EP 364 SOLID STATE PHYSICS

Course Coordinator Prof. Dr. Beire Gnl

INTRODUCTION

AIM OF SOLID STATE PHYSICS WHAT IS SOLID STATE PHYSICS AND WHY DO IT? CONTENT REFERENCES

EP364 SOLID STATE PHYSICS INTRODUCTION

Aim of Solid State Physics

Solid state physics (SSP) explains the properties of solid materials as found on earth. The properties are expected to follow from Schrdingers eqn. for a collection of atomic nuclei and electrons interacting with electrostatic forces. The fundamental laws governing the behaviour of solids are known and well tested.

EP364 SOLID STATE PHYSICS INTRODUCTION

Crystalline Solids

We will deal with crystalline solids, that is solids with an atomic structure based on a regular repeated pattern. Many important solids are crystalline. More progress has been made in understanding the behaviour of crystalline solids than that of noncrystalline materials since the calculation are easier in crystalline materials.
EP364 SOLID STATE PHYSICS INTRODUCTION

What is solid state physics?

Solid state physics, also known as condensed matter physics, is the study of the behaviour of atoms when they are placed in close proximity to one another. In fact, condensed matter physics is a much better name, since many of the concepts relevant to solids are also applied to liquids, for example.

EP364 SOLID STATE PHYSICS INTRODUCTION

What is the point?

Understanding the electrical properties of solids is right at the heart of modern society and technology. The entire computer and electronics industry relies on tuning of a special class of material, the semiconductor, which lies right at the metalinsulator boundary. Solid state physics provide a background to understand what goes on in semiconductors.
EP364 SOLID STATE PHYSICS INTRODUCTION

Solid state physics (SSP) is the applied physics

New technology for the future will inevitably involve developing and understanding new classes of materials. By the end of this course we will see why this is a non-trivial task.

So, SSP is the applied physics associated with technology rather than interesting fundamentals.

EP364 SOLID STATE PHYSICS INTRODUCTION

Electrical resistivity of three states of solid matter

How can this be? After all, they each contain a system of atoms and especially electrons of similar density. And the plot thickens: graphite is a metal, diamond is an insulator and buckminster-fullerene is a superconductor.

They are all just carbon!

EP364 SOLID STATE PHYSICS INTRODUCTION

Among our aims - understand why one is a metal and one an insulator, and then the physical origin of the marked features. Also think about thermal properties etc. etc.

CONTENT

Chapter 1. Crystal Structure Chapter 2. X-ray Crystallography Chapter 3. Interatomic Forces Chapter 4. Crystal Dynamics Chapter 5. Free Electron Theory

EP364 SOLID STATE PHYSICS INTRODUCTION

CHAPTER 1. CRYSTAL STRUCTURE

Elementary Crystallography

Solid materials (crystalline, polycrystalline, amorphous) Crystallography Crystal Lattice Crystal Structure Types of Lattices Unit Cell Directions-Planes-Miller Indices in Cubic Unit Cell

Typical Crystal Structures

(3D 14 Bravais Lattices and the Seven Crystal System)

Elements of Symmetry
EP364 SOLID STATE PHYSICS INTRODUCTION

CHAPTER 2. X-RAY CRYSTALLOGRAPHY

X-ray Diffraction Bragg equation X-ray diffraction methods Laue Method Rotating Crystal Method Powder Method Neutron & electron diffraction

EP364 SOLID STATE PHYSICS INTRODUCTION

CHAPTER 3. INTERATOMIC FORCES

Energies of Interactions Between Atoms Ionic bonding

NaCl Comparision of ionic and covalent bonding

Covalent bonding

Metallic bonding Van der waals bonding Hydrogen bonding

EP364 SOLID STATE PHYSICS INTRODUCTION

CHAPTER 4. CRYSTAL DYNAMICS

Sound wave Lattice vibrations of 1D cystal Chain of identical atoms Chain of two types of atoms Phonons Heat Capacity Density of States Thermal Conduction Energy of harmonic oscillator Thermal energy & Lattice Vibrations Heat Capacity of Lattice vibrations
EP364 SOLID STATE PHYSICS INTRODUCTION

CHAPTER 5. FREE ELECTRON THEORY

Free electron model Heat capacity of free electron gas Fermi function, Fermi energy Fermi dirac distribution function Transport properties of conduction electrons

EP364 SOLID STATE PHYSICS INTRODUCTION

REFERENCES

Core book: Solid state physics, J.R.Hook and H.E.Hall, Second edition (Wiley) Other books at a similar level: Solid state physics, Kittel (Wiley) Solid state physics, Blakemore (Cambridge) Fundamentals of solid state physics, Christman (Wiley) More advanced: Solid state physics, Ashcroft and Mermin
EP364 SOLID STATE PHYSICS INTRODUCTION

CHAPTER 1 CRYSTAL STRUCTURE

Elementary Crystallography Typical Crystal Structures Elements Of Symmetry

Objectives
By the end of this section you should:

be able to identify a unit cell in a symmetrical pattern know that there are 7 possible unit cell shapes be able to define cubic, tetragonal, orthorhombic and hexagonal unit cell shapes
Crystal Structure 18

matter

Matter

GASES

LIQUIDS and LIQUID CRYSTALS

SOLIDS

Crystal Structure

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Gases

Gases have atoms or molecules that do not bond to one another in a range of pressure, temperature and volume. These molecules havent any particular order and move freely within a container.

Crystal Structure

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Liquids and Liquid Crystals

Similar to gases, liquids havent any atomic/molecular order and they assume the shape of the containers. Applying low levels of thermal energy can easily break the existing weak bonds.

Liquid crystals have mobile molecules, but a type of long range order can exist; the molecules have a permanent dipole. Applying an electric field rotates the dipole and establishes order within the collection of Crystal Structure molecules.

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Crytals

Solids consist of atoms or molecules executing thermal motion about an equilibrium position fixed at a point in space. Solids can take the form of crystalline, polycrstalline, or amorphous materials. Solids (at a given temperature, pressure, and volume) have stronger bonds between molecules and atoms than liquids. Solids require more energy to break the bonds.
Crystal Structure 22

ELEMENTARY CRYSTALLOGRAPHY

SOLID MATERIALS
CRYSTALLINE Single Crystal POLYCRYSTALLINE AMORPHOUS
(Non-crystalline)

Crystal Structure

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Types of Solids

Single crsytal, polycrystalline, and amorphous, are the three general types of solids. Each type is characterized by the size of ordered region within the material. An ordered region is a spatial volume in which atoms or molecules have a regular geometric arrangement or periodicity.

Crystal Structure

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Crystalline Solid

Crystalline Solid is the solid form of a substance in which the atoms or molecules are arranged in a definite, repeating pattern in three dimension. Single crystals, ideally have a high degree of order, or regular geometric periodicity, throughout the entire volume of the material.

Crystal Structure

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Crystalline Solid

Single crystal has an atomic structure that repeats periodically across its whole volume. Even at infinite length scales, each atom is related to every other equivalent atom in the structure by translational symmetry
Single Pyrite Crystal

Amorphous Solid Single Crystal

Crystal Structure 26

Polycrystalline Solid

Polycrystal is a material made up of an aggregate of many small single crystals (also called crystallites or grains). Polycrystalline material have a high degree of order over many atomic or molecular dimensions. These ordered regions, or single crytal regions, vary in size and orientation wrt one another. These regions are called as grains ( domain) and are separated from one another by grain boundaries. The atomic order can vary from one domain to the next. The grains are usually 100 nm - 100 microns in diameter. Polycrystals with grains that are <10 nm in diameter are called nanocrystalline

Polycrystalline Pyrite form (Grain)

Crystal Structure 27

Amorphous Solid

Amorphous (Non-crystalline) Solid is composed of randomly orientated atoms , ions, or molecules that do not form defined patterns or lattice structures. Amorphous materials have order only within a few atomic or molecular dimensions. Amorphous materials do not have any long-range order, but they have varying degrees of short-range order. Examples to amorphous materials include amorphous silicon, plastics, and glasses. Amorphous silicon can be used in solar cells and thin film transistors.

Crystal Structure

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Departure From Perfect Crystal

Strictly speaking, one cannot prepare a perfect crystal. For example, even the surface of a crystal is a kind of imperfection because the periodicity is interrupted there. Another example concerns the thermal vibrations of the atoms around their equilibrium positions for any temperature T>0K.

As a third example, actual crystal always contains some foreign atoms, i.e., impurities. These impurities spoils the perfect crystal structure.
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Crystal Structure

CRYSTALLOGRAPHY
What is crystallography? The branch of science that deals with the geometric description of crystals and their internal arrangement.

Crystal Structure

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Crystallography
Crystallography is essential for solid state physics

Symmetry of a crystal can have a profound influence on its properties. Any crystal structure should be specified completely, concisely and unambiguously. Structures should be classified into different types according to the symmetries they possess.

Crystal Structure

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ELEMENTARY CRYSTALLOGRAPHY

A basic knowledge of crystallography is essential for solid state physicists;

to specify any crystal structure and to classify the solids into different types according to the symmetries they possess.

Symmetry of a crystal can have a profound influence on its properties. We will concern in this course with solids with simple structures.
Crystal Structure 32

CRYSTAL LATTICE
What is crystal (space) lattice? In crystallography, only the geometrical properties of the crystal are of interest, therefore one replaces each atom by a geometrical point located at the equilibrium position of that atom.

Platinum

Platinum surface
(scanning tunneling microscope)
Crystal Structure

Crystal lattice and structure of Platinum

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Crystal Lattice
y

An infinite array of points in space, Each point has identical surroundings to all others. Arrays are arranged exactly in a periodic manner.

B b

C O a A

D x

Crystal Structure

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Crystal Structure

Crystal structure can be obtained by attaching atoms, groups of atoms or molecules which are called basis (motif) to the lattice sides of the lattice point. Crystal Structure = Crystal Lattice + Basis

Crystal Structure

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A two-dimensional Bravais lattice with different choices for the basis

Basis
A group of atoms which describe crystal structure
y y B b O C F a A D G x E H B b O C a A D x E

a) Situation of atoms at the b) Crystal lattice obtained by corners of regular hexagons Crystal identifying all the atoms in (a) Structure 37

Crystal structure

Don't mix up atoms lattice points Lattice points infinitesimal points space Lattice points do necessarily lie at centre of atoms

with are in not the

Crystal Structure = Crystal Lattice

+ Basis

Crystal Structure

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Crystal Lattice

Bravais Lattice (BL)

All atoms are of the same kind All lattice points are equivalent

Non-Bravais Lattice (non-BL)

Atoms can be of different kind Some lattice points are not equivalent A combination of two or more BL

Crystal Structure

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Types Of Crystal Lattices

1) Bravais lattice is an infinite array of discrete points with an arrangement and orientation that appears exactly the same, from whichever of the points the array is viewed. Lattice is invariant under a translation.

Nb film
Crystal Structure 40

Types Of Crystal Lattices

2) Non-Bravais Lattice Not only the arrangement but also the orientation must appear exactly the same from every point in a bravais lattice.

The red side has a neighbour to its immediate left, the blue one instead has a neighbour to its right. Red (and blue) sides are equivalent and have the same appearance Red and blue sides are not equivalent. Same appearance can be obtained rotating blue side 180.
Honeycomb
Crystal Structure 41

Translational Lattice Vectors 2D

A space lattice is a set of points such that a translation from any point in the lattice by a vector;
P

Rn = n1 a + n2 b locates an exactly equivalent point, i.e. a point with the same environment as P . This is translational symmetry. The vectors a, b are known as lattice vectors and (n1, n2) is a pair of integers whose values depend on the lattice point.
Crystal Structure 42

Point D(n1, n2) = (0,2) Point F (n1, n2) = (0,-1)

Lattice Vectors 2D

The two vectors a and b form a set of lattice vectors for the lattice. The choice of lattice vectors is not unique. Thus one could equally well take the vectors a and b as a lattice vectors.

Crystal Structure

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Lattice Vectors 3D
An ideal three dimensional crystal is described by 3 fundamental translation vectors a, b and c. If there is a lattice point represented by the position vector r, there is then also a lattice point represented by the position vector where u, v and w are arbitrary integers.

r = r + u a + v b + w c

(1)

Crystal Structure

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Five Bravais Lattices in 2D

Crystal Structure

45

Unit Cell in 2D

The smallest component of the crystal (group of atoms, ions or molecules), which when stacked together with pure translational repetition reproduces the whole crystal.

S S b S a S S

S S S S S S S
Crystal Structure

S S S
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Unit Cell in 2D

The smallest component of the crystal (group of atoms, ions or molecules), which when stacked together with pure translational repetition reproduces the whole crystal.

The choice of unit cell is not unique. b S

S S

S a
Crystal Structure 47

2D Unit Cell example -(NaCl)

We define lattice points ; these are points with identical environments

Crystal Structure 48

Choice of origin is arbitrary - lattice points need not be atoms - but unit cell size should always be the same.

Crystal Structure

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This is also a unit cell it doesnt matter if you start from Na or Cl

Crystal Structure

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- or if you dont start from an atom

Crystal Structure

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This is NOT a unit cell even though they are all the same - empty space is not allowed!

Crystal Structure

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In 2D, this IS a unit cell In 3D, it is NOT

Crystal Structure

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Why can't the blue triangle be a unit cell?

Crystal Structure

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Unit Cell in 3D

Crystal Structure

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Unit Cell in 3D

Crystal Structure

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Three common Unit Cell in 3D

Crystal Structure

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UNIT CELL

Primitive
Single lattice point per cell Smallest area in 2D, or Smallest volume in 3D

Conventional & Non-primitive

More than one lattice point per cell Integral multibles of the area of primitive cell

Simple cubic(sc) Conventional = Primitive cell

Body centered cubic(bcc) Conventional Primitive cell

Crystal Structure 58

The Conventional Unit Cell

A unit cell just fills space when translated through a subset of Bravais lattice vectors. The conventional unit cell is chosen to be larger than the primitive cell, but with the full symmetry of the Bravais lattice. The size of the conventional cell is given by the lattice constant a.
Crystal Structure 59

Primitive and conventional cells of FCC

Crystal Structure

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Primitive and conventional cells of BCC

Primitive Translation Vectors:

1 + y z ) (x a1 = 2 1 + y +z ) ( x a2 = 2 1 y +z ) (x a3 = 2

Primitive and conventional cells

Body centered cubic (bcc): conventional primitive cell
b c a

Fractional coordinates of lattice points in conventional cell: 000,100, 010, 001, 110,101, 011, 111, Simple cubic (sc): primitive cell=conventional cell

c
a

Fractional coordinates of lattice points: 000, 100, 010, 001, 110,101, 011, 111

Crystal Structure

62

Primitive and conventional cells

b

Body centered cubic (bcc): primitive (rombohedron) conventional cell Fractional coordinates:
000, 100, 101, 110, 110,101, 011, 211, 200

Face centered cubic (fcc): conventional primitive cell

b
c a

Fractional coordinates:
000,100, 010, 001, 110,101, 011,111, 0, 0 , 0 ,1 , 1 , 1
Crystal Structure 63

Primitive and conventional cells-hcp

points of primitive cell

Hexagonal close packed cell (hcp): conventional =primitive cell

c

Fractional coordinates: 100, 010, 110, 101,011, 111,000, 001

b
a
Crystal Structure 64

Unit Cell

The unit cell and, consequently, the entire lattice, is uniquely determined by the six lattice constants: a, b, c, , and . Only 1/8 of each lattice point in a unit cell can actually be assigned to that cell. Each unit cell in the figure can be associated with 8 x 1/8 = 1 lattice point.
Crystal Structure 65

Primitive Unit Cell and vectors

A primitive unit cell is made of primitive translation vectors a1 ,a2, and a3 such that there is no cell of smaller volume that can be used as a building block for crystal structures. A primitive unit cell will fill space by repetition of suitable crystal translation vectors. This defined by the parallelpiped a1, a2 and a3. The volume of a primitive unit cell can be found by V = a1.(a2 x a3) (vector products)
Crystal Structure

Cubic cell volume = a3

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Primitive Unit Cell

The primitive unit cell must have only one lattice point. There can be different choices for lattice vectors , but the volumes of these primitive cells are all the same.
a1

P = Primitive Unit Cell NP = Non-Primitive Unit Cell

Crystal Structure

67

Wigner-Seitz Method
A simply way to find the primitive cell which is called Wigner-Seitz cell can be done as follows; 1. Choose a lattice point. 2. Draw lines to connect these lattice point to its neighbours. 3. At the mid-point and normal to these lines draw new lines.
The volume enclosed is called as a Wigner-Seitz cell.
Crystal Structure 68

Wigner-Seitz Cell - 3D

Crystal Structure

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Lattice Sites in Cubic Unit Cell

Crystal Structure

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Crystal Directions

We choose one lattice point on the line as an origin, say the point O. Choice of origin is completely arbitrary, since every lattice point is identical. Then we choose the lattice vector joining O to any point on the line, say point T. This vector can be written as; R = n1 a + n2 b + n3c

To distinguish a lattice direction from a lattice point, the triple is enclosed in square brackets [ ...] is used.[n1n2n3] [n1n2n3] is the smallest integer of the same relative ratios.
Crystal Structure

Fig. Shows [111] direction

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Examples

210

X=1,Y=,Z=0 [1 0] [2 1 0]
Crystal Structure

X= ,Y=,Z=1 [ 1] [1 1 2]
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Negative directions

When we write the direction [n1n2n3] depend on the origin, negative directions can be written as
[n1n2 n3 ]

Z direction

(origin) O
- Y direction
[n1n2 n3 ]

- X direction Y direction

R = n1 a + n2 b + n3c

Direction must be smallest integers.

X direction - Z direction
Crystal Structure 73

Examples of crystal directions

X=1,Y=0,Z=0

[1 0 0]

X = -1 , Y = -1 , Z = 0
Crystal Structure

[110]
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Examples

We can move vector to the origin.

X =-1 , Y = 1 , Z = -1/6 [-1 1 -1/6] [6 6 1]

Crystal Structure 75

Crystal Planes

Within a crystal lattice it is possible to identify sets of equally spaced parallel planes. These are called lattice planes. In the figure density of lattice points on each plane of a set is the same and all lattice points are contained on each set of planes.

The set of planes in 2D lattice.

b a

b a

Crystal Structure

76

Miller Indices
Miller Indices are a symbolic vector representation for the orientation of an atomic plane in a crystal lattice and are defined as the reciprocals of the fractional intercepts which the plane makes with the crystallographic axes. To determine Miller indices of a plane, take the following steps; 1) Determine the intercepts of the plane along each of the three crystallographic directions 2) Take the reciprocals of the intercepts 3) If fractions result, multiply each by the denominator of the smallest fraction
Crystal Structure 77

Example-1
Axis
Intercept points Reciprocals Smallest Ratio

1 1

1/1 1/ 1/ (100)

(1,0,0)

Miller ndices

Crystal Structure

78

Example-2
Axis
Intercept points Reciprocals Smallest Ratio

1 1

1 1

0 (110)

1/1 1/ 1 1/

(0,1,0) (1,0,0)

Miller ndices

Crystal Structure

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Example-3
Axis
Intercept points Reciprocals (0,1,0) (1,0,0) Smallest Ratio

(0,0,1)

1 1

1 1

1 1 (111)

1/1 1/ 1 1/ 1

Miller ndices

Crystal Structure

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Example-4
Axis
Intercept points Reciprocals (0,1,0)
(1/2, 0, 0)

1/2 2

1 1

1/() 1/ 1 1/ (210)

Smallest Ratio

Miller ndices

Crystal Structure

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Example-5
Axis
Intercept points Reciprocals Smallest Ratio

1
1/1

1/

1/()

Miller ndices
Crystal Structure

(102)
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Example-6
Axis
Intercept points Reciprocals Smallest Ratio

-1
1/-1

1/

1/()

-1

Miller ndices
Crystal Structure

(102)
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Miller Indices
[2,3,3] 2 Plane intercepts axes at

3a , 2b , 2c 1 1 1 Reciprocal numbers are: , , 3 2 2

Indices of the direction: [2,3,3]

b
2

Indices of the plane (Miller): (2,3,3)

a
3

(200) (110) (100)

Crystal Structure

(111)

(100)
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Crystal Structure

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Example-7

Crystal Structure

86

Indices of a Family or Form

Sometimes when the unit cell has rotational symmetry, several nonparallel planes may be equivalent by virtue of this symmetry, in which case it is convenient to lump all these planes in the same Miller Indices, but with curly brackets.

{100} (100), (010), (001), (0 1 0), (00 1 ), ( 1 00) {111} (111), (11 1 ), (1 1 1), ( 1 11), ( 1 1 1 ), ( 1 1 1), ( 1 1 1 ), (1 1 1 )

Thus indices {h,k,l} represent all the planes equivalent to the plane (hkl) through rotational symmetry.
Crystal Structure 87

TYPICAL CRYSTAL STRUCTURES

3D 14 BRAVAIS LATTICES AND THE SEVEN CRYSTAL SYSTEM

There are only seven different shapes of unit cell which can be stacked together to completely fill all space (in 3 dimensions) without overlapping. This gives the seven crystal systems, in which all crystal structures can be classified. Cubic Crystal System (SC, BCC,FCC) Hexagonal Crystal System (S) Triclinic Crystal System (S) Monoclinic Crystal System (S, Base-C) Orthorhombic Crystal System (S, Base-C, BC, FC) Tetragonal Crystal System (S, BC) Trigonal (Rhombohedral) Crystal Crystal System (S) Structure

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Crystal Structure

89

Coordinaton Number
Coordinaton Number (CN) : The Bravais lattice points closest to a given point are the nearest neighbours. Because the Bravais lattice is periodic, all points have the same number of nearest neighbours or coordination number. It is a property of the lattice. A simple cubic has coordination number 6; a bodycentered cubic lattice, 8; and a face-centered cubic lattice,12.
Crystal Structure 90

Atomic Packing Factor

Atomic Packing Factor (APF) is defined as the volume of atoms within the unit cell divided by the volume of the unit cell.

1-CUBIC CRYSTAL SYSTEM

a- Simple Cubic (SC)

Simple Cubic has one lattice point so its primitive cell. In the unit cell on the left, the atoms at the corners are cut because only a portion (in this case 1/8) belongs to that cell. The rest of the atom belongs to neighboring cells. Coordinatination number of simple cubic is 6.

c a
Crystal Structure 92

a- Simple Cubic (SC)

Crystal Structure

93

Atomic Packing Factor of SC

Crystal Structure

94

b-Body Centered Cubic (BCC)

BCC has two lattice points so BCC is a non-primitive cell. BCC has eight nearest neighbors. Each atom is in contact with its neighbors only along the bodydiagonal directions. Many metals (Fe,Li,Na..etc), including the alkalis and several transition elements choose the BCC structure.
Crystal Structure

c a
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Atomic Packing Factor of BCC

APF B C C= V a to m s = 0 .6 V u n ict e l l

(0,433a)

Crystal Structure

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c- Face Centered Cubic (FCC)

There are atoms at the corners of the unit cell and at the center of each face. Face centered cubic has 4 atoms so its non primitive cell. Many of common metals (Cu,Ni,Pb..etc) crystallize in FCC structure.

Crystal Structure

97

3 - Face Centered Cubc

Crystal Structure

Atoms are all same.98

Atomic Packing Factor of FCC

V a t o m s 0,74 = 0 .6 APF B C C= FCC V u n ict e l l

(0,353a)

Crystal Structure

99

Unit cell contents

Counting the number of atoms within the unit cell
Atoms corner face centre body centre edge centre
lattice type P I F C

Shared Between: 8 cells 2 cells 1 cell 2 cells

Each atom counts: 1/8 1/2 1 1/2

cell contents 1 [=8 x 1/8] 2 [=(8 x 1/8) + (1 x 1)] 4 [=(8 x 1/8) + (6 x 1/2)] 2 [=(8 x 1/8) + (2 x 1/2)]
Crystal Structure 100

Example; Atomic Packing Factor

Crystal Structure

101

2 - HEXAGONAL SYSTEM

A crystal system in which three equal coplanar axes intersect at an angle of 60 , and a perpendicular to the others, is of a different length.

Crystal Structure

102

2 - HEXAGONAL SYSTEM

Crystal Structure

103 Atoms are all same.

Crystal Structure

104

3 - TRICLINIC 4 - MONOCLINIC CRYSTAL SYSTEM

Triclinic minerals are the least symmetrical. Their three axes are all different lengths and none of them are perpendicular to each other. These minerals are the most difficult to recognize.

Triclinic (Simple) 90 oa b c

Monoclinic (Simple) = = 90o, 90o a b c

Crystal Structure

Monoclinic (Base Centered) = = 90o, 90o a b c,

105

5 - ORTHORHOMBIC SYSTEM

Orthorhombic (Simple) = = = 90o abc

Orthorhombic (Basecentred) = = = 90o abc

Orthorhombic (BC) = = = 90o abc

Orthorhombic (FC) = = = 90o abc

Crystal Structure

106

6 TETRAGONAL SYSTEM

Tetragonal (P) = = = 90o a=bc

Crystal Structure

Tetragonal (BC) = = = 90o a=bc

107

7 - Rhombohedral (R) or Trigonal

Rhombohedral (R) or Trigonal (S) a = b = c, = = 90o

Crystal Structure 108

THE MOST IMPORTANT CRYSTAL STRUCTURES

Sodium Chloride Structure Na+ClCesium Chloride Structure Cs+ClHexagonal Closed-Packed Structure Diamond Structure Zinc Blende

Crystal Structure

109

1 Sodium Chloride Structure

Sodium chloride also crystallizes in a cubic lattice, but with a different unit cell. Sodium chloride structure consists of equal numbers of sodium and chlorine ions placed at alternate points of a simple cubic lattice. Each ion has six of the other kind of ions as its nearest neighbours.
Crystal Structure 110

Sodium Chloride Structure

If we take the NaCl unit cell and remove all the red Cl ions, we are left with only the blue Na. If we compare this with the fcc / ccp unit cell, it is clear that they are identical. Thus, the Na is in a fcc sublattice.

Crystal Structure

112

Sodium Chloride Structure

This structure can be considered as a facecentered-cubic Bravais lattice with a basis consisting of a sodium ion at 0 and a chlorine ion at the center of the conventional cell,
a / 2( x + y + z )

LiF,NaBr,KCl,LiI,etc The lattice constants are in the order of 4-7 angstroms.

2-Cesium Chloride Structure Cs+Cl

Cesium chloride crystallizes in a cubic lattice. The unit cell may be depicted as shown. (Cs+ is teal, Cl- is gold). Cesium chloride consists of equal numbers of cesium and chlorine ions, placed at the points of a body-centered cubic lattice so that each ion has eight of the other kind as its nearest neighbors.
Crystal Structure 114

Cesium Chloride Structure Cs+Cl

The translational symmetry of this structure is that of the simple cubic Bravais lattice, and is described as a simple cubic lattice with a basis consisting of a cesium ion at the origin 0 and a chlorine ion at the cube center
a / 2( x + y + z )

CsBr,CsI crystallize in this structure.The lattice constants are in the order of 4 angstroms.

Cesium Chloride Cs+Cl-

8 cell

3Hexagonal Close-Packed Str.

This is another structure that is common, particularly in metals. In addition to the two layers of atoms which form the base and the upper face of the hexagon, there is also an intervening layer of atoms arranged such that each of these atoms rest over a depression between three atoms in the base.

Crystal Structure

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Hexagonal Close-packed Structure

Bravais Lattice : Hexagonal Lattice He, Be, Mg, Hf, Re (Group II elements) ABABAB Type of Stacking a=b a=120, c=1.633a, basis : (0,0,0) (2/3a ,1/3a,1/2c)

Crystal Structure

118

Packing
Close pack
A A A A A A B A A B A A A B A A B A A

BA BA BA B A C C C BA BA B A A C C C C BA BA B A B A C C C Sequence ABABAB.. -hexagonal close pack Sequence ABCABCAB.. -face centered cubic close pack
Crystal Structure

Sequence AAAA - simple cubic Sequence ABAB - body centered cubic

119

Crystal Structure

120

4 - Diamond Structure

The diamond lattice is consist of two interpenetrating face centered bravais lattices. There are eight atom in the structure of diamond. Each atom bonds covalently to 4 others equally spread about atom in 3d.

Crystal Structure

121

4 - Diamond Structure

The coordination number of diamond structure is 4. The diamond lattice is not a Bravais lattice. Si, Ge and C crystallizes in diamond structure.

Crystal Structure

123

5- Zinc Blende

Zincblende has equal numbers of zinc and sulfur ions distributed on a diamond lattice so that each has four of the opposite kind as nearest neighbors. This structure is an example of a lattice with a basis, which must so described both because of the geometrical position of the ions and because two types of ions occur. AgI,GaAs,GaSb,InAs,

5- Zinc Blende

5- Zinc Blende
Zinc Blende is the name given to the mineral ZnS. It has a cubic close packed (face centred) array of S and the Zn(II) sit in tetrahedral (1/2 occupied) sites in the lattice.

Crystal Structure

126

ELEMENTS OF SYMMETRY

Each of the unit cells of the 14 Bravais lattices has one or more types of symmetry properties, such as inversion, reflection or rotation,etc.

SYMMETRY

INVERSION

REFLECTION

ROTATION

Crystal Structure

127

Lattice goes into itself through Symmetry without translation

Operation Inversion Reflection Rotation Rotoinversion
Crystal Structure

Element Point Plane Axis Axes

128

Inversion Center

A center of symmetry: A point at the center of the molecule. (x,y,z) --> (-x,-y,-z) Center of inversion can only be in a molecule. It is not necessary to have an atom in the center (benzene, ethane). Tetrahedral, triangles, pentagons don't have a center of inversion symmetry. All Bravais lattices are inversion symmetric.
Mo(CO)6

Crystal Structure

129

Reflection Plane

A plane in a cell such that, when a mirror reflection in this plane is performed, the cell remains invariant.

Crystal Structure

130

Examples

Triclinic has no reflection plane. Monoclinic has one plane midway between and parallel to the bases, and so forth.
Crystal Structure 131

Rotation Symmetry We can not find a lattice that goes into itself under other rotations
A single molecule can have any degree of rotational symmetry, but an infinite periodic lattice can not.

Crystal Structure

132

Rotation Axis
90

120

180

This is an axis such that, if the cell is rotated around it through some angles, the cell remains invariant. The axis is called n-fold if the angle of rotation is 2/n.
Crystal Structure 133

Axis of Rotation

Crystal Structure

134

Axis of Rotation

Crystal Structure

135

5-fold symmetry

Can not be combined with translational periodicity!

Crystal Structure 136

Group discussion

Kepler wondered why snowflakes have 6 corners, never 5 or 7.By considering the packing of polygons in 2 dimensions, demonstrate why pentagons and heptagons shouldnt occur. Empty space not allowed

Crystal Structure

137

Examples
90

Triclinic has no axis of rotation. Monoclinic has 2-fold axis (= 2/2 =) normal to the base.

Crystal Structure

138

Crystal Structure

139