, and other instrumentation
advances place us on the verge of another revolution in condensed-matter and
materials physics. Cooperation among universities, government laboratories, and
industry is essential to maintaining U.S. leadership in this revolution. This will
require mechanisms, including intellectual property provisions, that encourage this
cooperation.

TABLE 7.2 Bachelor’s Degrees Awarded in Selected Disciplines in the United

States, 1985-1995
Number of Bachelor’s Degrees
Change Change
Field 1985 1990 1995 (1985-1995) 1997 (1985-1997)
Biological Sciences 39,405 38,040 56,890 (+44%)
Physics * 5,013 4,950 4,263 (–15%) 3,826 (–24%)
Chemistry 10,701 8,289 10,016 (–6%)
Mathematics 15,389 14,674 13,851 (–10%)
Engineering 77,572 64,725 63,371 (–18%)
Geosciences 7,001 2,256 3,820 (–45%)
Computer Sciences 39,121 27,695 24,769 (–37%)
Materials/Metallurgy
Engineering 1,276 1,166 1,046 (–18%)
All Bachelor’s 990,877 1,062,151 1,174,436 (+19%)
*American Institute of Physics (AIP), Enrollments and Degrees Report, AIP, New York (April 1997).
SOURCE: National Science Foundation (NSF), Science and Engineering Degrees: 1966-1995, NSF
97-335, NSF, Washington, D.C. (1996).
there is an increase in the attractiveness of the physical sciences to U.S. under-

graduate and graduate students, the nation risks a future with insufficient human
resources to maintain leadership in science and technology. Intervention at the
secondary school level is an essential component of any effort to stimulate inter-
est in physical science careers.
Federal investments in condensed-matter and materials physics have in-
creased slightly in the past decade (see Figure 7.2), despite the general downturn
in federal support for R&D. However, these increases have been more than offset
by the operating costs of major new research facilities that have come online
during this period, notably synchrotrons at the laboratories of the U.S. Depart-
ment of Energy (DOE). These facilities, which include neutron sources and
microcharacterization centers as well as synchrotrons, serve more than 5,000
users per year, more than half of whom come from disciplines other than
condensed-matter and materials physics (see Figures 7.3 and 7.4). Setting aside
this stewardship responsibility for national facilities, federal investments in
condensed-matter and materials physics research have actually declined more
than 10 percent since 1985. Although budget statistics are not available, head
counts in physical research departments at major industrial laboratories in
physics-related industries have declined by a factor of two during the same pe-
riod, reducing further the nation’s research effort in condensed-matter and mate-
rials physics.

700
FUNDING (MILLIONS OF 1997 DOLLARS) 600

DOE (Major Facilities)1
500
2
DOE
400
300
3
NSF
200
DOD4
100
5
NASA
NIST6
0
1986 1988 1990 1992 1994 1996
Year
1
Major facilities operations supported by the DOE Division of Materials Sciences.
2
Doe Division of Materials Sciences (research).
3
NSF Division of Materials Research (research and facilities).
4
Estimates from CMMP-related DOD physics and materials research.
5
Estimates from CMMP-related NASA microgravity and space science programs.
6
Estimates from CMMP-related research and facilities operation at NIST.
FIGURE 7.2 Trends in federal investment in condensed-matter and materials physics,

1985-1997.
4000
3000
No. of Users
2000
1000
0
1983 1985 1987 1989 1991 1993 1995 1997
Fiscal Year
FIGURE 7.3 Growth in the number of users at Department of Energy synchrotron facili-
ties, 1982-1997.

Geosciences and Ecology Other

7% 2%
Applied Sciences and Engineering Life Sciences
7% 27%
Optical, General Physics

9%
Chemical Sciences
12%
Materials Sciences
36%
FIGURE 7.4 Use of national synchrotron facilities by scientific discipline shows that
more than half of the 4000 users in 1997 worked in fields other than condensed-matter
and materials physics.
CONDENSED-MATTER AND MATERIALS PHYSICS TODAY

The evolution in the practice of condensed-matter and materials physics in
response to these external forces and to developments within the field itself has
been dramatic. Partnerships across disciplines and among performers have proven
to be essential to continued progress in the field. Powerful new research facilities
have provided individual investigators with unprecedented access to the world of
atoms and electrons in materials. These facilities, developed and supported by
the condensed-matter and materials physics community, now provide unique
research capabilities to thousands of researchers from a wide range of scientific
disciplines. Finally, many of the institutions that practice condensed-matter and
materials physics have undergone fundamental change in response to changing
priorities and economic realities.
Condensed-matter and materials physics is inherently interdisciplinary, with
advances increasingly occurring at interfaces with chemistry, materials science,
atomic and molecular physics, engineering, biology, and other disciplines (see
Box 7.2). Major professional societies, including the Materials Research Society
and the Divisions of Materials Physics and High Polymer Physics of the Ameri-
can Physical Society, have positioned themselves to foster and serve this interdis-
ciplinary materials community. Interdisciplinary research represents a signifi-
cant challenge to the disciplinary boundaries inherent in university departments,
funding agencies, and the peer-review process. Bridging these barriers is an
important priority for the future of condensed-matter and materials physics. In
particular, mechanisms must be found to ensure that compelling interdisciplinary

BOX 7.2 Meeting the Interdisciplinary Challenge
Condensed-matter and materials physics is inherently interdisciplinary. Link-

ages to chemistry, materials science, atomic and molecular physics, and engineer-
ing have been essential to progress in the field. New linkages to biology are critical
to the future. Forefront research transcends boundaries within condensed-matter
and materials physics as well and often depends on an integration of theory and
experiment with the synthesis of special research samples and a variety of ad-
vanced characterization techniques. Advances in condensed-matter and materi-
als physics cluster at the interfaces between established disciplines, interfaces
that face institutional, funding, and disciplinary barriers.
Traditional scientific disciplines maintain and nurture the foundations of knowl-
edge. This is important to the scientific enterprise, but it also presents the potential
for barriers to interdisciplinary research as scientific disciplines evolve, developing
language and culture not readily understood by the practitioners of other disci-
plines. For example, biology is at a point where the atomic view of physicists is
having enormous impact, but physicists and biologists have difficulty communicat-
ing. This structural defect in the disciplinary organizational scheme must be ad-
dressed through education and budgetary incentives.
Institutions also present barriers to interdisciplinary research. University de-
partments are structured around scientific disciplines. As a result, new faculty who
wish to pursue research at the boundaries between disciplines can have difficulty
finding a home (and earning tenure). Furthermore, the individual-investigator
mode does not foster multidisciplinary teaming. The emergence of the multidisci-
plinary Materials Research Science and Engineering Centers, Science and Tech-
nology Centers, and Engineering Research Centers, sponsored by the National
Science Foundation, is a response to this issue.
Finally, the funding process can present barriers to interdisciplinary research.
Projects that fall outside traditional disciplines can easily be overlooked by a peer-
review community structured around those disciplines. The peer-review process
must include explicit capabilities for handling interdisciplinary proposals.
Universities can meet the interdisciplinary challenge through joint appointments
for faculty, by encouraging multidisciplinary centers, and by recognizing the value
of interdisciplinary research in tenure decisions. Government laboratories, which
have an easier time putting together multidisciplinary teams, should be encour-
aged to involve universities in those teams. Funding agencies have the most
leverage, as seen in the success of agency-sponsored multidisciplinary centers.
Proposals that assemble diverse teams, including physicists and biologists for
example, to tackle high-profile multidisciplinary problems should be encouraged.
Institutions that ignore the interdisciplinary challenge risk abandoning the scientific
frontier.
research proposals are not lost in the competition with other proposals that more
neatly fit the boundaries of established disciplines.
Partnerships across disciplines and among universities, government laborato-
ries, and industry are becoming increasingly important in bringing together the
resources and diverse skills needed to continue advancing knowledge in condensed-

matter and materials physics. For many leading-edge research projects, it is neither
practical nor cost-effective to assemble the required capital and intellectual re-
sources at a single location. Teams form and dissolve as research directions change,
and the diversity of institutions and performers ensures that a wide range of projects
and approaches can be accommodated. This is a fundamental strength of the U.S.
R&D system. Modern communications, an outgrowth of condensed-matter and
materials physics, is essential to these partnerships.
Another significant change in the practice of condensed-matter and materials
physics has been the emergence of major national research facilities. These
facilities, which include synchrotrons, neutron sources, and microcharacterization
centers, have had an extraordinary impact on the ability of researchers to investi-
gate ever-smaller, lower cross-section, more dilute, and more complex systems.
Accordingly, there has been a spectacular increase in the use of these facilities.
These powerful tools transcend condensed-matter and materials physics to serve
large user communities from other disciplines, including biology, which now
consumes more than 25 percent of the beam time at national synchrotron facili-
ties. As a result, condensed-matter and materials physics is having a significant
impact on many fields with which it had little connection just a decade ago.
Institutional change is never comfortable, and it is a continuing challenge to
U.S. space science. Research organizations are being expected to improve organi-
zational effectiveness and resource utilization, create new partnerships, and serve
customers better. Customers, ranging from corporate manufacturing arms to
sponsors to facility users, are increasingly involved and demanding. All sectors
of condensed-matter and materials physics underwent profound change in recent
years. Industrial laboratories were downsized and redirected. Government labo-
ratories struggled with substantial reductions in resources, increased regulation,
and mission and operational reform. Research universities came under increas-
ing pressure to reduce overhead, cut costs, and become more responsive to the
public and to industry. All of these changes have potentially positive outcomes,
and condensed-matter and materials physics is particularly well positioned to
contribute effectively in this new environment. However, great care will be
required to navigate these changes while preserving the research infrastructure of
the nation for the long term.
MEASURING PERFORMANCE AND ECONOMIC IMPACTS

The Government Performance and Results Act (GPRA), passed in 1993,
provides a timetable for agencies to develop strategic plans and criteria for mea-
suring their performance against established goals. These plans and performance
measures, which were intended to be in place by 1997, will form the basis for
evaluating the effectiveness of agency programs and developing budgets. This
represents a major challenge for fundamental science, in which the important

impacts tend to be unpredictable, dilute across the spectrum of research activities,

and frequently are separated by decades from the initial research results.
GPRA establishes a framework in which agencies provide inputs in order to
produce outputs, which have intended outcomes for society and the economy.
Inputs might be person-years and equipment-years of effort, for example, while
outputs are the direct results of an agency’s inputs, and outcomes are the broader
impacts that result. For research, these concepts are summarized in Table 7.3.
Within condensed-matter and materials physics, the discovery of high-temperature
superconductivity represents an output, while the commercialization of supercon-
ducting technology would be an outcome. Agencies are required to develop perfor-
mance criteria for both outputs and outcomes. This requirement is a substantial
challenge for agencies involved in fundamental research, for which the outputs
TABLE 7.3 Inputs, Outputs, and Outcomes of R&D

Performance Indicators
Category Concepts Proxies Correlates
Inputs Person-years Expenditures
Equipment-years
Outputs Ideas, discoveries Papers, prizes
Inventions Patents, invention-
disclosures
Human capital Degrees awarded
Technology transfer CRADAs, licenses Cost-shared dollars
Outcomes or Broad advance of Papers, citations,
Impacts human knowledge expert evaluations
New products Patents, citations Licenses, license
royalties, product
announcements, new
product sales
Productivity Measured productivity
improvements growth
Income growth Benefit/cost ratio or New firms, induced
rate of return investment
Excitement about Science News articles
science
Health, environment, New drug applications Emissions levels
etc.
Cooperation and CRADAs
knowledge flow
SOURCE: Adam B. Jaffee, “Measurement issues” in L.M. Branscomb and J. Keller, eds., Investing
in Innovation, MIT Press, Cambridge, Mass. (1997).

(ideas and discoveries) are difficult to measure, and the outcomes (the advance of
knowledge or the introduction of new products), are difficult to quantify or relate to
specific programs. Consequently, proxy indicators related to the desired outputs or
outcomes are developed for research activities. These proxies might include pa-
pers, prizes, and patents to take the place of ideas and discoveries in measuring
research outputs, and citations and productivity growth to take the place of ad-
TABLE 7.4 Economic Growth Rates Attributable to R&D Investments

Rate of Returna
Author(s) and Year of Study (Percent)
Firm-level Studies
Link (1983) 3
Bernstein-Nadiri (1989b) 7
Schankerman-Nadiri (1986) 13
Lichtenberg-Siegel (1991) 13
Bernstein-Nadiri (1989a) 15
Clark-Griliches (1984) 19
Griliches-Malresse (1983) 19
Jaffe (1986) 25
Griliches (1980) 27
Mansfield (1980) 28
Griliches (1986) 36
Schankerman (1981) 49
Minasian (1969) 54
Industry-level Studies
Terleckyj (1980) NSb
Griliches-Lichtenberg (1984a) 4
Patel-Soete (1988)c 6
Mohnen-Nadiri-Prucha (1986) 11
Terleckyj (1974) 15
Wolff-Nadiri (1987) 15
Sveikauskas (1981) 16
Bernstein-Nadiri (1988) 19
Link (1978) 19
Griliches (1980) 21
Bernstein-Nadiri (1991) 22
Scherer (1982, 1984) 36
a For studies for which Nadiri (1993) reports a range of possible returns, the midpoint of that range is
provided in this table.
b Not significantly different from zero in a statistical sense. This result, however, may be a reflection
of limitations in the quantity of data used in the study.
c Economy-level study (all industries grouped together).
SOURCE: M.I. Nadiri, “Innovations and Technological Spillovers,” Working Paper No. 4423,
National Bureau of Economic Research, Cambridge, Mass. (1993).

vances in knowledge or the introduction of new products in measuring outcomes.

Although inherently imperfect, the use of multiple proxy indicators in combination
with peer review probably represents the most likely (and most reasonable) perfor-
mance measurement approach for fundamental research under GPRA.
This discussion of performance measures raises a key issue: the rate of
economic return on R&D investments. Specific data are not available for
condensed-matter and materials physics, although powerful evidence abounds,
such as the economic impact of the transistor, magnetic materials, fiber optics,
and the solid-state laser. Numerous studies of economic return have been per-
formed for the broader R&D enterprise. These studies, many of which are listed
in Table 7.4, indicate average rates of return of 15 to 20 percent per year. This is
an extraordinary indication of the value of research. Unfortunately, these data do
not provide information on the impact of adjustments (either up or down) in the
level of R&D investment and are therefore not useful in determining absolute
funding levels.

The Next Decade
Condensed-matter and materials physics lies at the heart of many of the

scientific and technological challenges of our time. Progress in condensed-matter
and materials physics drives our fundamental understanding of the materials and
phenomena that enable technological advances; and condensed-matter and mate-
rials physics is entering a new era driven by new capabilities in synchrotron and
neutron research, atomic-scale visualization, nanofabrication, and computing.
These capabilities provide opportunities to examine the behavior of materials at
levels of complexity and with degrees of microscopic control that are unprec-
edented. The new era promises to revolutionize our understanding of materials,
expanding our knowledge beyond the physics of idealized systems to touch the
real materials that enrich our lives. Fundamental understanding of electronic and
optical phenomena, complex assemblies of atoms and multicomponent materials,
nonequilibrium phenomena, and biological phenomena will fuel advances in
technologies ranging from microelectronics to structural materials to medicine.
The stage is set. The new era holds the promise of revolutionary develop-
ments in condensed-matter and materials physics that will contribute to economic
growth, national security, and the quality of life. Success will require investing in
human capital and research infrastructure, establishing partnerships across disci-
plines and institutions, integrating research and education, and maintaining ex-
cellence with relevance.
MAKING THE RIGHT INVESTMENTS

Progress in condensed-matter and materials physics has been enabled by
sustained investments in long-term research by federal agencies and at large
288

THE NEXT DECADE 289
industrial laboratories. In recent years, in response to new competitive environ-

ments, industry has shifted away from long-term physical sciences research and
toward nearer-term research and development. At the same time, the govern-
ment’s discretionary expenditures (which include R&D investments) have been
constrained by efforts to balance the federal budget amidst growing entitlement
outlays. Additional pressure on condensed-matter and materials physics funding
comes from the field’s responsibility to develop and operate large national facili-
ties for materials research, such as synchrotrons and neutron sources, that are
heavily utilized by a growing community of users from many scientific and
engineering disciplines. As a result, although the resources available to con-
densed-matter and materials physics are substantial, there are severe constraints
in comparison to the overall need to maintain the nation at the forefront of
fundamental research in this technologically critical area.
As a fraction of gross domestic product, federal investment in R&D has
dropped by about half over the past 30 years. This trend of declining investment
threatens U.S. leadership in science, including condensed-matter and materials
physics. At the same time, it is estimated that half of the economic growth in the
last half century has come from technological innovation that requires leadership in
science. The President’s budget request for FY 1999 reflects these concerns,
placing increased priority on science and technology and showing strong gains for
many federal research agencies. In addition, the bipartisan Fritz-Rockefeller bill
(S. 2217) calls for a doubling of federal investment in civilian research over the
next 12 years. This bill, known as the Federal Research Investment Act, is sup-
ported by a coalition of more than 100 science, engineering, and technology orga-
nizations. A parallel effort to increase support for defense R&D is also under way.
Human Capital
Many economists attribute current economic growth to investments in hu-
man capital, the capacity to generate new ideas that organize and rearrange exist-
ing resources to achieve productivity gains. Examples range from new ways of
processing steel and polymers, to the soaring performance of electronic and
optical systems, to the growth in software and computer applications. These
advances share common characteristics of innovation and integration of knowl-
edge—the economics of ideas. Human capital, enabled by investments in educa-
tional and research institutions, drives economic growth by providing the new
ideas that allow escape from a traditional economic future limited by scarcity of
resources and the law of diminishing returns.
Unlike physical resources, which are limited in a finite world, the potential
of human capital is nearly limitless. But it is not free. A commitment to educa-
tion, to research, and to the free exchange of information and ideas is essential. In
the modern global economy, world leadership is impossible without leadership in
human capital.

In condensed-matter and materials physics, human capital is a product of the

education system and the collective learning of universities, industry, and gov-
ernment laboratories. It is nourished by sustained investments in fundamental
research and by maintaining close interactions among condensed-matter and
materials physics performers, with other scientific disciplines, and with industry.
The reservoirs of human capital include school teachers, the professoriate as both
educators and researchers, and researchers and policy makers in government and
industry. These reservoirs also include institutions—research universities and
government and industrial laboratories—that provide the environment and infra-
structure for generating and preserving knowledge and from which new ideas can
emerge.
Human capital is probably the single most important investment for science
and technology. Human capital in condensed-matter and materials physics occu-
pies a special place in the national economy, underpinning many of the techno-
logical advances that drive economic growth. The U.S. system of graduate
education, research universities, government and industrial laboratories, and na-
tional facilities for condensed-matter and materials physics is the envy of the
world. Maintaining this leadership requires continued commitment to strength-
ening these institutions. In addition, condensed-matter and materials physicists
must play a crucial role in engaging undergraduates in research and improving
their understanding of science and technology. These investments are needed to
develop the human capital essential for leadership in condensed-matter and mate-
rials physics and related technologies.
Facilities and Infrastructure

Condensed-matter and materials physics encompasses a broad array of insti-
tutions and research modes, ranging from individual investigators to multi-
disciplinary teams, from bench science to large national facilities, and from fun-
damental to applications-oriented research. This diversity is representative of the
diversity of the field and is essential to its success. Maintaining an appropriate
balance among performers, institutions, and research modes is a continuing chal-
lenge for condensed-matter and materials physics. There are no clear boundaries.
For example, large facilities are used primarily by individual investigators (often
from fields other than condensed-matter and materials physics), and applications-
oriented research often leads to breakthroughs in fundamental science. Priorities
for infrastructure investments in facilities, laboratories, and institutions must be
assessed in the context of this diversity and interdependence.
Infrastructure
Laboratories, instrumentation, and facilities for performing state-of-the-art
condensed-matter and materials physics are becoming increasingly expensive to

THE NEXT DECADE 291
develop and operate. At the same time, more universities are competing effec-
tively for federal research dollars. It is becoming increasingly apparent that the
needed infrastructure cannot be duplicated at even a few dozen universities, let
alone the more than 180 institutions nationwide that grant physics Ph.D.s. It is
estimated that nearly half of university laboratories in the physical sciences re-
quire refurbishment in order to be used effectively. Government institutions,
including the DOE laboratories, are also burdened with an aging infrastructure.
At the same time, there has been a significant increase in the availability of
modern research infrastructure at major national and regional research facilities
and centers. These facilities provide needed infrastructure on a shared basis. In
addition, there is substantial research infrastructure at government laboratories
(beyond the major facilities) that is contributing to alleviating this problem. The
number of guest researchers from universities and industry at DOE national
laboratories has skyrocketed in the past 15 years, and more could be accommo-
dated with modest investments. An integrated solution, combining revitalization
of university laboratories with modernization and increased community utiliza-
tion of government laboratories, seems to provide the most cost-effective option
to serve the infrastructure needs of the condensed-matter and materials physics
community (see Box 8.1).
Materials Microcharacterization and Processing Facilities

The dozens of materials microcharacterization and processing centers dis-
tributed among universities and government laboratories provide access to elec-
tron microscopes, accelerators, and other microanalytical and processing equip-
ment that is beyond the means of individual investigators. They also provide
expertise in the operation of these facilities that greatly enhances their accessibil-
ity. As a result, state-of-the-art microcharacterization and processing capabilities
are available to virtually all researchers on a shared basis. In addition, like larger
facilities, these centers establish an environment where cross-disciplinary re-
search is naturally encouraged.
BOX 8.1 Recommendations for Materials Research

Infrastructure and Microcharacterization and
Processing Facilities
• Increased investment in modernization of the condensed-matter and mate-

rials physics research infrastructure at universities and government laboratories.
• Increased investment in state-of-the-art instrumentation and fabrication ca-
pabilities, including centers for instrumentation R&D, nanofabrication, and materi-
als synthesis and processing.

Microcharacterization facilities also provide a resource for advancing micro-

characterization science and developing new and better instrumentation. The
United States has lagged in this area except in scanning-tunneling microscopy.
Modest investments in research at these facilities could contribute to impressive
performance gains in electron optics, visualization, virtual operation, and other
improvements. Such investments are needed to ensure that the existing infra-
structure is used effectively and that U.S. scientists have access to the best
technology.
The committee recognizes the essential role of regional and national centers
for atomic-scale visualization, nanofabrication, materials synthesis and process-
ing, high-field magnetism, and other specialized capabilities to support leading-
edge condensed-matter and materials physics research. There should be explicit
recognition of the importance of these centers and the need to strengthen their
role in instrumentation development. In addition, attention should be given to the
education of the next generation of instrument scientists (see Box 8.1).
Neutron and Synchrotron Facilities

In recent years, federal expenditures for the operation of large materials
research facilities, such as neutron-scattering and synchrotron radiation sources,
have received considerable attention because of the magnitude of these expendi-
tures in comparison to the core research budgets of the agencies that fund them.
In FY 1998, the estimated U.S. Department of Energy (DOE) Basic Energy
Sciences (BES) operating budgets for these facilities exceeded $253 million. The
bulk of this amount, $235 million, was provided by the materials sciences and
chemical sciences programs of BES. This represented approximately 38 percent
of BES’s total budget authority. Over the past decade, facility costs have almost
doubled (in inflation-adjusted dollars), while the core research budgets of the
BES materials sciences and chemical sciences programs have remained essen-
tially constant.
At the same time, there is increasing recognition that much of the research
performed at these facilities (particularly at synchrotron sources) is in scientific
and technological areas other than materials and chemical sciences. There have,
therefore, been proposals that federal programs more closely linked to these other
research areas should provide significant facility operating funds.
Two national synchrotron radiation facilities have been constructed recently:
the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory,
for ultraviolet and soft x-ray research, and the Advanced Photon Source (APS) at
Argonne National Laboratory, for x-ray research. In addition, the National Syn-
chrotron Light Source (NSLS) at Brookhaven National Laboratory, the Stanford
Synchrotron Radiation Laboratory (SSRL) at the Stanford Linear Accelerator
Center, the Cornell High Energy Synchrotron Source (CHESS) at Cornell Uni-
versity, the Synchrotron Radiation Center (SRC) at the University of Wisconsin,

THE NEXT DECADE 293
and the Synchrotron Ultraviolet Radiation Facility II (SURF II) at the National
Institute of Standards and Technology remain highly active and productive.
In contrast, construction of the Advanced Neutron Source, which was to
have been a reactor source at Oak Ridge National Laboratory, was canceled in
1995. In addition, the High Flux Beam Reactor at Brookhaven National Labora-
tory is currently not operating, and there is opposition to restarting it. On a
positive note, the neutron-scattering facilities at the National Institute of Stan-
dards and Technology have been recently upgraded and the High Flux Isotope
Reactor (HFIR) at Oak Ridge is being upgraded. Nevertheless, the neutron-
scattering field now depends on an array of facilities that is even smaller than
what was already found inadequate by national review committees in the 1980s
and early 1990s.
As a consequence of these concerns, the DOE’s Basic Energy Sciences
Advisory Committee (BESAC) recently established reviews of its existing and
proposed neutron and synchrotron radiation facilities. BESAC considered the
neutron situation at a meeting in Washington, D.C., on February 5-6, 1996.
Drawing on reports from several national panels, BESAC made the following
recommendations for neutron-scattering facilities:
• Construct a 1 MW, upgradable short-pulse spallation neutron source, now

known as the Spallation Neutron Source (SNS).
• Upgrade existing neutron scattering facilities at the High Flux Beam Re-
actor at Brookhaven National Laboratory, the High Flux Isotope Reactor at Oak
Ridge National Laboratory, and the Los Alamos Neutron Scattering Center at
Los Alamos National Laboratory.
BESAC further emphasized that the proposed construction and upgrades,

while critically important to the future of neutron-scattering science in the United
States, must not come at the expense of other BES research activities and must
take explicit recognition of the additional operating and instrument development
needs involved.
Considerable progress has been make toward implementing these recom-
mendations. The conceptual design for SNS has been completed, and construc-
tion funding for the project has been included in the FY 1999 budget. SNS will
be constructed at Oak Ridge National Laboratory by a consortium of five DOE
national laboratories. In addition, the proposed upgrades at the High Flux Isotope
Reactor and the Los Alamos Neutron Scattering Center are under way.
The committee recommends priority construction of SNS as well as up-
grades to existing neutron-scattering facilities, provided that these projects do not
come at the expense of the core research programs of BES (see Box 8.2).
To address issues related to the operation and scientific roles of synchrotron
facilities, BESAC established the Panel on Synchrotron Radiation Sources and
Sciences in 1997. This panel was charged to assess the scientific importance of

BOX 8.2 Recommendations for

Major Materials Research Facilities
• Prompt construction of the Spallation Neutron Source as well as upgrades

to existing neutron scattering facilities.
• Increased funding for operations and upgrades at synchrotron facilities
including research and development on fourth-generation sources.
• Consideration of the broad utilization of synchrotron and neutron-scattering
facilities across scientific disciplines and sectors when establishing budgets for the
agencies that operate these facilities.
synchrotron radiation over the next decade, determine the size and nature of the
user community both globally and by facility, and assess the operation of the
facilities including their plans and vision for the future. The panel was also asked
to make detailed recommendations under various budget scenarios and to con-
sider the consequences of closing one or more of the BES synchrotron facilities.
In its report to BESAC, the panel concluded unanimously that “. . . shutdown
of any one of the four DOE/BES synchrotron light sources over the next decade
would do significant harm to the nation’s science research capabilities and would
considerably weaken our international competitive position in this field.” The
panel recommended the following actions (in priority order):
1. Continue operation of the three hard x-ray sources (APS, NSLS, and
SSRL) for their large user communities, with a modest investment for general
user support and for R&D on a fourth-generation x-ray source. (Recommended
expenditures at both NSLS and SSRL were $3 million per year above the FY
1998 DOE-requested levels.)
2. Develop new beam lines at APS and modernize existing facility beam
lines at NSLS. (Recommended expenditures were $8 million per year at APS and
$3 million per year at NSLS.)
3. Fund ALS at the FY 1998 DOE-requested level of $35 million.
The panel also recommended funding proposed upgrades to the NSLS and
SSRL facilities at an estimated cost of $27 million per year over 3 years. These
upgrades should be carried out under a special initiative separate from the normal
budgeting process. For example, BES might seek partnerships with other divi-
sions within DOE and with other agencies such as the National Institutes of
Health (NIH) or could request a budget add-on. This recommendation was
intermediate in priority between the second and third priorities above.
The committee recommends support for operations and upgrades at existing
synchrotron facilities (including modest investments for user support), as well as

THE NEXT DECADE 295
R&D on a fourth-generation x-ray source. Synchrotron and neutron-scattering

facilities are used extensively by researchers in various scientific disciplines, but
the operating funds for the facilities are drawn from the agencies and programs
that developed the facilities. The committee recommends that this fact be taken
into account when the budgets of agencies operating these facilities are formu-
lated (see Box 8.2).
In light of the extensive use of the synchrotron radiation facilities by fields
other than materials and chemical sciences, the panel considered funding models
that included contributions from other agencies. Their conclusion was that this is
not practical. Rather, the panel endorsed BES’s stewardship of synchrotron
radiation sources, and urged BES to build on the broad impact of these facilities,
especially in fields related to health and the environment, to increase its own base
budget. The panel did, however, recommend diversification of the funding
sources for special initiatives such as the proposed SSRL and NSLS upgrades.
There are synchrotron and neutron facilities supported by agencies other
than DOE, including the National Science Foundation (NSF) and the U.S. De-
partment of Commerce (DOC). These facilities are used by scientists supported
by these and other federal and private agencies and institutions. Given the con-
siderable cost of operating and improving these facilities, it is important that
there be coordinated, interagency (including at least DOE, NSF, DOC, and NIH)
consideration of, and planning for, neutron and synchrotron radiation facilities.
The respective roles of these agencies in funding the construction, instrumenta-
tion, upgrading, and operation of these facilities should be delineated. However,
each facility should have one agency that provides support for basic operations,
and the broad utilization of synchrotron and neutron-scattering facilities across
scientific disciplines and sectors should be considered in establishing the budgets
for the agencies that operate these facilities. A committee of the National Re-
search Council is considering interagency issues related to national facilities.
REDEFINING ROLES AND RELATIONSHIPS

The national R&D enterprise includes the funding agencies as well as essen-
tial components in industry, universities, and government laboratories. Industry
is by far the largest performer of R&D in the United States, with expenditures of
$133 billion in FY 1997, compared with $72 billion for the remaining sectors.
Industrial R&D, however, is heavily weighted toward near-term development;
industry provided only one-fourth of the $31 billion of U.S. investment in basic
research in FY 1997. Universities and government laboratories are the largest
performers of basic or fundamental research. Universities play a unique role
in education, while government laboratories provide the infrastructure for
multidisciplinary research and large facilities. Recently, many states have be-
come significantly involved in the R&D enterprise, providing funds to stimulate
the research competitiveness of their states. The states, responding to correla-

tions between R&D activity and regional economic development, are becoming
important resources for research support.
Within condensed-matter and materials physics, there are many approaches
to the conduct of research, ranging from individual investigators to large multi-
disciplinary teams and from bench-scale experiments to studies at major national
facilities. There is also a diversity of federal sponsors for condensed-matter and
materials research, led by DOE, NSF, and the defense agencies. No single
approach can span the diversity of research problems, and an effective national
research program requires balance among a variety of performers and approaches.
Achieving this balance requires an appreciation of the R&D roles of industry,
universities, and government laboratories and of how to establish relationships
among performers that encourage research synergy, funding leverage, and scien-
tific productivity. The diversity of performers, institutions, and funding sources
is a fundamental strength of condensed-matter and materials physics, essential to
progress in a field that embraces both fundamental and applications-oriented
research and spans both small and big science.
Role of Research Universities

Research universities are the bedrock of the U.S. R&D system. They are
embedded in our communities with a holistic mission in knowledge creation,
integration, and transfer. The desired outcomes are increased human capital
(particularly in the form of trained students), opportunities for an improved qual-
ity of life (created by the advancement of knowledge), and an enlightened gen-
eral public. Long the envy of the world, U.S. research universities face serious
challenges over the next decade. Curricula will have to be overhauled to respond
to the needs of industry in the global marketplace. Costs, which have escalated
faster than the inflation rate for more than 2 decades, will have to be contained.
Outreach to communities and businesses will have to be improved to create a
public that understands and supports research and can compete in a technological
economy. Underrepresented groups must be attracted to research careers in order
to ensure an adequate supply of future talent. These challenges will have to be
met in an environment of increasing research infrastructure costs, while adjusting
to the impact of new information technology that will make distance learning and
remote participation in research a reality.
Within condensed-matter and materials physics, universities face the daunt-
ing challenge of determining how to support and distribute new R&D infrastruc-
ture. It will simply not be possible to duplicate the infrastructure now available at
major research universities across the university system. A system of teaming
will have to be established, among universities and between universities and
government laboratories, to ensure broad access to the best research facilities.
The time it takes to obtain a physics Ph.D. is approaching 7 years. This is
costly and undesirable, particularly when industry, the permanent employer of

THE NEXT DECADE 297
the majority of physics Ph.D. recipients, places a higher premium on flexibility

and just-in-time learning than on in-depth knowledge within a narrow field.
Graduate programs in applied physics and engineering physics appear to have
bridged this gap successfully at several universities. Perhaps the time has come
to redefine the physics Ph.D. or develop a professional degree for the industrial
physicist.
The steady decline in the number of undergraduate physics majors over the
past 2 decades represents a major challenge to the field. Continued reliance on
foreign students to fill graduate physics programs and provide human capital to
U.S. industry is unwise in a global economy when offshore educational and
employment opportunities can be expected to improve. The survival of the field
and its continued impact on the U.S. economy depend on making physics rel-
evant to U.S. students. Diversity presents the major opportunity here. Although
the enrollment of women in physics has doubled over the past 2 decades, women
only accounted for 12 percent of physics doctorates granted in 1997. African-
American and Hispanic enrollments have not changed in recent years and only
represented 1 to 2 percent of new physics doctorates in 1997. National demo-
graphic trends dictate that continued leadership in physics will require participa-
tion by these underrepresented groups.
Research universities serve a variety of customers, including students, industry,
research sponsors, and the general public. Continued success over the next decade
will require increased attention to the special needs of these customers, from outreach
programs to engage students and the public, to exchange programs with industry to
promote better understanding of market drivers. Within condensed-matter and
materials physics, particular attention must be given to designing a curriculum that
communicates the excitement and impact of physics to beginning undergraduates
and that is more responsive to the needs of industry in graduate programs.
Role of Government Laboratories

Government laboratories, particularly the large multiprogram laboratories,
represent a national R&D asset of enormous capability. These laboratories have
the infrastructure and human capital to address large-scale problems of national
importance that transcend traditional disciplinary boundaries and require access
to special facilities. Within condensed-matter and materials physics, government
laboratories conduct multidisciplinary research related to national missions in
energy, defense, commerce, and space. These laboratories also develop and
operate the nation’s most powerful research tools for materials research, includ-
ing synchrotrons, neutron sources, and microcharacterization facilities. Such
facilities are an essential part of the R&D fabric of the nation, serving thousands
of scientists from universities and industry.
A particular strength of the laboratories is the performance of long-term,
large-scale, multidisciplinary research in an applications context. Such research

requires a critical mass of resources to integrate across disciplines and apply a

variety of tools to address a problem. In the past, this approach led to the
development in large industrial laboratories of the transistor, synthetic polymers,
and the solid-state laser. Today, with industry focusing on global competitive-
ness and nearer-term development, government laboratories represent the princi-
pal national resource for research on this scale. Realizing the full potential of this
resource requires a continuing commitment to long-term, multidisciplinary re-
search and development at the laboratories and effective research integration
with universities and industry. Facilitating this integration and the related re-
search and development partnerships is an important role of the government
laboratories. In addition, the connection of program offices to research should be
strengthened through exchanges at all levels between the agencies and the re-
search community.
The government laboratories also represent a powerful resource for re-
search infrastructure and integration. The success of the major materials-
research facilities at these laboratories suggests that broader use of the entire
infrastructure by universities and industry should be encouraged. This is al-
ready happening; the number of guest scientists performing research on site has
more than doubled at many laboratories over the past decade. The government
laboratories can also assist by providing access to state-of-the-art infrastructure
for thesis research and by facilitating the formation of teams involving shared
resources and effort with universities and industry to address appropriate re-
search topics. Better utilization of the government laboratories can signifi-
cantly reduce the infrastructure problems currently being encountered in other
sectors of the R&D establishment.
Interactions with Industry

Condensed-matter and materials physics occupies a special position in sci-
ence: fundamental research at the technological frontier. It is one of those rare
fields for which the distance between basic research and technological develop-
ment is small and the concept of “strategic intent” is applicable to research. As a
result, condensed-matter and materials physics finds itself closer to industry than
any other subfield of physics, and industry has a tradition of involvement in
condensed-matter and materials physics as a practitioner, partner in research, and
employer of condensed-matter and materials physicists. Interactions with indus-
try are vital to the development of the field and its impact on the economy.
A primary interaction is between industry and universities. Here, industry is
looking for talent to promote growth and innovation—talent that is the product of
graduate schools. Curricula in physics (including condensed-matter and materi-
als physics) have evolved little over the past decade. At the same time, industry
has undergone extensive change, and the pace of the worldwide technology en-
terprise has accelerated greatly. Industrial input is needed to help physics educa-

THE NEXT DECADE 299
tion adapt and become more flexible so that it can better serve the future needs of
industry and the nation.
R&D interactions with industry involve both universities and government
laboratories. For large companies with in-house R&D capabilities, access to
unique skills or facilities at universities or government laboratories drives the
interaction. These interactions often involve a financial commitment by the
company to the partner organization. For smaller companies, many that have no
R&D capabilities of their own, interactions with universities and government
laboratories may be the only way to assemble the necessary R&D resources to
address a technical barrier. The success of cooperative research interactions
depends critically on pursuing projects that contribute to the core missions of all
involved organizations. An urgent need is the development of workable intellec-
tual property arrangements, particularly between industry and universities (see
Box 8.3).
Industry interactions with universities and government laboratories help pro-
vide a strategic context for condensed-matter and materials physics research.
This is extremely important in a field that has such a direct impact on the economy
and for which there are insufficient resources to explore every opportunity.
Choices have to made, and interactions with industry provide useful input as to
what may be important. As a first step, physics departments should become more
involved in the industrial liaison programs at their universities, and government
laboratories should engage in cost-shared research in their competency areas with
industry to provide a window on technology. These interactions should not drive
condensed-matter and materials physics research at universities and government
laboratories, but they can provide a context for appreciating the broader implica-
tions of the research.
The Importance of Partnerships

Condensed-matter and materials physics is an ecosystem that involves a
wide variety of performers, institutions, and research styles. The vitality of this
ecosystem depends on establishing productive relationships among the partici-
pants. Partnerships are important in all branches of science, as noted in the 1996
report Endless Frontier, Limited Resources by the Council on Competitiveness.
The central finding of that report was that “R&D partnerships hold the key to
meeting the [R&D] challenge that our nation now faces.” This point is especially
important in condensed-matter and materials physics, where a range of perform-
ers and approaches is often required in order to span the expertise and capabilities
required to make progress.
Within condensed-matter and materials physics, there is a tradition of part-
nerships among universities, government laboratories, and industry. These part-
nerships include informal collaborations, the use of unique facilities, personnel
exchanges, consulting, and subcontracts and other formal relationships including

BOX 8.3 The Intellectual Property Bottleneck

A major impediment to collaboration between scientists from different institu-
tions arises from policies and expectations concerning intellectual property (IP).
When investigators from different institutions wish to work together, they must typ-
ically enter into a formal written agreement that addresses, among other things,
inventions, patents, copyrights, and trade secrets. Such agreements are often
prepared by attorneys representing their respective institutions. Negotiating these
agreements has always been problematic. With intensified scrutiny of the eco-
nomic rewards of research, these negotiations have become increasingly time con-
suming and frustrating.
No two institutions view IP in the same way, and views seem to evolve over
time. The patent concerns of very large companies center on freedom of action.
As both sources and users of IP, large companies are frequently cross-licensed
with major competitors in common fields of endeavor. This helps to prevent a
large company from being denied access to important patents. The strength of a
large company’s patent portfolio plays a major role in establishing the terms and
conditions of these cross-licensing agreements and also can provide additional
income through direct licensing to other companies. Extensive cross-licensing of
patents implies a lack of exclusivity, although know-how and trade secrets may still
be handled in an exclusive fashion.
Small companies typically view things very differently. One or two key patents
can be the basis for the company’s existence. Exclusivity can mean the difference
between success and failure. Universities are sources of IP but are generally not
users in the commercial sense. Sale or licensing of IP, exclusively or nonexclu-
sively, can provide income to the institution, income to the inventors, and evidence
of the institution’s value to society. Government laboratories are similar to univer-
sities, although legislation authorizing cooperative research and development
agreements (CRADAs) for jointly sponsored research between government labo-
ratories and industries has helped to facilitate IP negotiations. In today’s environ-
ment of intense economic pressure, it is not surprising that agreement on terms
and conditions for joint work with IP-generating potential is often difficult to achieve,
particularly when the agreements are being negotiated by individuals other than
those who want to work together.
With sufficient perseverance IP agreements can usually be put in place, although
often with considerable delay and expense. Too often the enthusiasm for the interac-
tion or the timeliness of the work expires before an agreement is struck. In addition,
existing agreements tend not to be precedent-setting, and negotiations between the
same institutions frequently begin anew, often with different sets of attorneys, when a
new project is proposed. A particular irony is that the likelihood that valuable patents
will be generated decreases as the proposed work becomes more fundamental in
nature, yet the fervor of the negotiations seems to endure undiminished.
Although difficult to quantify, it is clear that the present system is time consuming,
inefficient, expensive, and a major obstacle to the investment of industry in university
research. Industry has established its IP practices over decades, and these prac-
tices appear to work smoothly in the industrial sector. Universities and govern-
ment laboratories, on the other hand, have IP practices that reflect different priorities
and are still evolving. CRADAs are an important first step, but improved industry-
government-university cooperation in research depends critically on achieving mu-
tual understanding and convergence on IP issues among the sectors.

THE NEXT DECADE 301
cooperative research and development agreements (CRADAs). CRADA part-

nerships, although not without controversy, have been enormously successful in
bringing together government laboratories and industry. Box 8.4 summarizes the
important characteristics of successful R&D partnerships. Partnerships within
and among funding agencies are also becoming increasingly common as tradi-
tional barriers yield to the advantages of leverage and working together. The
states are also playing an important role, providing key support to facilitate
partnerships that have an impact on regional economies.
Recreating the fertile research environment of the major industrial laboratories
of the past 50 years is a high priority for condensed-matter and materials physics.
That environment, which has significantly diminished in U.S. industry, was ex-
tremely productive in both science and technology. In effect, these laboratories
functioned as national laboratories, before divestiture and global economic forces
required them to adopt a nearer-term, more focused approach to R&D. The ex-
traordinary success of these laboratories resulted from their ability to integrate
long-term fundamental research, cross-disciplinary teams that included experimen-
talists and theorists, materials synthesis and processing, and a strategic intent. The
elements of this fertile ground still exist in condensed-matter and materials physics
in the form of potential partnerships among universities, government laboratories,
and industry. Federal R&D agencies should encourage partnerships that recreate
BOX 8.4 Recommendations for R&D Partnerships
The committee encourages R&D partnerships among universities, government

laboratories, industry, and government agencies in order to
• Optimize the use of infrastructure and facilities,

• Enable cross-disciplinary research,
• Improve university and government laboratory appreciation of industry pri-
orities and needs,
• Share the risks and returns of long-term research, and
• Assemble teams that can emulate the fertile research environment of the
large industrial research laboratories of the past half century.
These partnerships should be fostered by
• Making resources available through special programs that encourage

partnerships,
• Developing effective protocols for intellectual property issues in cooperative
research,
• Encouraging university and government laboratory internships and sabbat-
icals in industry, and
• Requiring partners to have a stake in the partnership (e.g., for universities
and government laboratories, the partnership should add value to core missions).

this environment in appropriate subfields of condensed-matter and materials phys-

ics. This will require the development of management systems and intellectual
property practices appropriate for such multisector initiatives.
INTEGRATING RESEARCH AND EDUCATION

Support for fundamental research in an education-rich environment charac-
terizes the U.S. research university and distinguishes it from universities in many
countries. The U.S. research university has indeed been, over the past 50 years,
the envy of the world. During the Cold War, much of the research activity in
these institutions was concentrated in physical sciences and engineering. As a
branch of physics with intimate links to engineering, condensed-matter and mate-
rials physics played a key role during this period in contributing to the research
strength, national defense, and economic health of the country. Its strong quan-
tum mechanical foundations, coupled with intimate links to the world of technol-
ogy, have been key features. Soon after the end of World War II, many of the
U.S.’s leading universities created applied physics departments and programs
that emphasized this link between physics and technology.
Today, with strong currents of change in the external environment, discussed
elsewhere in this report, we must reexamine the role in society of physics in
general and condensed-matter and materials physics in particular. To succeed in
coming decades, we must continue to pioneer new, often interdisciplinary, re-
search directions that address societal needs. In parallel, we are challenged to do
a better job of educating our students in a time of diminishing resources. To do
both well, we need to be more effective in integrating the teaching and research
components of academe’s mission, as is increasingly recognized nationally.
The National Science Foundation (NSF) highlighted, in its 1995 document
NSF in a Changing World, the importance of integrating education and research.
Along with the development of intellectual capital, physical infrastructure, and
promotion of partnerships, the integration of research and education forms one of
the four core strategies of NSF. A decade ago, NSF pioneered the creation of
Science and Technology Centers (STCs) and Engineering Research Centers
(ERCs), which focus both on interdisciplinary research and on the integration of
research and education. Many other excellent examples of undergraduate partici-
pation in research exist both in independent study, such as the NSF Research
Experience for Undergraduates (REU) Program, and in classroom-based activi-
ties. In addition, there is a national call to better integrate research and education
in graduate programs. To encourage this integration, NSF is supporting a number
of summer workshops for beginning science and engineering faculty and gradu-
ate students planning faculty careers.
The experience gained from these efforts, as well as the intrinsic nature of
condensed-matter and materials physics research, should allow physics, applied
physics, and materials-oriented faculty to make key contributions to campus-wide

THE NEXT DECADE 303
efforts to integrate research and education. To make this possible, we must work
proactively on many fronts. Universities and departments must be at the forefront
of this effort and can greatly increase the attraction of physics in basic ways.
1. Bring the excitement of research and discovery into education at an ear-

lier stage. The intimate relationship between technology and daily life provides
us with many opportunities to show this relationship to our students: quantum
mechanics in the real world, “seeing atoms” with tunneling microscopes, super-
conductivity, magnetism, and so on.
2. Take a more holistic approach to education, combining depth with breadth.
The importance of interdisciplinary education and research are particular strengths
of condensed-matter and materials physics. New linkages need to be forged with
other sciences, applied sciences, and engineering. Team-teaching that both high-
lights the fundamentals and illustrates concepts from different fields can broaden
horizons for both students and faculty.
3. Departments should consider new professional degree programs that link
undergraduate physics education with, for example, engineering-oriented disci-
plines. Professional master’s programs in engineering physics areas such as
instrumentation science, materials synthesis, and biotechnology, for example,
would be of particular importance to the condensed-matter and materials physics
community. Such programs would enhance the value of these degrees and be
particularly suited to training of the industrial physicist.
4. Joint academic appointments across departments, to break down disci-
plinary barriers, need to be encouraged. Campuses should experiment with the
creation of “virtual departments,” which would aid intellectual restructuring to
better achieve their research and education missions in changing times.
5. Most Ph.D. dissertations in condensed-matter and materials physics are
experimental. Many of today’s graduate students are very strong in computer
skills but have little hands-on experimental experience. This critical imbalance
in experimental skills can be corrected by requiring undergraduates to have re-
search experiences in faculty laboratories or summer internships in industry or at
national laboratories.
6. Applied physics departments and programs can serve as a critical link to
industrial liaison programs, which generally are strong in colleges of engineer-
ing. The inclusion of an appropriate subset of physics and condensed-matter and
materials physics faculty and students would help to provide a critical link with
our technological future.
A RESEARCH STRATEGY FOR CONDENSED-MATTER AND

MATERIALS PHYSICS
Managing scientific research is a delicate matter. If one invested only in
winning projects in the right fields, the impact would presumably be enormous.

In reality, science proceeds on a broad front, with many advances dependent on

progress in other branches of science and technology, and breakthroughs coming
at unexpected times with unanticipated benefits. One need only consider the
discovery of high-temperature superconductivity to appreciate this unpredict-
ability. Nevertheless, there are important choices to be made. The desired output
of federal investments in science and technology is the creation of new knowl-
edge and discoveries; the desired outcome is improved economic growth, national
security, and quality of life. Although specific scientific breakthroughs cannot be
planned, the environment in which science is performed can be optimized to
encourage successful outputs and outcomes.
Discovery
Encouraging discovery is critical to the strategic success of condensed-
matter and materials physics. Incremental progress is not sufficient to maintain
leadership in science or technology. Although discovery cannot be predicted, it
often occurs when researchers explore the boundaries between fields and when
advances in instrumentation make possible new measurements. Both can be en-
couraged within the federal R&D system. Funding must be made available for
research at the interfaces between disciplines. For example, the new field of
molecular mechanics falls between structural biology and macromolecular phys-
ics. New mechanisms must be developed to encourage and evaluate interdiscipli-
nary proposals, which are often lost in a peer-review process organized according
to traditional disciplines. A multiplicity of funding sources is also essential to
ensure that bold, new ideas are given an opportunity to succeed. Increased
flexibility for agency program managers to take risks in funding decisions should
also be encouraged. New facilities and instrumentation create new opportunities
in condensed-matter and materials physics, and continued support for facilities
and for broad access to them must be emphasized. Finally, the strategic context
of the research should be understood, particularly in condensed-matter and mate-
rials physics, where the coupling to technology is so strong. The strategic context
of a research area encompasses the related technological issues and opportunities.
A broad appreciation of strategic context is important both in planning research
and in recognizing significant potential research developments. This apprecia-
tion is most effectively acquired through interactions with industry through re-
search partnerships, personnel exchanges, and consulting arrangements.
Scientific Themes
Chapters 1 through 6 of this report identify the key scientific questions that
are expected to drive the subfields of condensed-matter and materials physics for
the next decade. Specific areas of emphasis for future condensed-matter and
materials physics research are suggested. In this section, the committee addresses

THE NEXT DECADE 305
a broader question: Where is the field headed? In particular, what strategic

themes are expected to unite the field and catalyze scientific and technical
progress (see Box 8.5). Maintaining scientific excellence, a long-term perspec-
tive, and a world-class environment for research are essential. The research
environment has been the subject of much of this chapter, and recommendations
have been given for investing in facilities and infrastructure, encouraging part-
nerships across disciplines and institutions, integrating research and education,
and encouraging discovery. We turn now to strategic scientific themes for con-
densed-matter and materials physics.
The committee identified 10 scientific themes that span and underpin the
subfield-specific scientific priorities of condensed-matter and materials physics
as described in the body of this report. These themes, which are listed in Box 8.5,
represent high-level strategic priorities for condensed-matter and materials phys-
ics research over the next decade.
• The quantum mechanics of large, interacting systems focuses on the emer-

gent phenomena that result when large collections of atoms are brought together
to form a material. Important examples include Bose-Einstein condensation,
high-temperature superconductivity, and colossal magnetoresistance. These
emergent phenomena are bringing quantum mechanics into the world of our
experience.
• The realm of reduced dimensionality includes thin films, surfaces and
interfaces, artificially structured materials, polymer chains, and nanoclusters. An
improved understanding of thin-film growth, self-assembly, and materials prop-
erties at reduced dimensions is essential to technological advances ranging from
BOX 8.5 Strategic Scientific Themes in Condensed-Matter

and Materials Physics
• The quantum mechanics of large, interacting systems

• The structure and properties of materials at reduced dimensionality
• Materials with increasing complexity in composition, structure, and function
• Nonequilibrium processes and the relationship between molecular and me-
soscopic properties
• Soft condensed matter and the physics of large molecules, including biolog-
ical structures
• Controlling electrons and photons in solids on the atomic scale
• Understanding magnetism and superconductivity
• Properties of materials under extreme conditions
• Materials synthesis, processing, and nanofabrication
• Moving from empiricism toward predictability in the simulation of materials
properties and processes

displays to catalysis. Reduced dimensionality also provides opportunities to

extend understanding of fundamental phenomena including phase transitions,
magnetism, morphological development and strain, and novel quantum effects.
• Continued progress in condensed-matter and materials physics depends
on the ability to understand materials at increasing levels of compositional, struc-
tural, and functional complexity. Advances in atomic-scale visualization, syn-
chrotron and neutron sources, and computational capabilities are providing op-
portunities to extend fundamental understanding beyond model systems to the
structure and properties of real materials. Examples include highly correlated
systems, multicomponent magnets and superconductors, and polymer blends.
• Nonequilibrium processes include phenomena such as friction, fracture,
microstructural evolution, and pattern formation. These phenomena occur away
from mechanical and thermal equilbrium and, in many cases, are controlled by
processes that develop both at the atomic and mesoscopic scales. The ability to
bridge length scales and to understand complex patterns in fluids and solidifica-
tion is essential to continued progress.
• There has been a spectacular increase in soft condensed-matter research
over the past decade. This field emphasizes the softness and fluidity of materi-
als—the physics of large molecules. Its importance derives from the pervasive
use of polymers, complex fluids, and macromolecular systems in medicine, in-
dustry, and consumer products. Research in soft condensed matter has strong
connections to biology, especially through fundamental understanding derived
from synchrotron and neutron sources and from investigations of molecular me-
chanics and energy flow.
• The fundamental understanding of electrons and photons in solids under-
pins the Information Age. Driven by the need for faster, cheaper, more compact
information-processing and communication technologies, the limits of electronic
and photonic phenomena are relentlessly challenged. The future of these tech-
nologies depends on the ability to control electrons and photons in solids at the
near-atomic level.
• Magnetism and superconductivity are interrelated phenomena of enor-
mous fundamental and technological importance. Although much progress has
been made, the basic understanding of magnetism is incomplete, and there is no
agreement as to why high-temperature superconductivity occurs. Research is
needed in many areas including low-dimensional magnetism, nanoscale magne-
tism, and high-temperature superconducting phenomena.
• Research on the structure and properties of materials under extreme con-
ditions of pressure, temperature, and magnetic field continues to provide one
of the most powerful means to test theories and explore novel phenomena in
condensed-matter and materials physics.
• Materials synthesis is an area of extreme importance to condensed-matter
and materials physics. In many areas of condensed-matter and materials physics
research, the availability of research samples of sufficient quality and size is the

THE NEXT DECADE 307
limiting step to continued progress. The United States has lagged in the develop-
ment of materials-synthesis and processing capabilities despite strong recom-
mendations from the National Research Council report, Materials Science and
Engineering for the 1990s: Maintaining Competitiveness in the Age of Materials.1
Access to facilities for nanofabrication and crystal growth is needed, as well as
increased emphasis on processing research.
• The increasing power of computers foreshadows a shift from empriricism
toward increased predictability in materials development. Although in its in-
fancy, this shift presents significant challenges to and opportunities for materials
theory and computional physics. The prospects for accelerating progress in
condensed-matter and materials physics through simulation of complex systems
are truly revolutionary.
Excellence with Relevance

Condensed-matter and materials physics is science at the technological fron-
tier. The fundamental understanding of materials and materials phenomena is
central to continuing advances in almost all areas of modern technology. Enor-
mous societal benefits have been derived from condensed-matter and materials
physics research. The continued impact of condensed-matter and materials phys-
ics depends on maintaining leadership across the broad spectrum of condensed-
matter and materials physics research activities. It requires strategic investments
in research, facilities and infrastructure, and human capital. It requires a research
system that encourages discovery and partnerships. It requires an integra-
tion of contributions from a diversity of research approaches, institutions, and
disciplines.
The recommendations of this report are intended to encourage continued
excellence with relevance in condensed-matter and materials physics. Guidance
is provided on strategic priorities for scientific themes and the research environ-
ment. Urgent facilities and infrastructure needs are addressed. The importance
of partnerships involving universities, government laboratories, and industry and
spanning disciplines and agencies is emphasized. These partnerships are essen-
tial to leverage resources, enable cross-disciplinary research, and provide a stra-
tegic context for condensed-matter and materials physics research. The integra-
tion of research and education is also discussed along with recommendations for
improving condensed-matter and materials physics education.
Condensed-matter and materials physics lies at the heart of revolutionary
advances in broad areas of science and technology. The next decade promises
exciting new discoveries and powerful technology impacts as new capabilities in
synchrotron and neutron research, atomic-scale visualization, nanofabrication,
1Materials Science and Engineering for the 1990s: Maintaining Competitiveness in the Age of
Materials, National Academy Press, Washington, D.C. (1989).

computing, and many other areas probe the secrets of materials and materials-
related phenomena. This is a new era, as vast new arenas ranging from subtle
quantum phenomena, to macromolecular science, to the realm of complex mate-
rials become increasingly accessible to fundamental study. It is a time of excep-
tional opportunity to perform pioneering research at the technological frontier—
a frontier enabled by advances in condensed-matter and materials physics.

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Committee on Condensed-Matter and Materials Physics

Commission on Physical Sciences, Mathematics, and Applications

National Research Council

NATIONAL ACADEMY PRESS

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International Standard Book Number 0-309-06349-3

Copyright 1999 by the National Academy of Sciences. All rights reserved.

Printed in the United States of America

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VENKATESH NARAYANAMURTI, Harvard University, Chair

DONALD C. SHAPERO, Director

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BOARD ON PHYSICS AND ASTRONOMY

ROBERT C. DYNES, University of California, San Diego, Chair

DONALD C. SHAPERO, Director

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COMMISSION ON PHYSICAL SCIENCES, MATHEMATICS,

PETER M. BANKS, Environmental Research Institute of Michigan, Co-chair

NORMAN METZGER, Executive Director

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1. Identify future opportunities and priorities in the field.

The committee was composed of individuals whose backgrounds reflect the

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Lowenberg, Tom Lubensky, C. Macosko, Richard Martin, Denis McWhan, Jim

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Phillip W. Anderson, Princeton University,

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1 Electronic, Optical, and Magnetic Materials and Phenomena:

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Optical Materials and Phenomena, 56

2 New Materials and Structures 93

3 Novel Quantum Phenomena 137

4 Nonequilibrium Physics 168

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5 Soft Condensed Matter: Complex Fluids, Macromolecular Systems,

6 New Tools for Research 225

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Electronic Structure, 231

7 Changes in the R&D Landscape 274

8 The Next Decade 288

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Condensed-matter and materials physics plays a central role in many of the

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2 CONDENSED-MATTER AND MATERIALS PHYSICS

improved public understanding of science, better education of scientists and engi-

• The intellectual vitality of the field must be nurtured, particularly by

In this report the committee makes a number of recommendations for steps

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The different modes of research—benchtop experiments, larger collabora-

• The National Science Foundation, the U.S. Department of Energy, the

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