SOLID STATE PHYSICS 1

PH 222
2
+ + +
- - - +
+ -
+
- - +
-
 CLASSIFICATION OF SOLIDS

SOLID MATERIALS

AMORPHOUS
CRYSTALLINE POLYCRYSTALLINE
(Non-crystalline)

Single Crystal

Crystal Structure 3
 SINGLE CRYSTALS
 Single crystals have a periodic atomic structure across its
whole volume.
 At long range length scales, each atom is related to every
other equivalent atom in the structure by translational or
rotational symmetry

Single Pyrite
Crystal

Amorphous
Solid
Single Crystals
4
 POLYCRYSTALLINE SOLIDS
 Polycrystalline materials are made up of an aggregate of many small single
crystals (also called crystallites or grains).
 Polycrystalline materials have a high degree of order over many atomic or
molecular dimensions.
 Grains (domains) are separated 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 less than 10 nm in diameter are nanocrystalline

Polycrystalline
Pyrite form
(Grain)

5
 AMORPHOUS SOLIDS
• Amorphous (Non-crystalline) Solids are made up 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.

6
 CRYSTALLOGRAPHY
Crystallography is a branch of science that deals with the geometric
description of crystals and their internal atomic arrangement.
It’s important the symmetry of a crystal because it has a profound influence
on its properties.
Structures should be classified into different types according to the
symmetries they possess.
Energy bands can be calculated when the structure has been determined.

7
 CRYSTAL LATTICE
What is a crystal 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 Crystal lattice and

(scanning tunneling microscope) structure of Platinum
8
 Crystal Lattice
y
• An infinite array of points
in space, B C D E
b α
• Each point has identical
O a A x
surroundings to all others.

• Arrays are arranged in a

periodic manner.

9
 Crystal Structure

• Crystal structures 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

10
A two-dimensional Bravais lattice
with different choices for the basis
 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

S S S
b S S S S S
a
S S S S S

12
Unit Cell in 3D

Crystal Structure 13
Three common Unit Cells in 3D

14
Unit Cell

• The unit cell and, consequently, the

entire lattice, is uniquely determined by
the six lattice constants: a, b, c, α, β
and γ.
• 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.

15
 PRIMITIVE CELL

It is the smallest unit cell in volume constructed by primitives. It

consists of only one full atom
A primitive cell is one, which has got the points or atoms only at the
corners of the unit cell.
If a unit cell consists of more than one atom, then it is not a primitive
cell.
Example for primitive cell :Simple Cubic unit cell
Examples for non-primitive cell: BCC and FCC unit cell.
Bravais Lattice

The foundation of ANY Crystal structure is the Bravais lattice.

Definitions of Bravais Lattice

Infinite array of discrete points that appear exactly the same from whichever of the
points the array is viewed.

All the points with position vectors R = n1a1 + n2a2 + n3a3

Where; a1, a2, a3 are three vectors not all in the same plane and n 1, n2 , n3 are integer
values.

A discrete set of vectors, not all in the same plane, closed under vector addition or
subtraction.

The vectors used to define a Bravais lattice, a1, a2, a3 , are called the primitive vectors.
 TYPICAL CRYSTAL STRUCTURES
3D – 14 BRAVAIS LATTICES AND SEVEN CRYSTAL TYPES

• 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 System (S)

18
 CRYSTALS SYSTEMS

The space lattices formed by unit cells are marked by the

following symbols.
Primitive lattice: P having lattice points only at the
corners of the unit cell.
Body centred lattice: I having lattice points at
the corners as well as at the body centre of the unit
cell.
Face centred lattice :F having lattice points at the
corners as well as at the face centres of the unit cell.
Base centred lattice: C having lattice points at the
corners as well as at the top and bottom base
centres of the unit cell.
Crystal Structure 20
 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.

21
 INTRODUCTION TO CRYSTAL PHYSICS

‘What is Crystal Physics?

Crystal Physics’ or ‘Crystallography’ is a

branch of physics that deals with the study of
all possible types of crystals and the physical
properties of crystalline solids by the
determination of their actual structure by using
X-rays, neutron beams and electron beams.
 POLYCRYSTALLINE SOLIDS
 Polycrystalline materials are made up of an aggregate of
many small single crystals (also called crystallites or grains).
 Polycrystalline materials have a high degree of order over
many atomic or molecular dimensions.
 Grains (domains) are separated 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 less than 10 nm in diameter are
nanocrystalline

Polycrystalline
Pyrite form
(Grain)

13
ATOMIC ARRANGEMENT IN CRYSTALS

(a) mono (or) single

crystals
(b) polycrystalline solids
(c) amorphous solids
 CRYSTALS SYSTEMS

The space lattices formed by unit cells are marked by the

following symbols.
Primitive lattice: P having lattice points only at the
corners of the unit cell.
Body centred lattice: I having lattice points at
the corners as well as at the body centre of the unit
cell.
Face centred lattice :F having lattice points at the
corners as well as at the face centres of the unit cell.
Base centred lattice: C having lattice points at the
corners as well as at the top and bottom base
centres of the unit cell.
MILLER INDICES
PROCEDURE FOR FINDING MILLER INDICES
DETERMINATION OF MILLER INDICES
IMPORTANT FEATURES OF MILLER INDICES
CRYSTAL DIRECTIONS
SEPARATION BETWEEN LATTICE PLANES
[d-spacing]
 MILLER INDICES
The crystal lattice may be regarded as made up of an infinite set of
parallel equidistant planes passing through the lattice points which
are known as lattice planes.
In simple terms, the planes passing through lattice points are
called ‘lattice planes’.
For a given lattice, the lattice planes can be chosen in a different
number of ways.

DIFFERENT LATTICE PLANES

 MILLER INDICES

Miller indices is defined as the reciprocals of the intercepts

made by the plane on the three crystallographic axes which is
used to designate plane in the crystal.

Miller indices are set of three possible integers represented

as (h k l) which is used to designate plane in the crystal ,is
the reciprocal of the intercept made by the planes on the
crystallographic axes.
 Another 2D example
Miller Indices for directions in 2D

This direction is  [4 2]
Normally, we ‘take out’ the common factor
Miller Indices with magnitude  2[2 1]

Miller indices → [53] And then omit it! Miller Indices  [2 1]

We will see an example
STEPS in the determination of Miller indices for directions soon

 Position the vector, such that start (S: (x1, y1)) and end points (E: (x2, y2)) are lattice points
and note the value of the coordinates. Subtract to obtain: ((x2x1), (y2y1)).
 Write these number in square brackets, without the ‘comma’: [* *].
 ‘Remove’ the common factors. (Note: keep the common factor, preferably outside the bracket, if the length has to be
preserved in further computations).
How to find the Miller Indices for an arbitrary direction?  Procedure
 Consider the example below.
 Subtract the coordinates of the end point from the starting point of the vector denoting the
direction  If the starting point is A(1,3) and the final point is B(5,1)  the difference
(BA) would be (4, 4).

 Enclose in square brackets, remove comma and

write negative numbers with a bar  [4 4]

 Factor out the common factor  4[11]

 If we are worried about the direction and

magnitude then we write  4[11]

 If we consider only the direction then we

write  [11]
 Needless to say the first vector is 4 times
in length
 The magnitude of the vector [11]  [11]
is (1) 2  (1) 2  2
Further points
 General Miller indices for a direction in 3D is written as [u v w].
 The length of the vector represented by the Miller indices is: u 2  v 2  w2

Important directions in 3D represented by Miller Indices (cubic lattice)

Z  Three important set of directions related
[011]
to the cube are:
[001] (i) cell edge ([001] type),
(ii) face diagonal ([011] type),
(iii) body diagonal ([111] type).
Memorize
these
[101] Body diagonal

[010]
Y [111]
[100] Face diagonal

[110]
X [110]
Procedure as before
• (Coordinates of the final point  coordinates of the initial point).
• Reduce to smallest integer values.
 MILLER INDICES
Procedure for finding Miller Indices
Step 1: Determine the intercepts of the plane along the axes
X,Y and Z in terms of the lattice constants a,b and c.
Step 2: Determine the reciprocals of these numbers.
Step 3: Find the least common denominator (lcd)
and multiply each by this lcd.
Step 4:The result is written in paranthesis. This is
called the `Miller Indices’ of the plane in
the form (h k l).

This is called the `Miller Indices’ of the plane in the form

(h k l).
 ILLUSTRATION PLANES IN A CRYSTAL

Plane ABC has intercepts of 2 units along X-axis, 3

units along Y-axis and 2 units along Z-axis.
DETERMINATION OF ‘MILLER INDICES’

Step 1:The intercepts are 2,3 and 2 on the three axes.

Step 2:The reciprocals are 1/2, 1/3 and 1/2.

Step 3:The least common denominator is ‘6’. Multiplying each

reciprocal by lcd, we get, 3,2 and 3.

Step 4:Hence Miller indices for the plane ABC is (3 2 3)

 MILLER INDICES

IMPORTANT FEATURES OF MILLER INDICES

For the cubic crystal especially, the important features of Miller

indices are,

A plane which is parallel to any one of the co-ordinate axes

has an intercept of infinity . Therefore the Miller index for
that axis is zero; i.e. for an intercept at infinity, the
corresponding index is zero.
 EXAMPLE

( 1 0 0 ) plane

Plane parallel to Y and Z axes

 EXAMPLE

In the above plane, the intercept along X axis is 1 unit.

The plane is parallel to Y and Z axes. So, the intercepts

along Y and Z axes are infinity.

Now the intercepts are 1, ⚮ and ⚮.

The reciprocals of the intercepts are = 1/1, 1/⚮ and 1/⚮.

Therefore the Miller indices for the above plane is (1 0 0).

Crystallographic Planes z
example a b c
1. Intercepts 1 1  c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2   c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
38
 Crystallographic Planes
z
example a b c c
1. Intercepts 1/2 1 3/4 
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3 
y

3. Reduction 6 3 4 a b

4. Miller Indices (634) x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)

39
 MILLER INDICES

IMPORTANT FEATURES OF MILLER INDICES

A plane passing through the origin is defined in terms of a

parallel plane having non zero intercepts.

All equally spaced parallel planes have same ‘Miller

indices’ i.e. The Miller indices do not only define a particular
plane but also a set of parallel planes. Thus the planes
whose intercepts are 1, 1,1; 2,2,2; -3,-3,-3 etc., are all
represented by the same set of Miller indices.
 MILLER INDICES

IMPORTANT FEATURES OF MILLER INDICES

It is only the ratio of the indices which is important in this

notation. The (6 2 2) planes are the same as (3 1 1) planes.

If a plane cuts an axis on the negative side of the origin,

corresponding index is negative. It is represented by a bar,
like (1 0 0). i.e. Miller indices (1 0 0) indicates that the
plane has an intercept in the –ve X –axis.
MILLER INDICES OF SOME IMPORTANT PLANES
 PROBLEMS

Worked Example:
A certain crystal has lattice parameters of 4.24, 10 and 3.66 Å on X,
Y, Z axes respectively. Determine the Miller indices of a plane
having intercepts of 2.12, 10 and 1.83 Å on the X, Y and Z axes.
Lattice parameters are = 4.24, 10 and 3.66 Å
The intercepts of the given plane = 2.12, 10 and 1.83 Å
i.e. The intercepts are, 0.5, 1 and 0.5.
Step 1: The Intercepts are 1/2, 1 and 1/2.
Step 2: The reciprocals are 2, 1 and 2.
Step 3: The least common denominator is 2.
Step 4: Multiplying the lcd by each reciprocal we get, 4, 2 and 4.
Step 5: By writing them in parenthesis we get (4 2 4)

Therefore the Miller indices of the given plane is (4 2 4) or (2 1 2).

 PROBLEMS

Worked Example:
Calculate the miller indices for the plane with intercepts 2a,
- 3b and 4c the along the crystallographic axes.

The intercepts are 2, - 3 and 4

Step 1: The intercepts are 2, -3 and 4 along the 3 axes

Step 2: The reciprocals are

Step 3: The least common denominator is 12.

Multiplying each reciprocal by lcd, we get 6 -4 and 3

Step 4: Hence the Miller indices for the plane is

 CRYSTAL DIRECTIONS

In crystal analysis, it is essential to indicate certain

directions inside the crystal.
A direction, in general may be represented in terms of
three axes with reference to the origin. In crystal
system, the line joining the origin and a lattice point
represents the direction of the lattice point.
 DESIRABLE FEATURES OF MILLER INDICES

The relation between the interplanar distance and the

interatomic distance is given by,

for cubic crystal.

If (h k l) is the Miller indices of a crystal plane then the

intercepts made by the plane with the crystallographic
axes are given as

where a, b and c are the primitives.

 SEPARATION BETWEEN LATTICE PLANES

Consider a cubic crystal of side ‘a’, and a plane ABC.

This plane belongs to a family of planes whose Miller indices are
(h k l) because Miller indices represent a set of planes.
Let ON =d, be the perpendicular distance of the plane A B C
from the origin.
SEPARATION BETWEEN LATTICE PLANES
 SEPARATION BETWEEN LATTICE PLANES

Let ⍺ ’, ℬ’ and y’
be the angles between co-ordinate axes X,Y,Z and ON respectively.

The intercepts of the plane on the three axes are,

(1)
 SEPARATION BETWEEN LATTICE PLANES

From the figure, we have,

(2)

From the property of direction of cosines,

(3)
 SEPARATION BETWEEN LATTICE PLANES

Using equation 1 in 2, we get,

(4)

Substituting equation (4) in (3), we get,

Now, let us consider the next parallel plane.

Let OM=d2 be the perpendicular distance of this

plane from the origin.

The intercepts of this plane along the three axes are

 SEPARATION BETWEEN LATTICE PLANES

• Therefore, the interplanar spacing between two

adjacent parallel planes of Miller indices (h k l ) is
given by, NM = OM – ON

[Link] spacing

(6)
 PROBLEMS

Worked Example

The lattice constant for a unit cell of aluminum is 4.031Å

Calculate the interplanar space of (2 1 1) plane.

a = 4.031 Å
(h k l) = (2 1 1)
Interplanar spacing

 d = 1.6456 Å
 PROBLEMS

Worked Example:
Find the perpendicular distance between the two planes indicated by
the Miller indices (1 2 1) and (2 1 2) in a unit cell of a cubic lattice
with a lattice constant parameter ‘a’.
We know the perpendicular distance between the origin and the plane is (1 2 1)

and the perpendicular distance between the origin and the plane (2 1 2),
 PROBLEMS

The perpendicular distance between the planes (1 2 1) and (2 1 2) are,

d = d1 – d2 =

(or) d = 0.0749 a.
 Characteristics of unit cell
• Number of atoms per unit cell
• Coordination number
• Atomic radius
• Atomic Packing factor or Packing Density
• Packing efficiency
• Theoretical density and linear density
• Number of atoms per unit cell: The number of
atoms present in the unit cell .
• Coordination number: The number of equidistant
nearest neighbouring atoms surrounding the
particular atom considered.
• Atomic Radius (r) : It is defined as half the distance
between the nearest neighbouring atoms in a crystal.
• Atomic Packing factor or Packing Density: It is the
ratio of the volume occupied by the atoms in an unit
cell (v) to the volume of the unit cell (V). It is also
called packing fraction or packing density.
SIMPLE CUBIC STRUCTURE
BODY CENTRED CUBIC STRUCTURE
FACE CENTERED CUBIC STRUCTURE
HEXAGONAL CLOSED PACKED STRUCTURE
PROBLEMS
Simple Cubic Structure (SC)
• Rare due to poor packing (only Po has this structure)
• Close-packed directions are cube edges.

Coordination # = 6
(# nearest neighbors)

1 atom/unit cell
One atom per unit cell

1/8 x 8 = 1
 Atomic Packing Factor

• APF for a simple cubic

structure = 0.52 Volume of an
atoms atom
4
unit cell 1 p (0.5a) 3
a 3
APF =
R=0.5a a3 Volume of unit cell
 Body Centered Cubic Structure (BCC)
How is ‘a’ and ‘R’ related for an BCC?
[a= unit cell dimension, R = atomic radius].
All atoms are identical 2 atoms/unit cell

• Exhibited by Cr, Fe, Mo, Ta, W

•Close packed directions are cube diagonals.
• Coordination number = 8
Body Centered Cubic Structure (BCC)
ATOMIC PACKING FACTOR: BCC
• APF for a body-centered
cubic structure = 0.68
Close-packed
direction - diagonal
4R
a=
3
Face Centered Cubic Structure (FCC)
• Exhibited by Al, Cu, Au, Ag, Ni, Pt
• Close packed directions are face diagonals.
• Coordination number = 12
• 4 atoms/unit cell

All atoms are identical

6 x (1/2 face) + 8 x 1/8 (corner) = 4 atoms/unit cell

 FACE CENTERED CUBIC STRUCTURE

The atoms in a FCC unit cell touches along

the face diagonal.
Each and every corner atom is shared by
eight adjacent unit cells.
Therefore each and every corner atom
contributes 1/8 of its part to one unit cell.
So the total number of atoms contributed by
the corner atoms is x 8 = 1.
 FACE CENTERED CUBIC STRUCTURE

Two unit cells share each and every face centered

atom.

Therefore, the contribution of a face centered atom

to unit cell is 1/2.

So, the total number of atoms contributed by the

face centred atoms = ½ x 6 = 3.

The total number of atoms present in a FCC unit

cell = 1+3 = 4.
 FACE CENTERED CUBIC STRUCTURE

COORDINATION NUMBER
In its own plane it touches four face centered atoms.
The face centered atoms are its nearest neighbors.

In a plane, which lies just above this corner atom, it

has four more face centered atoms as nearest
neighbors.

Similarly, in a plane, which lies just below this corner

atom it has yet four more face centered atoms as its
nearest neighbors.
 FACE CENTERED CUBIC STRUCTURE

Therefore the number of nearest neighbours i.e., co-ordination

number for FCC unit cell = 4+4+4 = 12
ATOMIC RADIUS (R)
Consider the figure , AB = AC = ‘a’
and AC = 4r.
From the triangle ABC,
AC2 = AB2 + BC2
AC2 = a2 + a2
AC2 = 2a 2 ; AC =
i.e. 4r =
Therefore atomic radius =
 Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74
maximum achievable APF
Close-packed directions:
length = 4R = 2 a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister & atoms volume
Rethwisch 8e. 4 3
unit cell 4 p ( 2a/4) atom
3
APF =
3 volume
a
unit cell
72
 FACE CENTERED CUBIC STRUCTURE
Atomic Packing Factor

APF =
v = 4  4/3 pr3: V = a3

APF =

Substituting r = , we get,

APF = = = 0.74

Thus 74 percent of the volume of the FCC unit cell is occupied by atoms and the
remaining 26 percent volume of the unit cell is vacant or void space.
 HEXAGONAL CLOSED PACKED STRUCTURE
It consists of three layers of atoms.
The bottom layer has six corner atoms
and one face centred atom.
The middle layer has three full atoms.
The upper layer has six corner atoms
and one face centred atom.
Each and every corner atom
contributes 1/6 of its part to one unit cell.
The number of total atoms contributed
by the corner
atoms of both top and bottom layers is
1/6 x 12 = 2.
 Linear Density Number of atoms
• Linear Density of Atoms  LD =  Unit length of direction vector

[110]
ex: linear density of Al in [110]
direction 
a = 0.405 nm

# atoms
a 2
LD = = 3.5 nm-1
Adapted from
Fig. 3.1(a),
length 2a
Callister &
Rethwisch 8e.

75
Theoretical Density, r
Mass of Atoms in Unit Cell
Density =  =
Total Volume of Unit Cell

nA
 =
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.022 x 1023 atoms/mol

76
 Diamond Lattice Structure

•Exhibited by Carbon (C), Silicon (Si) and

Germanium (Ge).
•Consists of two interpenetrating FCC lattices,
displaced along the body diagonal of the cubic
cell by 1/4 the length of the diagonal.
• Also regarded as an FCC lattice with two
atoms per lattice site: one centered on the
lattice site, and the other at a distance of a/4
along all axes, ie an FCC lattice with the two-
point basis.
Diamond Lattice Structure

a = lattice constant
Diamond Lattice Structure
8 atoms at each corner, 6 atoms on each face, 4
atoms entirely inside the cell
DIAMOND CUBIC (DC) STRUCTURE

1. Number of atoms per unit cell

 Total number of atoms per unit cell = 1 + 3 + 4 = 8
2. Atomic radius

3. Coordination number
The coordination number of diamond is 4.
4. Packing factor

Packing factor = 0.34%

Since the packing density is very low, it is termed as very loosely

packedstructure.
 Examples of elements with Cubic Crystal Structure

Fe Cu
Po

n=1 SC n=2 BCC n=4 FCC/CCP

n=8 DC
C (diamond)
 UNIT-I IMPORTANT FORMULAE
The relation between the interplanar distance and the
interatomic distance is given by,

for cubic crystal.

If (h k l) is the Miller indices of a crystal plane then the

intercepts made by the plane with the crystallographic
axes are given as where a, b and c are the primitives.
UNIT-I IMPORTANT FORMULAE
THE RECIPROCAL LATTICE

Two types of lattice are of great importance

 Direct lattice (which is the Bravais lattice that determines a
given reciprocal lattice)
 Reciprocal Lattice
 THE RECIPROCAL LATTICE

a j  ak
b i  2 , i  x, y, z  b i  a j  2ij
ai   a j  a k 
 
THE RECIPROCAL LATTICE
The reciprocal lattice of a Bravais lattice is the set of all vectors K such that
eiK □R  1
for all real lattice position vectors R.

Reciprocal lattice: The set of all wave vectors K that yield plane waves
with the periodicity of a given Bravais lattice.

Direct lattice position vectors: R = n1a1 + n2a2 + n3a3

Reciprocal lattice vectors: G = k1b1 + k2b2 + k3b3

where the primitive vectors a2 a 3

b1 
of the reciprocal lattice are:
2 a1  a2  a 3
a3 a 1
b2 
1
2 a  a2  a 3 and {n } i and {k1,k2,k3}
are integers
a a
b3  21 2
a 1  a 2  a 3 
259
Notes:
The direct crystal has the dimension of L while the reciprocal lattice has the dimension of L -1

Why do we need a reciprocal lattice?

Reciprocal lattice provides a simple geometrical basis for understanding:
• All things of “wave nature” (like behavior of electron and lattice vibrations in crystals”
• The geometry of x-ray and electron diffraction patterns
THE RECIPROCAL LATTICE
• the reciprocal lattice is defined in terms of a Bravais lattice

• the reciprocal lattice is itself one of the 14 Bravais lattices

• the reciprocal of the reciprocal lattice is the original direct lattice

e.g., simple cubic direct lattice

a3 
a1  axˆ
azˆ

a2  ayˆ
 RECIPROCAL LATTICE TO SIMPLE CUBIC (SC) LATTICE
The simple cubic primitive lattice which has the primitive
vectors a1=ax, a2=ay and a3=az, has a volume of the cell equal to
Vcell = a3

The corresponding primitive  a k in the reciprocal lattice can

a j vectors
be obtained as bi  2 a   a  a  , i  x, y, z  b i  a j  2ij
i j k

 b1   2 / a  x
 Vcell=  2 / a  3
b 2   2 / a  y
 b   2 / a  z
 3

 
RECIPROCAL LATTICE TO BCC

a1  1 a x  y  z 
 2
a 2  2 a  x  y  z 
1
a  1 a x  y  z 
 3 2
RECIPROCAL LATTICE OF FCC IS BCC
FCC primitive vectors:

Note: not orthogonal

a 2 (y z-
a 2  a3 4 ˆˆ ˆ 4 1
b1   x) 3 
2 2
a a 2 (yˆ zˆ-
a1  a2  a3 (2)
8 xˆ)

4 1 4 1
b2  (zˆ + xˆ- b3  (xˆ+ yˆ-
a 2 a 2
→ BCC reciprocal
y ˆ) lattice zˆ)lattice constant 4π/a
with
RECIPROCAL LATTICE OF BCC IS FCC
BCC primitive vectors (not orthogonal):

a 2 (2y
a 2  a3 4 ˆ  2z)
ˆ 4 1
b1   3 
2 2
a a 2 (yˆ
a1  a2  a3 (4)
8 zˆ)
4 1  4 1
b 2  a 2(zˆ + b 3  a 2(xˆ+
xˆ) y ˆ)
→ FCC reciprocal lattice with lattice constant 4π/a
 Reciprocal Lattices to SC, FCC and BCC
Direct lattice Reciprocal lattice Volume
SC  a  ax  b1   2 / a  x
1
 
a 2  ay b 2   2 / a  y  2 / a  3
 a  az  b   2 / a  z
 3  3
FCC  b1  2   x  y  z 
a1  12 a x  y  a
 1 a y  z 
 2  x  y  z 
a
 2 2 b 
 2 a
a  1 a  z  x  b  2  x  y  z  4 2 / a  3
 3 2  3 a
BCC
 b1  2  y  z 
 
 a
b 2  a  x  z 
2
2 2 / a  3
b  2  x  y 
a1  1 a x  y  z 
 2  3 a
a 2  2 a  x  y  z 
1
a  1 a x  y  z 
 3 2
Note:
G= k1b1+ k2b2+ k3b3

1. Eg. Find G for the sc primitive reciprocal lattice for

k1=1, k2=-2 and k3=3

2. Show that reciprocal lattice of the reciprocal lattice

is the bravais lattice

EEE539 Solid State Electronics

• Wigner-Seitz primitive unit cell and first Brillouin zone
The Wigner–Seitz cell around a lattice point is defined as the locus of points in space that are closer
to that lattice point than to any of the other lattice points.

The cell may be chosen by first picking a lattice point. Then, lines are drawn to all nearby (closest)
lattice points. At the midpoint of each line, another line (or a plane, in 3D) is drawn normal to
each of the first set of lines.

1D case
3D case: BCC
2D case Important
 FIRST BRILLOUIN ZONES
The Wigner-Seitz cell of the reciprocal lattice is called the first Brillouin
zone (FBZ).

Wigner-Seitz cell: primitive cell with lattice point at its center

d.l. FCC d.l. BCC

r.l. BCC r.l. FCC
1st Brillouin zone: 1st Brillouin zone:

enclosed region is W-S cell

for 2D hexagonal lattice

rhombic dodecahedron
truncated octahedron
270
• Miller indices

y
x

Easier way to get the indices:

Reciprocals of the intercepts
 X-RAY DIFFRACTION
 X- Ray Sources
 Diffraction: Bragg’s Law
 Crystal Structure Determination
Generation of X-rays
 X-rays can be generated by decelerating electrons.
 This is achieved by bombarding a target (say Cu) with an electron beam.
 The resultant spectrum of X-rays generated (i.e. X-rays versus Intensity plot) consists of
intense peaks on a ‘continuous/broad’ background.
 The intense peaks can be ‘utilized’ as monochromatic radiation and be used for X-ray
diffraction studies.

Beam of electrons Target X-rays

An accelerating (or decelerating) charge radiates electromagnetic radiation

Mo Target impacted by electrons accelerated by a 35 kV potential shows the emission
spectrum as in the figure below (schematic)

Intense peak, nearly X-ray sources with different  for

K monochromatic doing XRD studies

Target  Of K
White K Metal radiation (Å)
Intensity

radiation
Mo 0.71
Characteristic radiation → Cu 1.54
due to energy transitions Co 1.79
in the atom
Fe 1.94
Cr 2.29

0.2 0.6 1.0 1.4

Wavelength ()

The high intensity nearly monochromatic K x-rays can be used as a radiation source for
X-ray diffraction (XRD) studies  a monochromator can be used to further decrease the
spread of wavelengths in the X-ray
 X-ray sources with different  for doing XRD studies

Elements (KV)  Of K1  Of K2  Of Kβ Kβ-Filter

radiation radiation (Å) radiation (Å) (mm)
(Å)    
 
Ag 25.52 0.55941 0.5638 0.49707 Pd
0.0461
Mo 20 0.7093 0.71359 0.63229 Zr
0.0678
Cu 8.98 1.540598 1.54439 1.39222 Ni
0.017
Ni 8.33 1.65791 1.66175 1.50014 Co
0.0158
Co 7.71 1.78897 1.79285 1.62079 Fe
0.0166
Fe 7.11 1.93604 1.93998 1.75661 Mn
0.0168
Cr 5.99 2.2897 2.29361 2.08487 V
0.169

[Link] Darwin, Grandson of C. Robert Darwin developed the dynamic theory of scattering of x-rays (a tough theory!) in 1912
 Diffraction
 How X-rays interact with a crystalline array (of atoms, ions etc.) to give rise to the
phenomenon known as X-ray diffraction (XRD).
 Consider a special case of diffraction → a case where we get ‘sharp[1] diffraction
peaks’.
 Diffraction (with sharp peaks) (with XRD being a specific case) requires the following important
conditions to be satisfied:
Radiation related Coherent, monochromatic, parallel waves (with wavelength ).
&

Sample related Crystalline array of scatterers* with spacing of the order of (~) .
 Some comments and notes
 The waves could be:
 electromagnetic waves (light, X-rays…),
 matter waves** (electrons, neutrons…) or
 mechanical waves (sound, waves on water surface…).
 Not all objects act like scatterers for all kinds of radiation.
 If wavelength is not of the order of the spacing of the scatterers, then the number of peaks
obtained may be highly restricted (i.e. we may even not even get a single diffraction peak!).
 In short diffraction is coherent reinforced scattering (or reinforced scattering of coherent waves).
 In a sense diffraction is nothing but a special case of constructive (& destructive)
interference.
To give an analogy  the results of Young’s double slit experiment is interpreted as interference, while the result of
multiple slits (large number, diffraction grating) is categorized under diffraction.

* With a de Broglie wavelength

XRD  the first step
A beam of X-rays directed at a crystal interacts with the electrons of the atoms in the crystal.
The electrons oscillate under the influence of the incoming X-Rays and become secondary sources
of EM radiation.
The secondary radiation is in all directions.
The waves emitted by the electrons have the same frequency as the incoming X-rays  coherent.
The emission can undergo constructive or destructive interference.

Secondary
Incoming X-rays emission

Oscillating charge re-radiates  In phase with

the incoming x-rays
Some points to recon with ...
 We can get a better physical picture of diffraction by using Laue’s formalism* (leading to the Laue’s
equations).
 However, a parallel approach to diffraction is via the method of Bragg, wherein diffraction can be
visualized as ‘reflections’ from a set of planes.
 As the approach of Bragg is easier to grasp we shall use that in this elementary text.

 Let us consider a coherent wave of X-rays impinging on a crystal with atomic planes at an
angle  to the rays.
 Incident and scattered waves are in phase if the:
i) in-plane scattering is in phase and
ii) scattering from across the planes is in phase.

In plane scattering is in phase

Incident and scattered
waves are in phase if A Laue diffraction pattern
Scattering from across planes is in phase with ‘sharp’ peaks.

 *Max von Laue’s postulate: If (i) crystals have a periodic arrangement of atoms and if (ii)
x-rays are waves (concepts which were not confirmed till then), then crystals should act like
a diffraction grating for x-rays. Both these postulates (i & ii) were proved by a single
experiment by Laue (published in 1912 which won him the noble prize in 1914).
 Let us consider in-plane scattering
A B

X Y
Atomic Planes

Extra path traveled by incoming waves  AY

These can be in phase if
Extra path traveled by scattered waves  XB  incident = scattered

A B

X Y
 BRAGG’s EQUATION

 A portion of the crystal is shown for clarity- actually, for destructive interference to occur
many planes are required (and the interaction volume of x-rays is large as compared to that shown in the schematic).
 The scattering planes have a spacing ‘d’.
 Ray-2 travels an extra path as compared to Ray-1 (= ABC). The path difference between
Ray-1 and Ray-2 = ABC = (d Sin + d Sin) = ([Link]).
 For constructive interference, this path difference should be an integral multiple of :
n = 2d Sin  the Bragg’s equation. (More about this sooner).
 The path difference between Ray-1 and Ray-3 is = 2([Link]) = 2n = 2n. This implies that if Ray-1
and Ray-2 constructively interfere Ray-1 and Ray-3 will also constructively interfere. (And so forth).
Laue versus Bragg*
 In Laue’s picture constructive and destructive interference at various points in space is
computed using path differences (and hence phase differences) given a crystalline array of
scatterers.
 Bragg simplified this picture by considering this process as ‘reflections from atomic planes’.
(More about the Bragg’s viewpoint soon).

 *Sir William Henry Bragg and William Lawrence Bragg (this won the father and son team the noble prize in
1915).

[1]
[1]

“The
“The important
important thing
thing in
in science
science is
is not
not so
so much
much to
to obtain
obtain new
new facts
facts as
as to
to discover
discover new
new ways
ways of
of
thinking
thinking about
about them”.
them”. William
William Lawrence
Lawrence Bragg.
Bragg.
[1] [Link]
 Reflection versus Diffraction
 Though diffraction (according to Bragg’s picture) has been visualized as a reflection from a
set of planes with interplanar spacing ‘d’  diffraction should not be confused with
reflection (specular reflection).
Reflection Diffraction
Occurs throughout the bulk
Occurs from surface (though often the penetration of x-rays in only of the
order of 10s of microns in a material)

Takes place at any angle Takes place only at Bragg angles

~100 % of the intensity may be reflected Small fraction of intensity is diffracted

If n = 2d Sin is the Bragg’s equation, then what is the (famous) Bragg’s

law?

Braggs Law
 The diffracted beam appears to be specularly reflected from a set of crystal lattice planes.
 Angle of incidence = Angle of reflection.
Understanding the Bragg’s equation
 n = 2d Sin
The equation is written better with some descriptive subscripts:
n Cu K  2 d hkl Sin hkl If this equation is satisfied, then  is Bragg n Cu K  2 d hkl Sin hkl
Bragg

 n is an integer and is the order of the reflection

(i.e. how many wavelengths of the X-ray go on to make the path difference between planes).
Note: if hkl reflection (corresponding to n=1) occurs at hkl then 2h 2k 2l reflection (n=2) will occur at a higher angle 2h 2k 2l.

 Bragg’s equation is a negative statement

 If Bragg’s eq. is NOT satisfied  NO ‘reflection’ can occur
 If Bragg’s eq. is satisfied  ‘reflection’ MAY occur
(How?- we shall see this a little later).
 The interplanar spacing appears in the Bragg’s equation, but not the interatomic
spacing ‘a’ along the plane (which had forced incident = scattered); but we are not free
to move the atoms along the plane ‘randomly’
  For large interplanar spacing the angle of reflection tends towards zero → as d increases, Sin
decreases (and so does ).
 The smallest interplanar spacing from which Bragg diffraction can be obtained is /2 →
maximum value of  is 90, Sin is 1  from Bragg equation d = /2.
Order of the reflection (n)  For Cu K radiation ( = 1.54 Å) and d110= 2.22 Å
n Sin = n/2d 

1 0.34 20.7º • First order reflection from (110)  110

• Second order reflection from (110) planes  110
2 0.69 43.92º
• Also considered as first order reflection from (220) planes  220

Relation between dnh nk nl and dhkl e.g. a d 220 1

a d 220  
Cubic crystal
d hkl  8 d110 2
h2  k 2  l 2
a a d hkl a d110
d nh nk nl  d nh nk nl   d110  d 220 
(nh)  (nk )  (nl )
2 2 2
n h k l
2 2 2 n 2 2

In XRD nth order reflection from (h k l) is “considered” as 1st order reflection from (nh nk nl).

n  2 d hkl Sin hkl d nh nk nl 1 d hkl

 λ=2 Sinθhkl
d hkl n n
Alternate way of writing
Bragg’s equation   2d nh nk nl Sin   nh nk nl 
Note: the ‘n’ is absorbed both in the ‘d’ and the .
We explicitly write  nh nk nl to show that this reflection occurs at a different angle (higher angle as compred to  h k l
Forward and Back Diffraction
Here a guide for quick visualization of forward and backward scattering (diffraction) is presented
  What is  (theta) in the Bragg’s equation?

  is the angle between the incident x-rays and the set of parallel atomic planes (which have a
spacing dhkl). Which is 10 in the above figure.
 Usually,  in this context implies Bragg (i.e. the angle at which Bragg’s equation is satisfied).
 It is NOT the angle between the x-rays and the sample surface (note: specimens could be
spherical or could have a rough surface).
 What do the terms ‘sharp’ and ‘diffuse’ mean with regard to peaks and
scattering?
 Sharp peaks are obtained from crystalline materials (using parallel, monochromatic
radiation), while typically a broad peak is obtained from an amorphous material. The sharp
peak is referred to as a Bragg peak.
 Defects (like point defects, thermal vibration, partial ordering) in the crystal can give rise to
low intensity scattering between the Bragg peaks. This is termed as diffuse scattering.

ystals
ob tain e d from cr
s are
o ntra st sharp peak
In c

Note the broad peak

SAD pattern (TEM ) from the

amorphous sample

XRD pattern showing the formation of amorphous

structure in the suction cast (Cu64Zr36)96Al4 alloy
 Important
points

Þ Presence of additional atoms/ions/molecules in the UC

 at lattice points (as we may chose a non-primitive unit cell)
 or as a part of the motif (Basis)
can alter the intensities of some of the reflections
Þ Some of the reflections may even go missing

 Position of the ‘reflections’/‘peaks’ tells us about the lattice type.

 The Intensities tells us about the motif (Basis).
 Selection / Extinction Rules
 As we have noted before even if Bragg’s equation is satisfied, ‘reflections may go missing’
 this is due to the presence of additional atoms in the unit cell.
 The reflections present and the missing reflections due to additional atoms in the unit cell are
listed in the table below.

Bravais Lattice* Reflections which may be present Reflections necessarily absent

Simple all None
Body centred (h + k + l) even (h + k + l) odd
Face centred h, k and l unmixed (i.e. all even or all odd) h, k and l mixed

End centred (C centred) h and k unmixed h and k mixed

Structure Allowed Reflections

SC All
BCC (h + k + l) even
FCC h, k and l unmixed
Either,  h, k and l are all odd or
DC
 all are even & (h + k + l) divisible by 4
* Note that the lattice has to be decorated with ‘atomic species’ for diffraction to actually occur (lattices by themselves do not give Bragg
diffraction !!!!).
 h2 + k2 + l2 SC FCC BCC DC
Allowed reflections in 1 100
SC*, CCP, BCC* & DC
2 110 110
crystals
3 111 111 111
4 200 200 200
5 210
6 211 211
7
Note these reflections were present in CCP
8 220 220 220 220
9 300, 221
Cannot be expressed as (h2+k2+l2)
10 310 310
11 311 311 311
12 222 222 222
13 320
14 321 321
15
16 400 400 400 400
17 410, 322
18 411, 330 411, 330
* lattice decorated with 19 331 331 331
monoatomic/monoionic motif
Crystal structure determination
 As diffraction occurs only at specific Bragg angles, the chance that a reflection is observed
when a crystal is irradiated with monochromatic X-rays at a particular angle is small (added
to this the diffracted intensity is a small fraction of the beam used for irradiation).
 The probability to get a diffracted beam (with sufficient intensity) is increased by either
varying the wavelength () or having many orientations (rotating the crystal or having
multiple crystallites in many orientations).
 The three methods used to achieve high probability of diffraction are shown below.

Many s (orientations) Powder

λ  fixed
Monochromatic X-rays
Powder specimen Method θ  variable

Laue λ  variable
Panchromatic X-rays Single  Technique θ  fixed

Rotating Crystal
λ  fixed
Monochromatic X-rays  Varied by rotation
Method θ  rotated
Only the powder method (which is commonly used in materials science) will be considered in this text.
 THE POWDER METHOD
 In the powder method the specimen has crystallites (or grains) in many orientations (usually
random).
 Monochromatic* X-rays are irradiated on the specimen and the intensity of the diffracted
beams is measured as a function of the diffracted angle.
 In this elementary text we shall consider cubic crystals.

d hkl Cubic  a
  2 d Sin (1) Cubic crystal (2)
h2  k 2  l 2
(2) in (1)

4 a 2
sin 2
 4 a 2
  2
2
 (h 2  k 2  l 2 )  2 sin 2 
h  k2  l2 

 2
(h 2  k 2  l 2 )  sin 2 
a2  ( h 2
 k 2
 l 2
) 
4 sin 2

* In reality this is true only to an extent

 POWDER METHOD
 In the powder sample there are crystallites in different ‘random’ orientations (a polycrystalline sample
too has grains in different orientations)
 The coherent x-ray beam is diffracted by these crystallites at various angles to the incident direction
 All the diffracted beams (called ‘reflections’) from a single plane, but from different crystallites lie on a
cone.
 Depending on the angle there are forward and back reflection cones.
 A diffractometer can record the angle of these reflections along with the intensities of the reflection
 The X-ray source and diffractometer move in arcs of a circle- maintaining the Bragg ‘reflection’
geometry as in the figure (right) Usually the source is
fixed and the
detector and sample
Different cones are rotated
for different
reflections

Also called Debye ring

Determination of Crystal Structure from 2 versus Intensity Data in Powder Method

 In the power diffraction method a 2 versus intensity (I) plot is obtained from the
diffractometer (and associated instrumentation).
 The information of importance obtained from such a pattern is the ‘relative intensities*’
and the absolute value of the intensities is of little importance (the longer we irradiate the sample the more will be
the intensity under the peak) (for now).

 I is really diffracted energy (as Intensity is Energy/area/time).

 A table is prepared as in the next slide to tabulate the data and make calculations to find the
crystal structure (restricting ourselves to cubic crystals for the present).

* Relative intensity: Intensity of any peak divided by

the intensity of the ‘strongest’ peak. Powder diffraction pattern from Al

Intensity (I) has units of Radiation: Cu K,  = 1.54 Å

[Energy/area/time] → but here it
is plotted as arbitrary units. Increasing
d This is peak (sometimes called a
line- a hangover from Debye
Scherrer camera usage)

Usually in degrees () Increasing


 Determination of Crystal Structure (lattice type) from 2 versus Intensity Data

The following table is made from the 2 versus Intensity data (obtained from a XRD experiment on a
powder sample (empty starting table of columns is shown below- completed table shown later).

n 2→  Intensity Sin Sin2  ratio

1 21.5

2 25

3 37
4 45
5 47
6 58
7 68
Powder diffraction pattern from Al Radiation: Cu K,  = 1.54 Å

These are Miller indices in reciprocal

space (these are not planes they
correspond to planes in real space)

Note:
 This is a schematic pattern
 In real patterns peaks or not idealized  peaks  broadened
 Increasing splitting of peaks with g 
(1 & 2 peaks get resolved in the high angle peaks)
 Peaks are all not of same intensity
 No brackets are used around the indexed numbers
(the peaks correspond to planes in the real space)

Note that there are no brackets

around the indices!
Powder diffraction pattern from Al Radiation: Cu K,  = 1.54 Å

Note:
 Peaks or not idealized  peaks  broadened.

111
 Increasing splitting of peaks with g .
 Peaks are all not of same intensity.
 There is a ‘noisy’ background.
 Here the background is subtracted
(else we may have a varying background).
200

220

311
222

400
In low angle peaks K1 & K2 peaks merged K1 & K2 peaks resolved in high angle peaks
(in 222 and 400 peaks this can be seen)
 What will determine how many peaks I will get?

 1)   smaller the wavelength of the X-rays, more will be the number of peaks possible.
 From Bragg’s equation: [=2dSin], (Sin)max will correspond to dmin. (Sin)max=1.
Hence, dmin=/2. Hence, if  is small then planes with smaller d spacing (i.e. those which
occur at higher 2 values) will also show up in a XRD patter (powder pattern). Given that
experimentally  cannot be greater than 90.

 2) Lattice type  in SC we will get more peaks as compared to (say) FCC/BCC. Other things being
equal.

 3) Lower the symmetry of the crystal, more the number of peaks (e.g., in tetragonal crystal
the 100 peak will lie at a different 2 as compared to the 001 peak).

 
  2dSin  2d min  d min
 Sin  max 2
 Determination of Crystal Structure (lattice type) from 2 versus Intensity Data
Let us assume that we have the 2 versus intensity plot from a diffractometer
 To know the lattice type we need only the position of the peaks (as tabulated below)

# 2  Sin Sin2  ratio Index d

1 38.52 19.26 0.33 0.11 3 111 2.34
2 44.76 22.38 0.38 0.14 4 200 2.03
3 65.14 32.57 0.54 0.29 8 220 1.43
4 78.26 39.13 0.63 0.40 11 311 1.22
5 82.47 41.235 0.66 0.43 12 222 1.17
6 99.11 49.555 0.76 0.58 16 400 1.01
7 112.03 56.015 0.83 0.69 19 331 0.93
8 116.60 58.3 0.85 0.72 20 420 0.91
9 137.47 68.735 0.93 0.87 24 422 0.83
10 163.78 81.89 0.99 0.98 27 333 0.78

Note that Sin cannot be > 1

From the ratios in column 6 we conclude Note
that FCC (h 2  k 2  l 2 )  sin 2 
a
Using   2 d Sin 1.54  2 d111 Sin111  2 0.33
o
3
a  4.04 A  Al We can get the lattice parameter  which correspond to that for Al

Note: Error in d spacing decreases with  → so we should use high angle lines for lattice parameter calculation
XRD_lattice_parameter_calculation.ppt
 Another example
Given the positions of the Bragg peaks we find the lattice type

Whole
Ratios Dividing Sin2 by
2→  Sin Sin2  number Index
of Sin2 0.134/3 = 0.044667 ratios
1 21.5 0.366 0.134 1 3 111
2 25 0.422 0.178 1.33 3.99 4 200
3 37 0.60 0.362 2.70 8.10 8 220
4 45 0.707 0.500 3.73 11.19 11 311
5 47 0.731 0.535 4 11.98 12 222
6 58 0.848 0.719 5.37 16.10 16 400
7 68 0.927 0.859 6.41 19.23 19 331

 FCC lattice
Applications of XRD

Bravais lattice determination

We have already seen these applications

Lattice parameter determination

Determination of solvus line in phase diagrams

Long range order

Crystallite size and Strain

Determine if the material is amorphous or crystalline

Determine if the material is amorphous or crystalline Schematic
s
Crystal
Intensity →

Schematic of difference between

the diffraction patterns of various phases

Sharp
peaks

0 90 180
Diffraction angle (2) →
Monoatomic gas

Intensity →
No peak

Liquid / Amorphous solid

Intensity →

Diffraction angle (2) →

0 90 180
Diffuse
Peak
Diffraction angle (2) →
Continued…
0 90 180
 Amorphous solid
Diffuse peak from Actual diffraction
Cu-Zr-Ni-Al-Si pattern from an
Metallic glass amorphous solid

 A amorphous solid, which shows glass transition in a Differential Scanning Calorimetry

(DSC) plot is also called a glass. In ‘general usage’ a glass may be considered equivalent to a
amorphous solid (at least loosely in the structural sense).
 In the XRD pattern obtained from a glass, the sharp peaks (which are present in the glass) are
missing. Only a broad diffuse peak survives→ the peak corresponds to the average spacing between
atoms which the diffraction experiment ‘picks out’
(XRD patterns) courtesy: Dr. Kallol Mondal, MSE, IITK
 Examples
 1. X ray diffraction of copper which has face centered cubic structure is
done using x ray with a wave length of 0.154 nm. One peak in the XRD is
found at 2 = 43.2 deg.
What are the miller indices for this peak? Given that atomic radius of
cupper is 0.128 nm.

2. Molybdenum has a BCC crystal structure and an atomic radius of

0.1363 nm. compute the interplanar spacing for the (111) set of
planes.
3. Determine the expected diffraction angle for the first-order
reflection from the (113) set of planes for FCC platinum when
monochromatic radiation of wavelength 0.154 nm is used. Given
that atomic radius of platinum is 0.1387 nm.
Lattice Dynamics
Lattice dynamics above T=0
•Crystal lattices at zero temperature posses long range order – translational
symmetry (e.g., generates sharp diffraction, …).
•At T>0 ions vibrate with an amplitude that depends on temperature – because
of lattice symmetries, thermal vibrations can be analyzed in terms of collective
motion of ions which can be populated and excited just like electrons – unlike
electrons, phonons are bosons.

139
Hooke's Law

• One of the properties of elasticity is that it takes about twice as much

force to stretch a spring twice as far. That linear dependence of
displacement upon stretching force is called Hooke's law.

It takes twice
as much force
Fspring  k .x to stretch a
spring twice

Spring constant k
F as far.

2F 
 SOUND WAVES

•• Mechanical waves
It corresponds areatomic
to the waves vibrations
which propagate through
with a long λ. a material
medium (solid, liquid, or gas) at a wave speed which depends on
• the elastic and inertial properties of that medium. There are two
basic typesofofatoms
Presence wave has no significance
motion in this
for mechanical wavelength
waves: limit,
longitudinal
since and
waves λ>>a, so therewaves.
transverse will no scattering due to the presence of
atoms.

Longitudinal Waves

Transverse Waves
SOUND WAVES

• Sound waves propagate through solids. This tells us that wavelike

lattice vibrations of wavelength long compared to the interatomic
spacing are possible. The detailed atomic structure is unimportant for
these waves and their propagation is governed by the macroscopic
elastic properties of the crystal.

• We discuss sound waves since they must correspond to the low

frequency, long wavelength limit of the more general lattice
vibrations considered later in this chapter.

• At a given frequency and in a given direction in a crystal it is possible

to transmit three sound waves, differing in their direction of
polarization and in general also in their velocity.
Normal Modes of Vibration
One dimensional model # 1: The Monatomic Chain
• Consider a
Monatomic Chain of
Identical Atoms
with nearest-neighbor,
“Hooke’s Law”
type forces (F = - Kx) between the atoms.
• This is equivalent to a force-spring model, with masses m & spring
constants K.
 One Dimensional Model # 1:
The Monatomic Chain
• This is the simplest possible solid.
• Assume that the chain contains a very large number
(N  ) of atoms with identical masses m. Let the atomic
separation be a distance a.
• Assume that the atoms move only in a direction parallel to
the chain.
• Assume that only nearest-neighbors interact with each
other (the forces are short-ranged).
a a a a a a

Un-2 Un-1 Un Un+1 Un+2

• Consider the simple case of a
monatomic linear chain with only
nearest-neighbor interactions.
• Expand the energy near the a
a
equilibrium point for the nth atom.
Then, the
0
Newton’s 2 nd
Law
equation of motion becomes:
Un-1 Un Un+1

..
This can be seen as follows.
The total force on the nth
atom is the sum of 2 forces: a a
The force to the right is:
K (u n 1  u n )
The force to the left is: Un-1 Un Un+1

K (u n  u n 1 )
Total Force = Force to the right – Force to the left
..
The Equation of Motion of each atom is of
this [Link] the value of ‘n’ changes.
• Assume that all atoms oscillate with the same amplitude
A & the same frequency ω. Assume harmonic solutions
for the displacements un of the form:
un  A exp i  kx  t  
dun
 i A exp i  kxn0  t  
.
0
n un 
dt
d 2 un ..
u n  2   i   2 A exp i  kxn0  t  
..
2

dt u n   un 2

Undisplaced 0 Displaced
xn  na xn  na  un
Position: Position:
• Put all of this into the equation of motion:
..

• Now, carry out some simple math manipulation:

 Equation of Motion for the nth Atom
..
mu n  K (un 1  2un  un 1 )

 m
2
Ae

i kxn0 t   K  Ae
 i kxn10 t   2A e  i kxn0 t   Ae  i kxn10 t 

k ( n  1) a kna k ( n  1) a
kna
2 i  kna t 
 m A e  K Ae 
i  kna  ka t 
 2A e
i  kna t 
 Ae
i  kna  ka t 

2
 m A e
i  kna t 
 K  Ae
i  kna  t 
e
ika
 2A e
i  kna t 
 Ae
i  kna t 
e
 ika

Cancel Common Terms & Get:
m 2  K  eika  2  e ika 
• Mathematical Manipulation finally gives:

• After more manipulation, this simplifies to

Solution to the Normal
Mode Eigenvalue Problem
for the monatomic chain.

• The maximum allowed frequency is:

• The physical significance of these results is that, for the

monatomic chain, the only allowed vibrational frequencies ω must
be related to the wavenumber k = (2π/λ) or the wavelength λ in this way.

• This result is often called the “Phonon Dispersion Relation” for

the chain, even though these are classical lattice vibrations &
there are no (quantum mechanical) phonons in the classical theory.
 “Phonon Dispersion Relations” or Normal Mode
Frequencies or ω versus k relation for the monatomic chain.
w
K
max  2
m
Vs   / k
C A
B

k
–л/a 0 л/a 2л/a

Because of BZ periodicity with a period of 2π/a, only the first

BZ is needed. Points A, B & C correspond to the same
frequency, so they all have the same instantaneous atomic
displacements.
 Monatomic Chain 4K ka
 sin
Dispersion Relation m 2
Some Physics Discussion
• We started from the Newton’s 2nd Law equations of motion for N
coupled harmonic oscillators. If one atom starts vibrating, it does not
continue with constant amplitude, but transfers energy to the others in a
complicated way. That is, the vibrations of individual atoms are not
simple harmonic because of this exchange of energy among them.
• On the other hand, our solutions represent the oscillations of
N UNCOUPLED simple harmonic oscillators.
• As we already said, these are called the Normal Modes of the
system. They are a collective property of the system as a whole
& not a property of any of the individual atoms. Each mode represented
by ω(k) oscillates independently of the other modes.
• The physical significance of wave numbers k outside of the
First Brillouin Zone [-(π/a)  k  (π/a)]?
• At the Brillouin Zone edge:
• This k value corresponds to the maximum frequency. A detailed
analysis of the displacements shows that, in that mode, every atom
is oscillating π radians out of phase with it’s 2 nearest neighbors.
That is, a wave at this value of k is A STANDING WAVE.
• Briefly look in more detail at the group velocity, vg.
• The dispersion relation is:
4K ka
 sin
• So, the group velocity is: m 2
vg  (dω/dk) = a(K/m)½cos(½ka)
vg = 0 at the BZ edge [k =  (π/a)]
• This tells us that a wave with λ corresponding to a zone edge
wavenumber k =  (π/a) will not propagate.
That is, it must be a standing wave!
• At the BZ edge, the displacements have the form (for site n):
Un= Uoeinka = Uo ei(nπ/a) = Uo(-1)n
 Group Velocity, vg in the 1st BZ
vg  (dω/dk) At the 1st BZ Edge,
= vg = 0
a(K/m)½cos(½ka) • This means that a wave
with λ corresponding to
a zone edge
wavenumber
k =  (π/a)
Will Not
Propagate!
• That is, it must be a
1st BZ Standing Wave!
One Dimensional Model # 2:
The Diatomic Chain
• Consider a Diatomic Chain of Two Different Atom Types with
nearest-neighbor, Hooke’s Law type forces (F = - kx) between the
atoms. This is equivalent to a force-spring model with two
different types of atoms of masses, M & m connected by identical
springs of spring constant K.
(n-2) (n-1) (n) (n+1) (n+2)
K K K K
M M m M a)
m
a

b)

Un-2 Un-1 Un Un+1 Un+2

• This is the simplest possible model of a diatomic crystal.

• a is the repeat distance, so, the nearest-neighbor separation is (½)a
• This model is complicated due to the presence of 2 different atom
types, which, in general, move in opposite directions.

M m M m M

Un-2 Un-1 Un Un+1 Un+2

• The GOAL is to find the dispersion relation ω(k) for this model.
• There are 2 atom types, with masses M & m, so there will be 2
equations of motion, one for M & one for m.
..
M u n  K (un1  un )  K (un  un1 ) Equation of Motion
 K (un1  2un  un1 ) for M

..
mu n .. K (un  un1 )  K (u n1  un2 )
-1
Equation of Motion
mu n  K (un  2un1  un2 ) for m
-1
• As before, assume harmonic (plane wave) solutions for the atomic
displacements Un:

M m M m M

Un-2 Un-1 Un Un+1 Un+2

un  A exp i  kxn0  t   xn0  na / 2 Displacement

for M
un   A exp i  kxn0  t   Displacement
for m
α = complex number which determines the relative amplitude and phase of
the vibrational wave. Put all of this into the two equations of motion.

u n   2 A exp i  kxn0  t  

..
Carry out some simple math
manipulation as follows:
 Equation of Motion for the nth Atom (M)
..
M u n  K (un1  2un  un1 )
 k  n 1 a  k  n 1 a
 kna
i

t   i

 t   kna
i

t  i  t  


 2 MAe  K   Ae   2 Ae  2    Ae   
 2  2  2

 
 
 kna
i

 t    kna
i

t  i ka
 kna
i

t 
 kna
i t   i ka 


 2 MAe  2 
 K   Ae  2  e 2  2 Ae  2    Ae  2  e 2 
 
 
Cancel Common Terms
 i
ka
i
ka

 M  K   e  2   e 
2 2 2 eix  e ix  2 cos x
 
 ka 
 M  2 K 1   cos 
2

 2 
 Equation of Motion for the (n-1)th Atom (m)
..
m u n 1  K (un  2un 1  un  2 )
 k  n 1 a  k  n 1 a  k  n2  a
i

t   i  kna t  i

t  i t  


 A 2 me  K  Ae  2   2 Ae   
2 2 2
  
 Ae 
 
 
 kna
i

t   i ka  i  kna 
t 
 kna
i

t   i ka
 kna
i t   i 2 ka 


 2 mAe  2 
e 2
 K  Ae  2   2 Ae  2  e 2  Ae  2  e 2 
 
 
Cancel Common Terms
i
ka
 i
ka
 ika 
 me
2
 K  1  2 e  e 
2 2

 
 ka 
 i
ka
i
ka
  m  2 K  cos   
2
 m  K  e  2  e 
2 2 2
 2 
 
eix  e  ix  2 cos x
• The Equation for M becomes:

(1)
• The Equation for m becomes:

(2)
• (1) & (2) are two coupled, homogeneous, linear
algebraic equations in the 2 unknowns α & ω as
functions of k.
• More algebra gives:   2 K cos( ka / 2) 2 K   2
M

2K   m2
2 K cos( ka / 2)
• Combining (1) & (2) & manipulating:
• Cross multiplying & manipulating with (1) & (2):
2 K cos( ka / 2) 2K   2M
 
2K   m2
2 K cos( ka / 2)
ka
4 K cos ( )  4 K 2  2 K  2 ( M  m)   4 Mm
2 2

2
ka
4 K 2 (1  cos 2 ( ))  2 K  2 ( m  M )   4 Mm  0
2

m  M sin 2
(ka / 2)
  2K (
4
)  4 K
2 2
0
mM mM

b  b 2  4ac
The 2 roots are: x1,2 
2a
K ( m  M ) m  M 4sin 2
( ka / 2) 1/ 2
 
2
K [( ) 
2
]
mM mM mM
 • So, the resulting quadratic equation for ω2 is:

• The two solutions for ω2 are:

• Since the chain contains N unit cells, there will be

2N normal modes of vibration, because there are
2N atoms and 2N equations of motion for masses
M & m.
 Solutions to the Normal Mode Eigenvalue Problem
ω(k) for the Diatomic Chain

w
A
B ω+ = “Optic” Modes
C

ω- = “Acoustic” Modes
–л/a 0 л/a 2л/a k

• There are two solutions for ω2 for each wavenumber k. That is, there are
2 branches to the “Phonon Dispersion Relation” for each k.
• From an analysis of the displacements, it can be shown that, at point A,
the two atoms are oscillating 180º out of phase, with their center of
mass at rest. Also, at point B, the lighter mass m is oscillating & M is at
rest, while at point C, M is oscillating & m is at rest.
 Acoustic & Optic Branches
• In particular, ALL MATERIALS with 2 atoms per unit cell
are observed to have two very different
kinds of vibrational normal modes.
These are called
The Acoustic Branch & The Optic Branch
 The Acoustic Branch
• This branch received it’s name because it contains long wavelength
vibrations of the form ω = vsk, where vs is the velocity of sound. Thus, at
long wavelengths, it’s ω vs. k relationship is identical to that for ordinary
acoustic (sound) waves in a medium like air.
The Optic Branch
• This branch is always at much higher vibrational frequencies than the
acoustic branch. So, in real materials, a probe at optical frequencies is
needed to excite these modes.
• Historically, the term “Optic” came from how these modes were
discovered. Consider an ionic crystal in which atom 1 has a positive charge
& atom 2 has a negative charge. As we’ve seen, in those modes, these atoms are
moving in opposite directions. (So, each unit cell contains an oscillating dipole.) These
modes can be excited with optical frequency range electromagnetic radiation.
THE FREE ELECTRON MODEL
 Free Electron Theory

• Conductors fall into 2 main

classes; metals & semiconductors.
• Here, we focus on metals.
• A metal is loosely defined as a solid
with valence electrons that are not
tightly bound to the atoms but are
relatively easily able to move
through the whole crystal.
• The room temperature resistivity
of metals is in the range:
 ( RT ) metals ;10  10   m
6 8

• Experiments show that  increases with

the addition of small amounts of
impurities. The resistivity normally
decreases monotonically with decreasing
temperature & it can be reduced by the
addition of small amounts of impurity.
 Some Common Properties of Metals:
[Link] Physical Strength
[Link] Density
[Link] Electrical Conductivity
[Link] Thermal Conductivity
5.…….etc.
•In this chapter, we outline a surprisingly simple
theory which does a very good job of explaining
many of these common properties of metals.
 “The Free Electron Model”
•We begin with the assumption that
conduction
electrons exist & that they consist of the
valence electrons from the metal atoms.
•Thus, metallic Na, Mg & Al are assumed to have
1, 2 & 3 mobile electrons per atom, respectively.
•This model seems at first as if it is
Way Too Simple!
•But, this simple model works remarkably
well for many metals & it can be used to
help to explain many properties of metals.
•According to this
Free Electron Model (FEM),
the valence electrons are responsible for the
conduction of electricity, & for this reason these
electrons are called
“Conduction Electrons”.
•As an example, consider Sodium (Na). The electron
configuration of the Free Na Atom is:
1s2 2s2 2p6 3s1

•Core
The outer electron in the third atomicValence
Electrons shell Electrons
(n = 3, bound)
(tightly ℓ = 0) is the electron which is responsible for the physical &
chemical properties of Na. (loosely bound)
 Fermi-Dirac Statistics

•The Fermi Energy EF is

essentially the same as the
Chemical Potential μ.
β  (1/kT)
EF is called The Fermi Energy.
Note the following:
• When E = EF, the exponential term = 1 & FFD = (½).
• In the limit as T → 0:

Ll
• At T = 0, Fermions occupy the lowest energy levels.
• Near T = 0, there is little chance that thermal agitation
will kick a Fermion to an energy greater than EF.
Fermi Function at T = 0 & at
a Finite Temperature
1 fFD=? At 0°K
f FD  ( E  E F ) / k BT
1 e For E < EF
1
fFD(E,T) f FD  ( E  EF ) / k BT
1
1 e

0.5 f FD
For

E >
1 EF
0
( E  EF ) / k BT
1 e

E
E<EF EF E>EF
Fermi-Dirac Distribution
Consider T  0 K
1
For E > EF : f ( E  EF )   0
1  exp ()

For E < EF : 1
f ( E  EF )   1
1  exp ()

E
A step function!
EF

0 1 f(E)
Fermi-Dirac Distribution
Temperature Dependence
 Assumptions of the FEG Model
1. Metals have high electrical conductivity and no apparent activation energy,
so at least some of their electrons are “free” and not bound to atoms
2. Coulomb potential energy of positive ions U  1/r is screened by bound
electrons and is weaker at large distances from nucleus
3. Electrons would have lowest U (highest K) near nuclei, so they spend less
time near nuclei and more time far from nuclei where U is not changing
rapidly
4. Therefore model the behavior of the free
electrons with U = 0 inside the volume of the
metal and a finite potential step at the surface.
Assume each atom has n0 free electrons, where
n0 = chemical valence. Assume that resistance
comes from electrons interacting with lattice
through occasional collisions:
Properties of the FEG: Fermi Energy and Density of States
Time-independent 2 2
    U   E
Schrödinger Equation: 2m
2 2 2mE
With U = 0:     E  2
   2
  2   k 2
2m 

Solutions have
 
i ( k r t )
1. Wave functions:   Ae Traveling waves (plane waves)

2. Energies:  2k 2
E Parabolic energy “bands”
2m

kx
 Properties of the FEG
By using periodic boundary conditions for a cubic solid with edge L and
volume V = L3, we define the set of allowed wave vectors:
2nx 2n y 2nz
kx  ky  kz  nx , n y , nz  1,  2,  3, ...
L L L
3
2
This shows that the volume in k-space per solution is:  
 L 
1 V Just as in the case
And thus the density of states in k-space is: N (k )  
 2 / L  3 8 3 of phonons!

Since the FEG is isotropic, the surface of ky

kF
constant E in k-space is a sphere. Thus
for a metal with N electrons we can kx
calculate the maximum k value (kF) and
the maximum energy (EF). kz
Fermi sphere
 Fermi Wave Vector and Energy
Taking into account the spin degeneracy of the electron, N electrons will be
accommodated by N/2 energy states, so:
1/ 3
 # states 
# states  
 volume 
 volume  
N V 4 
 3  k F3 
2 8  3 
 N
k F   3 2 
V 

 3 2 n  1/ 3

And the maximum energy is easily found: EF 

 2 k F2  2
2m

2m
 3 2 n 
2/3

These quantities are called the

Fermi wavevector and Fermi
energy in honor of Enrico
Fermi, who (along with Arnold
Sommerfeld) did the most to
apply quantum mechanics to
calculate the properties of solids
in the late 1920s.
 Density of States N(E)
We often need to know the density of electron states, which is the number of
states per unit energy, so we can quickly calculate it:

The differential number of

electron states in a range of dN  N ( E )dE  N (k )dk
energy dE or wavevector dk is:

dk N (k ) V / 8 3 mV
This allows: N ( E )  N (k )   
dE dE / dk  2 k / m  2 8 3 k

1/ 2
Now using the
general relation:
 2mE 
k  2  we get: N (E) 
V
 23
 2 m 3
E 1/ 2

  
 Utility of the Density of States
EF

With N(E) we can immediately

total energy  N ( E ) E dE
calculate the average energy per E   0
EF
electron in the 3-D FEG system: # electrons
 N ( E ) dE
0

We can simplify by using the relation: N ( E )  CE1/ 2

EF E
2 5/ 2 F
C E 3/ 2
dE E
5 3
E  0
EF
 0
E
 EF
2 3/ 2 F 5
C  E 1/ 2 dE E
0
3 0
 EXAMPLES

The density of copper is 8.96 gm/cm3, and its atomic weight

is 63.5 gm/mole.
(a) Calculate the Fermi energy for copper. Assume one atom
of cu contributes one free electron and give your answer in
electron volts.

(b) What is the corresponding electron velocity?

(c) At what temperature would the characteristic thermal energy

(kBT, where kB is Boltzman constant and T is Kelvin temperature)
equal the Fermi energy for copper?
H. Limitations of the FEG Model—and Beyond
The FEG model of Drude, augmented by the results of quantum mechanics in the years
after 1926, was extremely successful in accounting for many of the basic properties of
metals. However, strict quantitative agreement with experiment was not achieved. We
can summarize the flawed assumptions behind the FEG model as follows:

1. The free-electron approximation

The positive ions act only as scattering centers and is assumed to have no effect on
the motion of electrons between collisions.

2. The independent electron approximation

Interactions between electrons are ignored.

3. The relaxation time approximation

The outcome of a electron collision is assumed to be independent of the state of
motion of an electron before the collision.
A comprehensive theory of metals would require abandoning these rather crude
approximations. However, a remarkable amount of progress comes from abandoning
only the free-electron approximation in order to take into account the effect of the
lattice on the conduction electrons.