Lecture 6 - Synthesis of Nanomaterials

Synthesis of Nanomaterials
Junior Research Seminar

Spring 2004
4 May 2004
Junior Research Seminar: Nanoscale Patterning and Systems

Teri W. Odom
Approaches to Nanoscale Structures

Teri W. Odom
Chemical approaches to nanostructures

Zero dimensional structures
One dimensional structures
Three dimensional structures

Teri W. Odom
Zero Dimensional (0D) Growth

Teri W. Odom
Nanoparticle Growth within Dendrimers
Polymer macromolecules (poly

(amido amine)) bind limited
numbers of metal ions (Cu, Ag, Au,
Pt, Pd)
Driving force for encapsulation
includes electrostatics, steric
confinement, covalent bonds
Reducing agent causes the metal
ions to coalesce
Nanoparticles as small as 1 nm
Useful composite material

Metal particles not aggregated
Dendrimer branches control
access of other molecules
Terminal groups on dendrimer can
be used to control solubility,
linking to surfaces
R. Crooks, Acc. Chem. Res. 34, 181 (2001)

E.W. Meijer, Chem. Rev. 99, 1665 (1999)

Teri W. Odom
Reverse Micelles
Spherical water in oil droplets

surfactant is sodium bis(2-ethylhexyl)
sulfosuccinate) Na(AOT)
Size of water content depends on
relative surfactant concentration
Reduction of metal ions or

precipitation forms particles
Semiconductor particles (CdS) from 1
- 4 nm
Metals from 1 - 12 nm
M.P. Pileni, J. Phys. Chem. 97, 6961 (1993)
M.P. Pileni (France) Langmuir, 13, 3266 (1997)

Teri W. Odom
Cluster Growth within a Zeolite
Zeolite-OH + M(CH3)2
Intercalation of M ion into zeolite by ion exchange

Activation of M+ loaded zeolite
Reaction of activated M+ with H2S
Zeolite Y high dielectric, aluminosilicate host
Zeolite-OH + M(CH3)2
Zeolite-O-M(CH3) + CH4
H2S
Zeolite-O-M-SH + CH4
Repeat
Examples: MS nanoclusters CdS, ZnS, SnS, Ag2S

Calzeferri (U. Bern), J. Phys. Chem. B 103, 6397 (1999)

Teri W. Odom
Arrested Precipitation: General Approach
C.B. Murray (IBM)

Teri W. Odom
Arrested Precipitation
Aqueous reduction of metal

salts (Ag, Au) in the presence of
citrate ions
Strong reducing agent
Chemisorption of organic ligands

for handling
Distribution varies > 10%
II-VI ME nanocrystals (NCs) (M =

Zn, Cd, Hg; X = S, Se, Te)
Metal alkyls + organophosphine
chalcogenides
~200-250 C
Phosphine binding to M
controlled by temperature
Ostwald ripening allows for sizeselective aliquots; growth time for
1-2 nm NCs in minutes
Metal salts and stabilizers

(metal halides + inert solvent
+ R3P + long chain acids)
Schmid G. 1992. Chem. Rev. 92:170927

Teri W. Odom
Size-Dependent Properties:
Metallic Particles
Ag Nanoprisms Au Spheres Au Spheres

~100 nm
~50 nm
~100 nm
200nm
200 nm

Teri W. Odom
Ag Spheres Ag Spheres Ag Spheres

~80 nm
~40 nm
~120 nm
Size-Dependent Properties:
Semiconducting Particles
10 m
A. Libchaber (NEC) Science 298, 1759 (2002)
A.P. Alivisatos (U.C. Berkeley), Science 281, 2013 (1998)
Teri W. Odom


Teri W. Odom
One Dimensional (1D) Growth
Adapted after Y. Xia et al., Adv. Mat. 15, 353 (2003)

Teri W. Odom
Electrodeposition within Nanoporous Membranes
Alumina, polycarbonate track

etched, and silica membranes
5-10 m thick with pore sizes
down to 10 nm
M. Natan (Penn State), Science 294, 137 (2001)

Teri W. Odom
Templating against Existing 1D Nanostructures

GaN from ZnO Nanowires
P. Yang, Nature 422, 599 (2003)
TiC nanorods from MWNTs
C.M. Lieber, Chem. Mater., 8, 2041 (1996)

Teri W. Odom
Templating vs. Other Approaches?
Nanoscale structures generated by templating methods are

typically not crystalline
Number of defects is larger
Critical dimension (confined dimension) is larger; quantum size effects
usually not observed
Monodispersity is limited by the structure of template
Free-standing, 1D structures are difficult to obtain
What are the requirements for a general, synthetic approach

to nanowires?
Anisotropic growth
Equilibrium constraints
Control of catalyst size

Teri W. Odom
Laser-assisted Catalytic Growth
(1) Pulsed laser; (2) Focusing lens; (3) Composite target; (4) Furnace; (5) Cold finger; (6) Pump system
C.M. Lieber (Harvard), Science 279, 208 (1998)
Examples: InP, GaAs, InAs (Au colloids); GaN (Fe colloids)

Teri W. Odom
Chemical Vapor Deposition (CVD)
1 m

Teri W. Odom
Solution-based growth
Dissolution of anisotropic crystal

structures
Dissolve inorganic
metallopolymers in polar
solvents such as dimethyl
sulfoxide (DMSO) to form
hexagonally close packed,
linear chains ~2 nm in diameter
Example: Mo6Se6 wires
Other methods to obtain
anisotropy?
Reduction of an acid or salt in
elevated temperatures and
exploit Ostwald ripening
Decomposition of precursors in
the presence of capping ligands
(followed by fractionation for
size distribution)
Example: BaTiO3 and SrTiO3
(perovskite) nanostructures
F. diSalvo (Cornell), Science 273, 792 (1996)

P. Yang, Adv. Mat. 12, 1526 (2000)
H. Park (Harvard), J. Am. Chem. Soc. 124, 1186 (2002)

Teri W. Odom
Assembly of 0D nanoparticles
Organization of CdTe
nanoparticles into wires
Removal of stabilizer
Assembly over a week in the dark
Recrystallization
Ostwald ripening with Cd2+ and
Te2- ions
Diffusion of CdTe particles
N.A. Koltov (Okla. State), Science 297, 237 (2002)

Teri W. Odom


Teri W. Odom
Three dimensional (3D) nanostructures
Polymer emulsification
Reducing agent is also the solvent
In the presence of a capping reagent
and different ratios of seed source,
different types of structures
Example: reduction of silver nitrate by
ethylene glycol in the presence of
poly(vinyl pyrrolidone)
Replacement reactions
Conversion of one metal to one with a
higher reduction potential
Example: Replacement of Ag with Au
occurred along the crystal facets in
an order commensurate with their free
energies: {110} > {100} > {111}
Y. Xia (U. Wash.), Science 298, 2176 (2002); Nano. Lett., 2, 481 (2002)
Teri W. Odom
3Ag(s) + HAuCl4(aq)
Au(s) + 3AgCl(aq) + HCl(aq)
3D nanostructures: DNA-based assembly
Au nanostructures assembled by DNA

hybridization
Functionalize large and small Au particles with

different DNA strands
Introduce a linker strand that contains

complementary sequence to those on large
and small Au particles
C.A. Mirkin, Inorg. Chem. 39, 2258 (2000)

Teri W. Odom
3D nanostructures: NC superlattices
CdSe colloidal crystals

Introduce non-solvent to cause
aggregation and precipitation
Slow destabilization by
evaporation from a mixture of
solvents can result in ordered
superlattices
C.B. Murray, Annu. Rev. Mater. 30, 545 (2000)

Teri W. Odom
Lab 7: Synthesis of Nanomaterials

Gold colloids
CdSe nanocrystals

Teri W. Odom
Synthesis of CdSe Nanoparticles

CdO + oleic acid + octadecene
Heat to 250 C to dissolve the CdO
Selenium + octadecene + tributylphosphine
Heat to 150 C to dissolve the selenium
Transfer Se solution to the Cd solution
Take aliquots
http://www.mrsec.wisc.edu/EDETC/cineplex/CdSe/index.html
Teri W. Odom
Synthesis of Colloidal Gold

Make HAuCl4 solution in water and pour into a
beaker.
Weigh the HAuCl4 using a teflon-wrapped spatula
Heat the solution to boiling on a hot plate.
Add Na3C6H5O7 to the Au solution in the beaker.

Let the solution boil.
http://www.mrsec.wisc.edu/EDETC/cineplex/gold/index.html
Teri W. Odom
Gold Particles as a Chemical Sensor

Take a UV-Vis absorbance
spectrum of the Au colloid
solution.
Place 3 mL of the Au
colloid solution in each of
three glass vials. Add 3 mL
of water to dilute the colloid
solution.
Add 5-10 drops 1M NaCl to
the first vial dropwise.
Record what happens as
the salt solution is added.
Add 5-10 drops 1M
sucrose to the second vial
dropwise.
Teri W. Odom

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Synthesis of Nanomaterials

Junior Research Seminar

Junior Research Seminar: Nanoscale Patterning and Systems

Approaches to Nanoscale Structures

Junior Research Seminar: Nanoscale Patterning and Systems

Chemical approaches to nanostructures

One dimensional structures

Three dimensional structures

Junior Research Seminar: Nanoscale Patterning and Systems

Zero Dimensional (0D) Growth

Junior Research Seminar: Nanoscale Patterning and Systems

Nanoparticle Growth within Dendrimers

Polymer macromolecules (poly

Useful composite material

R. Crooks, Acc. Chem. Res. 34, 181 (2001)

Junior Research Seminar: Nanoscale Patterning and Systems

Spherical water in oil droplets

Reduction of metal ions or

M.P. Pileni, J. Phys. Chem. 97, 6961 (1993)

M.P. Pileni (France) Langmuir, 13, 3266 (1997)

Cluster Growth within a Zeolite

Intercalation of M ion into zeolite by ion exchange

Examples: MS nanoclusters CdS, ZnS, SnS, Ag2S

Junior Research Seminar: Nanoscale Patterning and Systems

Arrested Precipitation: General Approach

C.B. Murray (IBM)

Aqueous reduction of metal

Strong reducing agent

Chemisorption of organic ligands

II-VI ME nanocrystals (NCs) (M =

Metal salts and stabilizers

Schmid G. 1992. Chem. Rev. 92:170927

Ag Nanoprisms Au Spheres Au Spheres

Junior Research Seminar: Nanoscale Patterning and Systems

Ag Spheres Ag Spheres Ag Spheres

Chemical approaches to nanostructures

One dimensional structures

Three dimensional structures

Junior Research Seminar: Nanoscale Patterning and Systems

One Dimensional (1D) Growth

Adapted after Y. Xia et al., Adv. Mat. 15, 353 (2003)

Electrodeposition within Nanoporous Membranes

Alumina, polycarbonate track

M. Natan (Penn State), Science 294, 137 (2001)

Templating against Existing 1D Nanostructures

P. Yang, Nature 422, 599 (2003)

TiC nanorods from MWNTs

C.M. Lieber, Chem. Mater., 8, 2041 (1996)

Templating vs. Other Approaches?

Nanoscale structures generated by templating methods are

What are the requirements for a general, synthetic approach

Junior Research Seminar: Nanoscale Patterning and Systems

Laser-assisted Catalytic Growth

C.M. Lieber (Harvard), Science 279, 208 (1998)

Examples: InP, GaAs, InAs (Au colloids); GaN (Fe colloids)

Chemical Vapor Deposition (CVD)

Junior Research Seminar: Nanoscale Patterning and Systems

Dissolution of anisotropic crystal