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INTRODUCTION

WHAT IS SOLID STATE PHYSICS

AND WHY DO IT?

CONTENT

REFERENCES

solid materials as found on earth.

Schrdingers eqn. for a collection of atomic nuclei

and electrons interacting with electrostatic forces.

solids are known and well tested.

Crystalline Solids

with an atomic structure based on a regular

repeated pattern.

behaviour of crystalline solids than that of noncrystalline materials since the calculation are easier

in crystalline materials.

physics, is the study of the behaviour of atoms when

they are placed in close proximity to one another.

name, since many of the concepts relevant to solids

are also applied to liquids, for example.

right at the heart of modern society and technology.

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.

is the applied physics

developing and understanding new classes of

materials. By the end of this course we will see why

this is a non-trivial task.

technology rather than interesting fundamentals.

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.

one an insulator, and then the physical origin of the

marked features.

Also think about thermal properties etc. etc.

CONTENT

CHAPTER 1.

CRYSTAL STRUCTURE

Elementary Crystallography

amorphous)

Crystallography

Crystal Lattice

Crystal Structure

Types of Lattices

Unit Cell

Directions-Planes-Miller Indices in Cubic Unit Cell

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

Elements of Symmetry

CHAPTER 2.

X-RAY CRYSTALLOGRAPHY

X-ray

Diffraction

Bragg equation

X-ray diffraction methods

Laue Method

Rotating Crystal Method

Powder Method

Neutron & electron diffraction

CHAPTER 3.

INTERATOMIC FORCES

Ionic bonding

NaCl

Covalent bonding

Metallic bonding

Van der waals bonding

Hydrogen bonding

CHAPTER 4.

CRYSTAL DYNAMICS

Sound wave

Lattice vibrations of 1D cystal

Phonons

Heat Capacity

Density of States

Thermal Conduction

Energy of harmonic oscillator

CHAPTER 5.

FREE ELECTRON THEORY

Heat capacity of free electron gas

Fermi function, Fermi energy

Fermi dirac distribution function

Transport properties of conduction electrons

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

CRYSTAL STRUCTURE

Elementary Crystallography

Typical Crystal Structures

Elements Of Symmetry

Objectives

By the end of this section you should:

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

Crystal Structure

SOLIDS

19

Gases

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

20

order and they assume the shape of the containers.

Applying low levels of thermal energy can easily

break the existing weak bonds.

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.

21

Crytals

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

POLYCRYSTALLINE

AMORPHOUS

(Non-crystalline)

Single Crystal

Crystal Structure

23

Types of Solids

three general types of solids.

region within the material.

or molecules have a regular geometric arrangement

or periodicity.

Crystal Structure

24

Crystalline Solid

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

25

Crystalline Solid

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

(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

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

28

example, even the surface of a crystal is a kind of

imperfection because the periodicity is interrupted there.

around their equilibrium positions for any temperature T>0K.

crystal always contains some

foreign atoms, i.e., impurities.

These impurities spoils the

perfect crystal structure.

Crystal Structure

29

CRYSTALLOGRAPHY

What is crystallography?

The branch of science that deals with the geometric

description of crystals and their internal arrangement.

Crystal Structure

30

Crystallography

Crystallography is essential for solid state physics

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

31

ELEMENTARY

CRYSTALLOGRAPHY

for solid state physicists;

to classify the solids into different types according to

the symmetries they possess.

influence on its properties.

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

structure of Platinum

33

Crystal Lattice

y

An infinite array of

points in space,

Each

point

has

identical surroundings

to all others.

exactly in a periodic

manner.

Crystal Structure

34

Crystal Structure

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

35

different choices for the basis

Basis

A group of atoms which describe crystal structure

y

y

B

C

F

b

O

D

E

G

A

b

O

b) Crystal lattice obtained by

corners of regular hexagons Crystal identifying

all the atoms in (a)37

Structure

Crystal structure

lattice points

Lattice

points

infinitesimal

points

space

Lattice points do

necessarily lie at

centre of atoms

with

are

in

not

the

Crystal Structure

+ Basis

38

Crystal Lattice

All lattice points are equivalent

Some lattice points are not

equivalent

A combination of two or more BL

Crystal Structure

39

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

2) Non-Bravais Lattice

Not only the arrangement but also the orientation must

appear exactly the same from every point in a bravais lattice.

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

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

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

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

Lattice Vectors 2D

form a set of lattice

vectors for the lattice.

vectors is not unique.

Thus one could equally

well take the vectors a

and b as a lattice vectors.

Crystal Structure

43

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

Crystal Structure

(1)

44

Crystal Structure

45

Unit Cell in 2D

ions or molecules), which when stacked together with

pure translational repetition reproduces the whole

crystal.

Crystal Structure

S

46

Unit Cell in 2D

ions or molecules), which when stacked together with

pure translational repetition reproduces the whole

crystal.

The choice of

unit cell

is not unique.

S

a

Crystal Structure

47

environments

Crystal Structure

48

atoms - but unit cell size should always be the same.

Crystal Structure

49

Crystal Structure

50

Crystal Structure

51

This is NOT a unit cell even though they are all the

same - empty space is not allowed!

Crystal Structure

52

In 3D, it is NOT

Crystal Structure

53

be a unit cell?

Crystal Structure

54

Unit Cell in 3D

Crystal Structure

55

Unit Cell in 3D

Crystal Structure

56

Crystal Structure

57

UNIT CELL

Primitive

Single lattice point per cell

Smallest area in 2D, or

Smallest volume in 3D

Simple cubic(sc)

Conventional = Primitive cell

More than one lattice point per cell

Integral multibles of the area of

primitive cell

Conventional Primitive cell

Crystal Structure

58

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

Crystal Structure

60

Primitive Translation Vectors:

1

a1 ( x y z )

2

1

a2 ( x y z )

2

1

a3 ( x y z )

2

Body centered cubic (bcc):

conventional primitive cell

b

conventional cell:

000,100, 010, 001, 110,101, 011, 111,

primitive cell=conventional cell

000, 100, 010, 001, 110,101, 011, 111

a

Crystal Structure

62

b

c

a

primitive (rombohedron) conventional cell

Fractional coordinates:

000, 100, 101, 110, 110,101, 011, 211, 200

conventional primitive cell

Fractional coordinates:

c

a

0 , 0 ,1 , 1 , 1

Crystal Structure

63

points of primitive cell

conventional primitive cell

Fractional coordinates:

100, 010, 110, 101,011, 111,000, 001

b

a

Crystal Structure

64

Unit Cell

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

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.

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

66

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

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

69

Crystal Structure

70

Crystal Directions

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

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

71

Examples

210

X= ,Y=,Z=1

[ 1]

[1 1 2]

X=1,Y=,Z=0

[1 0]

[2 1 0]

Crystal Structure

72

Negative directions

direction

[n1n2n3]

depend on the origin,

negative

directions

can be written as

Z direction

[n1n2n3 ]

R = n1 a + n2 b + n3c

Direction must be

smallest integers.

(origin) O

- X direction

- Y direction

Y direction

[n1n2n3 ]

X direction

- Z direction

Crystal Structure

73

X=1,Y=0,Z=0

[1 0 0]

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

Crystal Structure

[110]

74

Examples

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

[-1 1 -1/6]

[6 6 1]

Crystal Structure

75

Crystal Planes

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.

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

(1,0,0)

1/1 1/ 1/

1

Miller ndices

Crystal Structure

(100)

78

Example-2

Axis

Intercept

points

Reciprocals

(0,1,0)

Smallest

Ratio

1/1 1/ 1 1/

1

Miller ndices

(110)

(1,0,0)

Crystal Structure

79

Example-3

(0,0,1)

Axis

Intercept

points

Reciprocals

(0,1,0)

(1,0,0)

Smallest

Ratio

1/1 1/ 1 1/ 1

1

Miller ndices

Crystal Structure

1

(111)

80

Example-4

Axis

Intercept

points

1/2

Reciprocals

(0,1,0)

(1/2, 0, 0)

Smallest

Ratio

1/() 1/ 1 1/

2

Miller ndices

Crystal Structure

(210)

81

Example-5

Axis

Intercept

points

Reciprocals

1/1

1/

1/()

Smallest

Ratio

Miller ndices

Crystal Structure

(102)

82

Example-6

Axis

Intercept

points

-1

Reciprocals

1/-1

1/

1/()

Smallest

Ratio

-1

Miller ndices

Crystal Structure

(102)

83

Miller Indices

[2,3,3]

2

3a , 2b , 2c

1 1 1

Reciprocal numbers are:

, ,

3 2 2

b

2

(200)

(110)

(100)

Crystal Structure

(111)

(100)

84

Crystal Structure

85

Example-7

Crystal Structure

86

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.

{111} (111), (11 1 ), (1 1 1), ( 1 11), ( 1 1 1 ), ( 1 1 1), ( 1 1 1 ), (1 1 1 )

plane (hkl) through rotational symmetry.

Crystal Structure

87

3D 14 BRAVAIS LATTICES AND THE SEVEN CRYSTAL SYSTEM

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.

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

88

Crystal Structure

89

Coordinaton Number

closest to a given point are the nearest neighbours.

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

the volume of atoms within the unit cell

divided by the volume of the unit cell.

a- Simple Cubic (SC)

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

Crystal Structure

93

Crystal Structure

94

is a non-primitive cell.

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

95

4R

a=

3

APF BCC

Crystal Structure

V atoms

= 0.68

V unit cell

(0,433a)

96

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

Crystal Structure

4R

a=

3

V atoms

0,74

= 0.68

APF BCC

FCC =

V unit cell

Crystal Structure

(0,353a)

99

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

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

Crystal Structure

101

2 - HEXAGONAL SYSTEM

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

Crystal Structure

104

3 - TRICLINIC

4 - MONOCLINIC CRYSTAL SYSTEM

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

= = 90o, 90o

a b c,

105

5 - ORTHORHOMBIC SYSTEM

Orthorhombic (Simple)

= = = 90o

a b c

Orthorhombic (Basecentred)

= = = 90o

a b c

Orthorhombic (BC)

= = = 90o

a b c

Crystal Structure

Orthorhombic (FC)

= = = 90o

a b c

106

6 TETRAGONAL SYSTEM

Tetragonal (BC)

= = = 90o

a = b c

Tetragonal (P)

= = = 90o

a = b c

Crystal Structure

107

a = b = c, = = 90o

Crystal Structure

108

CRYSTAL STRUCTURES

Diamond Structure

Zinc Blende

Crystal Structure

109

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

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

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.

Cs+Cl

cubic lattice. The unit cell may be

depicted as shown. (Cs+ is teal,

Cl- is gold).

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

Cs+Cl

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 )

lattice constants are in the order of 4

angstroms.

8 cell

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

117

Bravais Lattice : Hexagonal Lattice

He, Be, Mg, Hf, Re (Group II elements)

ABABAB Type of Stacking

Crystal Structure

basis : (0,0,0) (2/3a ,1/3a,1/2c)

118

Packing

Close pack

A

A

B

BA BA BA B A

C

C

C

BA BA B A

A

C

C

C

C

A

B

A

A

B

BA BA B A B A

C

C

C

Sequence AAAA

- simple cubic

Sequence ABABAB..

-hexagonal close pack

Sequence ABCABCAB..

-face centered cubic close pack

Crystal Structure

Sequence ABAB

- body centered cubic

119

Crystal Structure

120

4 - Diamond Structure

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

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

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

or more types of symmetry properties, such as

inversion, reflection or rotation,etc.

SYMMETRY

INVERSION

REFLECTION

Crystal Structure

ROTATION

127

Symmetry without translation

Operation

Element

Inversion

Point

Reflection

Plane

Rotation

Axis

Rotoinversion

Axes

Crystal Structure

128

Inversion Center

(x,y,z) --> (-x,-y,-z)

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

in this plane is performed, the cell remains invariant.

Crystal Structure

130

Examples

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

through some angles, the cell remains invariant.

Crystal Structure

133

Axis of Rotation

Crystal Structure

134

Axis of Rotation

Crystal Structure

135

5-fold symmetry

Crystal Structure

136

Group discussion

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

Monoclinic has 2-fold axis (= 2/2 =) normal to the

base.

Crystal Structure

138

Crystal Structure

139

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