UNIT - V CRYSTAL PHYSICS

Introduction
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.

Classification of Solids
Materials differ in their properties due to its crystal structure, based on which solids are
classified in to two types.
i. Crystalline materials - A substance is said to be crystalline when the arrangement of units
of matter is regular and periodic. A crystalline material has directional properties and
therefore called as anisotropic substance. A crystal has a sharp melting point.
It possesses a regular shape and if it is broken, all broken pieces have the same regular
shape. A crystalline material can either be a single (mono) crystal or a polycrystal. A single
crystal consists of only one crystal, whereas the polycrystalline material consists of many
crystals separated by well-defined boundaries.
Examples - Metallic crystals – Cu, Ag, Al, Mg etc,
Non-metallic crystals – Carbon, Silicon, Germanium.
ii. Amorphous materials - In amorphous solids, the constituent particles are not arranged in an
orderly manner. They are randomly distributed. They do not have directional properties and so
they are called as `isotropic’ substances. They have wide range of melting point and do not
possess a regular shape.
Examples - Glass, Plastics, Rubber etc.,

Crystallographic terms
i. Crystal - Three dimensional solid which consists of a periodic arrangement of atoms in
three dimensional space.
ii. Space lattice - A lattice is a regular and periodic arrangement of points in three dimension.
It is defined as an infinite array of points in three dimension in which every point has
surroundings identical to that of every other point in the array. The Space lattice is also called as
Crystal lattice.
iii. Basis - A crystal structure is formed by associating every lattice point with an unit assembly of
atoms or molecules identical in composition, arrangement and orientation. This unit assembly is
called the `basis’. When the basis is repeated with correct periodicity in all directions, it gives the
actual crystal structure. The crystal structure is real, while the lattice is imaginary.
iv. Unit cell - A unit cell is the smallest unit which, when repeated in space indefinitely,
will generate the space lattice.

Crystallographic axes -
Consider a unit cell consisting of three mutually perpendicular
edges OA, OB and OC as shown in figure 5.1. Draw parallel lines
along the three edges. These lines are taken as crystallographic axes
and they are denoted as X, Y and Z axes.

Fig . 5. 1
Lattice parameters –
Consider the unit cell as shown in figure 5.2. Let OA,
OB and OC are the intercepts made by the unit cell along X,
Y and Z axes respectively. These intercepts are known as
primitives. In crystallography the intercepts OA, OB and OC
are represented as a, b and c. The angle between X and Y
axes is represented as . Similarly the angles between Y and Z
and Z and X axes are denoted by  and  respectively as
shown in the figure 5.2. These angles ,  and  are called as
interaxial angles or interfacial angles. To represent a lattice,
the three interfacial angles and their corresponding intercepts Fig . 5. 2
are essential. These six parameters are said to be lattice
parameters.

Primitive cell - 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 called
as non-primitive cell.
Example for primitive cell : Simple Cubic unit cell.
Examples for non-primitive cell: BCC and FCC unit cell.
SEVEN CRYSTAL SYSTEMS
1. Cubic (isometric)
2. Tetragonal
3. Orthorhombic
4. Monoclinic
5. Triclinic
6. Rhombohedral
7. Hexagonal

S. Possible
Crystal system Axial lengths Interfacial angles Example
No lattice
1 Cubic a=b=c α = β = γ = 90 P, I, F Fe, Cu, Nacl
Ordinary
2 Tetragonal a=b≠c α = β = γ = 90 P, I white tin,
Indium
3 Ortho rhombic a≠b≠c α = β = γ = 90 P, I, F, C Topaz, S
FeSo4,
4 Mono clinic a≠b≠c α = β = 90 γ ≠ 90 P, C
Na2So4
CuSo4,
5 Triclinic a≠b≠c α ≠ β ≠ γ ≠ 90 P
K2Cr2O7
6 Rhombohedral a=b=c α = β = γ ≠ 90 P Calcite
Quartz,
7 Hexagonal a=b≠c α = β = 90 γ = 120 P
Tourmaline
CRYSTAL SYSTEMS
Crystals are classified into seven crystal systems on the basis of lattice parameters such as
axial lengths a, b, c and interfacial angles α, β, γ. They are 1. Cubic (isometric) 2. Tetragonal
3. Orthorhombic 4. Monoclinic 5. Triclinic 6. Rhombohedral 7. Hexagonal.
1.CUBIC SYSTEM
Here, three crystal axes are perpendicular to each other and axial lengths are same along all
the three axis.
Lattice paramters are a = b = c, α = β = γ = 90◦ Ex: Iron, Copper
2. TETRAGONAL SYSTEM
Here , three crystal axes are perpendicular to each other. Two of the three axial lenghts are
the same, but the third axial length is different.
Lattice paramters are a = b ≠ c, α = β = γ = 90◦ Ex: White tin, Indium
3. ORTHORHOMBIC SYSTEM
Here, three crystal axes are perpendicular to each other. All the three axial lengths are of
unequal lengths.
Lattice paramters are
a ≠ b ≠ c, α = β = γ = 90◦ Fig. 5.3 (a)
Ex: Sulphur, Topaz
4. MONOCLINIC SYSTEM
Here, two of the crystal axes are
perpendicular to each other, but the third is
obliquely inclined.Three axial lengths are
different.
Lattice paramters are
a ≠ b ≠ c, α = β = 90◦γ ≠ 90◦
Ex: Sodium sulphite, Fe3SO4.
5. TRICLINIC SYSTEM
Here, two of the crystal axes are not perpendicular to each other, axial lengths are also not
equal.
Lattice paramters are a ≠ b ≠ c, α ≠ β ≠ γ ≠ 90◦ Ex: Copper sulphate.
6. RHOMBOHEDRAL SYSTEM
Here, the three crystal axes are inclined to each other at an angle other than 90◦, three axial
lengths are equal along the axes.
Lattice paramters are a = b = c, α = β = γ ≠ 90◦ Ex: Calcite
7. HEXAGONAL SYSTEM
Here, two of the crystal axes are 120◦ apart, while the third is perpendicular to both of them.
The axial lengths are the same along the axes that are 120◦ apart, but axial length along the third axis
is different.
Lattice paramters are a = b ≠ c, α = β = 90◦γ = 120◦ Ex: Quartz, Tourmaline
 BRAVAIS LATTICES
According to Bravais, there are 14 possible ways of arranging points in space such that
environment looks same from each point.
1.CUBIC LATTICE
 Simple cubic has 8 corner atoms, 1 at each corners.
 BCC has 8 corner atoms 1 at each corners and another atom at the centre of the body.
 FCC has 8 corner atoms 1 at each of 8 corners. In addition there are 6 face centred atom 1 at
each of the 6 faces of the cubic.
2.TETRAGONAL LATTICE
 Simple tetragonal has 8 corner atoms, one at each corners.
 Body centred tetragonal has 8 corner atoms and 1 at the body centre.
3. ORTHORHOMBIC LATTICE
 Simple orthorhombic has 8 corner atoms.
 Body centred orthorombic there are 8 corner atoms and one atom at body centre.
 Face centred orthorombic has 8 corner atoms and 6 face centred atoms.
 Base centred orthorombic has 8 corner atoms and 2 atoms at the centre of 2 faces.
4. MONOCLINIC LATTICE
 Simple monoclinic has 8 corner
atoms, one at each corners.
 Base centred monoclinic has 8
corner atoms, one at each
corners and 2 atoms at the centre
of faces.
5.TRICLINIC LATTICE
 Simple monoclinic has 8 corner
atoms, one at each corners.
6.RHOMBOHEDRAL LATTICE
 Simple rhombohedral has 8
corner atoms, one at each
corners.
7.HEXAGONAL LATTICE Fig. 5.3 (b)
 Simple hexagonal has 12 corner atoms, one at each corners and 2 atoms at the centre of
2 hexagonal faces.

Characteristics of an unit cell

i) No of atoms per unit cell (n) - Number of atoms possessed by a unit cell
ii) Coordination number (CN) - Number of nearest atoms directly surrounding a particular
atom in a crystal.
iii) Nearest neighbouring distance (a) - Distance between the centers of two nearest
neighbouring atoms (2r).
iv) Atomic radius (r) - Half of the nearest neighbouring distance in a crystal.
v) Atomic packing factor (APF) - Ratio of the volume of atoms in the unit cell to the volume
of the unit cell. There is no unit for it since it is a ratio.
SIMPLE CUBIC (SC) STRUCTURE
In this structure, there is one atom at each of the 8 corners of unit cell. These
atoms touch each other along cubic edges.
No. of atoms per unit cells
It is the number of atoms possessed by the unit cell. There is one atom at
each corner of unit cell. Each corner atoms is shared by 8 adjacent unit cells.
1 1 Fig. 5.4 (a)
Share for one unit cell   share for one unit cell   8  1 atom
8 8
Total number of atoms in a unit cell = 1 atom
Coordination number
It is the number of nearest atoms directly surrounding a particular atom in a
crystal.Simple cubic unit cell has 8 corner atoms. Let us consider one of the corner
atom (X).
It is in direct touch with 6 adjacent unit cells edge atoms.
Hence, coordination number for simple cubic is 6. Fig. 5.4 (b)
Atomic Radius
It is half of the distance between two nearest neighboring atoms in a crystal.
Consider a face of unit cell of SC. The atoms touch each other along the edges. If ‘a’
is the side of the unit cell and ‘r’ its radius, then
2r  a ; r  a
2
Packing factor Fig. 5.4 (c)
It is defined as the ratio of total volume occupied by the atoms in the unit cell (v) to the volume
of unit cell (V).
𝑁𝑜.𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑝𝑒𝑡 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 ×𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑜𝑛𝑒 𝑎𝑡𝑜𝑚
P.F =
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
Number of atoms per unit cell = 1
4
Volume of one atom   r3
3
Total volume of unit cell = a3
4
1  r 3
P.F. =  3
a3
a
By substituting r 
2
3
a
4  
2 4  a 3 
P.F.    = 0.52×100
3 a 3
3 8 a 3
6
P.F. = 52 %
Thus 52 % volume of unit cell is occupied by the atoms and remaining 48 % volume is vacant.
Ex:- Polonium.
BODY CENTERED CUBIC (BCC) STRUCTURE
In this structure, the unit cell has one atom at each corner and one atom at
the body centre of the cube.
Number of atoms per unit cell
It is the number of atoms possessed by the unit cell. Each corner atom is
shared by 8 surrounding unit cells.
1 Fig. 5. 5 (a)
Share for one unit cell   share for one unit cell
8
1
Contribution due to corner atoms   8  1 atom
8
There is one atom at the body centre of each unit cell
Total number of atoms per unit cell = 1+1= 2 atoms Fig. 5. 5 (b)

Coordination number
It is the number of nearest atoms directly surrounding a particular atom in a crystal. In BCC
structure, the corner atoms do not touch each other. But all ‘8’ corner atoms
touch the body centre atom along the body diagonal. If body centered atom
is a reference atom, there are ‘8’ nearest neighbours. Hence, the
coordination number of BCC structure is ‘8’.
Atomic radius
It is half of the distance between two nearest neighboring atoms in
a crystal.Consider the atoms at A, G and O. These atoms lie in a straight
line along the body diagonal.
From the figure, Fig. 5. 5 (c)
AG = r+2r+r = 4r
 AG2 = (4r)2 = 16 r2 (1)
From the  ABC,
AC2 = AB2+BC2
= a2+a2 = 2a2
From the  ACG,
AG2 = AC2+CG2
= 2a2+a2
AG2= 3a2 (2)
Using (2) in (1),
3a2 = 16r2
3a 2 3a
r2  ; r
16 4
Packing factor
It is defined as the ratio of total volume occupied by the atoms in the unit cell (v) to the volume
of unit cell (V)
v
P.F 
V
Number of atoms per unit cell = 2
4
Volume of 1 atom in the unit cell   r3
3
3a
Atomic radius 
4
Volume of the unit cell = a3
4
2  r 3
P.F  3
a3
By substituting r,
3
 3a 
2  4  

 4 
P.F 
3 a 3

8  3 3a 3

3 a3  4  4  4
3
 = 0.68×100 ; P.F = 68 %
8
Thus packing factor is 68 %, which means 68 % of the volume of unit cell is occupied by atoms
and the remaining 32 % volume is vacant. Ex:- Tungsten, Chromium

FACE CENTERED CUBIC (FCC) STRUCTURE

In FCC structure, the unit cell has one atom at each corner of the cube
and one atom at the centre of each face.
Number of atoms per unit cell
It is the number of atoms possessed by the unit cell.
There are 8 corner atoms, one at each of its 8 corners. Each corner atom
is shared by 8 surrounding unit cells.
1
Share of each unit cell  of corner atoms
8 Fig. 5. 6 (a)
1
Number of atoms per unit cell due to corner atom   8 =1 atom
8
Each face centre atom is shared by 2 adjacent unit cells.
1
Hence number of atoms per unit cell due to face center atom   6 =3 atom
2
Total number of atoms per unit cell = 1+3 =4 atoms
Coordination number
It is the number of nearest atoms directly surrounding a particular
Fig. 5. 6 (b)
atom. Consider three mutually perpendicular planes with a common corner
atom. In each plane of I, II & III, there are four face centered atoms touch with common corner atom.
CN = 4+4+4 = 12
Therefore, coordination number is 12.
Atomic radius
It is half of the distance between two nearest neighbouring atoms.
Consider a face of ABCD in FCC structure. In which Face centered atom is touch with four
corner atoms along the face diagonal.
AC2 = AB2+BC2
AC2 = a2+a2
AC2 = 2a2 (1)
Interms of atomic radius, AC = 4r
AC2 = (4r)2 = 16 r2 (2)
2 2
Using (1) & (2), 2a = 16r
2a 2 a 2
r2  
16 8
a a
r 
8 2 2
Packing Factor Fig. 5. 6 (c)
It is defined as the ratio of total volume occupied by the atoms in a unit cell to the total volume
of a unit cell.
v
P.F 
V
Number of atoms per unit cell = 4
4
Volume of 1 atom   r3
3
a
Atomic radius 
2 2
Volume of unit cell = a3
3
 a 
 
4  r 3 16   2 2 
4
P.F  3   
3 3
a 3a
16  a 3
 3
3a  8  2 2

 = 0.74×100
3 2
P.F. = 74 %
Thus the packing factor is 74 % (ie) 74 % of the volume of unit cell is occupied by the atoms
and the remaining 26 % of volume is vacant. Ex:- Copper, Aluminum.

HEXAGONAL CLOSE-PACKED (HCP) STRUCTURE

 The unit cell has one atom at each of 12 corners of the hexagonal face, one atom each at the
centre of the two hexagonal faces.
 3 atoms symmetrically arranged inside the unit cell.
  There are 3 layers of atom in it.
 At the bottom layer, the central atom has 6 nearest neighbouring
atoms in the same plane.
 The middle layer at a distance of C/2 from the bottom layer has 3
atoms.
 The bottom layer is similar to top layer which is at a distance of ‘c’.
Number of atoms per unit cell:
It is the number of atoms possessed by the unit cell. Each corner
is shared by 6 surrounding unit cells.
Hence number of atoms per unit cell due to corner atom
1
  12  2 atoms Fig. 5. 7 (a)
6
Each face centered atom is surrounded by 2 unit cell
1
Number of atoms per unit cell due to face centered atom   2  1 atom
2
There are 3 atoms completely inside the unit cell which are not shared by
any other adjacent unit cell.
Total number of atoms per unit cell = 2+1+3 = 6 atoms
2. Coordination number:
 Consider the bottom layer the central atom has 6 nearest neighbouring
atoms in the same plane. Fig. 5. 7 (b)
 At a distance C/2 from the bottom layer, there are two layers, one above and other below the
bottom layer containing 3 atoms in each layer are also neighbouring atoms.
In total there are 3+6+3 = 12 nearest neighbouring atoms.
Coordination number is 12.
3. Atomic radius:
It is half of the distance between two nearest neighbouring atoms.
Here atoms are touch each other along the edges of the hexagon.
The nearest neighbouring distance a = 2r.
a
Atomic radius, r 
2
4. Packing Factor:
It is defined as the ratio of total volume occupied by the atoms in a unit
cell to the total volume of a unit cell.
𝑁𝑜.𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑝𝑒𝑡 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 ×𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑜𝑛𝑒 𝑎𝑡𝑜𝑚
P.F =
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 Fig. 5. 7 (c)
Number of atoms per unit cell = 6
4
Volume of one atom   r3
3
a
Atomic radius, r 
2
Calculation of c/a ratio:
Consider a triangle ABO in the bottom layer. Above these ABO atoms at a perpendicular
distance C/2, the next layer atom lies at point ‘c’.
AY
 ABO, a line AY is drawn perpendicular to BO, cos 30 o 
AB
a 3
AY = AB cos 30 o 
2
X is a centre of  ABO, then
2 a 3
AX = 
3 2
a
AX =
3
In the  ABO AC2 = AX2+CX2
a c
Substituting the values for AC = a, AX = , CX =
3 2
2
 a  c
2

a2 =     
 3  2
a2 c2
a2 = 
3 4
c2 a
 a2 
4 3
c 2 2a 2

4 3 Fig. 5. 7 (d)
2
c 8

a 3
c 8

a 3
Calculation of volume of unit cell:
The volume of unit cell can be calculated by multiplying the base area with the height of the
unit cell. The base area can be calculated by multiplying 6 with area of one equilateral triangle.
3a 2
Area of one equilateral triangle 
4
3a 2
Volume of unit cell  6  c
4
3 3a 2 c
V 
2
3
4 a
6  r 3 24   2
P.F. = 3  2
2
3 3a c 3  3 3a 2 c
2
 24  a 3  c
=
9 3a 2 c  8
2 a
P.F =
3 3c
By substituting c/a value
2 3 2 3
P.F = =
3 3 8 3 32 2

= = 0.74×100
3 2
Packing factor = 74 %
Therefore, 74 % of volume of unit cell is occupied by the atoms and the remaining 26 % volume is
vacant.

DIAMOND CUBIC (DC) STRUCTURE

This structure is a combination of two
interpenetrating FCC sub lattices.
Number of atoms per unit cell
It is the number of atoms possessed by the unit
cell. In the unit cell of diamond, the carbon atoms are
present at three different positions of the unit cell.
(i) Corner atoms (ii) Face centered atoms
(iii) Four atoms present fully inside unit cell.
Fig. 5. 8 (a)
Each corner atom is shared by 8 unit cells.
1
Number of atoms due to corner atoms per unit cell   8 =1 atom
8
1
Number of atoms per unit cell due to face centered atom   6 =3 atom
2
Inside unit cell, 4 atoms which are not shared by any other surrounding unit
cells.
Total number of atoms per unit cell = 1+3+4 = 8 atoms
Atomic radius
The corner atoms do not touch each other. But both face centered atoms
and corner atoms touch with the 4 atoms situated inside the unit cell.The atoms
X and Y are touch each other along the body diagonal with the position
X(0,0,0) and Y (a/4,a/4,a/4). Fig. 5. 8 (b)
A perpendicular is drawn from ‘Y’ atom which meets the unit cell at a point ‘Z’ which is at a
distance of a/4.
 XY2 = XZ2+ZY2
XY2 = XT2+TZ2+ZY2
2 2 2
a a a
     
4 4 4
3a 2 3a
XY2  XY 
16 ; 4
W.K.T, XY = 2r Fig. 5. 8 (c)

3a
 r
8
Coordination number
It is half of the distance between two nearest neighbouring atoms.
In this structure, first inner atom is touch with 3 nearest face centered atom and one corner
atom. So the coordination number for diamond = 4
Packing Factor
It is defined as the ratio of total volume occupied by the atoms in a unit cell to the total volume
of unit cell.
No.of atoms per unit cell ×volume of one atom
P.F = 𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
Number of atom per unit cell = 8
4
Volume of one atom   r3
3
3
Volume of unit cell = a
4
8  r 3
P.F  3
a3
3
 3a 
8  4  

 8  8  4  3  3  a 3
 
3 a3 3 a3  8  8  8
 3
 = 0.34×100
16
Thus 34 % volume of unit cell is occupied by atoms and the remaining 66 % volume is vacant.

MILLER INDICES
Definition
Miller indices are defined as the reciprocal of the intercepts made by the plane on the
crystallographic axes which are reduced to smallest numbers.
Procedure for finding Miller Indices:
Let us consider a plane ABC which cuts 1units along x – axis 2 unit along y – axis and 3 unit
along z- axis.
Step 1
Find the intercepts made by the plane ABC along the three axis interms of axial length.
 OA:OB:OC = pa:qb:rc [p =1,q = 2, r = 3]
 The intercepts are 1a : 2b: 3c
Step 2
Find the coefficients of intercepts, p, q, r
(i.e) 1,2,3
Step 3
1 1 1
Find the reciprocal of these numbers, , ,
p q r
1 1 1
(i.e) , ,
1 2 3
Step 4
Convert these reciprocals into whole numbers by multiplying each Fig. 5. 9
and every reciprocal with their least common multiplier.
1 1 1
Since 6 is the LCM in this case, we get 6  ,6  ,6 
1 2 3
We have 6 3 2
Step 5
Enclose these numbers in a bracket .i.e. (6 3 2). This is called Miller Indices of the plane. The
general notation for Miller Indices is (h k l).
Significance of Miller Indices
 The Miller Indices should be enclosed only in this bracket ( ).
 There should not be any commas in between the numbers.
 If the Miller Indices are say (6 3 2) means it should be read as six three two.
 The direction of plane can be represented by enclosing the Miller Indices in a square bracket
[h k l].

IMPORTANT FEATURES OF MILLER INDICES

 If a plane is parallel to any one of the coordinate axes , the corresponding intercept will be
infinite (∞) and therefore the corresponding Miller Index is zero
 Miller indices don’t define a particular plane but a set of equidistant parallel planes. They are
represented as < h k l >
a b c
 For a group of parallel planes < h k l > the intercepts can be represented as , ,
h k l
 A plane passing through the origin is defined in terms of a parallel plane having nonzero
intercepts.
 If a plane has negative intercept the corresponding Miller index will be written with a bar.
Ex. (1 1 1 )

RELATION BETWEEN INTERPLANAR SPACING AND LATTICE CONSTANT

It is perpendicular distance between successive parallel planes. Consider a plane ABC in Cubic
crystal with ‘a’ as length of cube edge and Miller Indices of (h k l)
 A normal ON is drawn to the plane ABC from the origin plane. Let ON be the interplanar
spacing (d). This plane ABC makes the intercepts OA, OB, OC on the crystallographic axis X, Y, Z.
 ' ,  ' and ' are the angles between the axis X, Y, Z and the normal ON respectively.
1 1 1
OA: OB: OC = : :
h k l
By multiplying by lattice constant ‘a’
a a a
OA: OB: OC = : :
h k l
a a a
OA = , OB = , OC =
h k l
From the  OAN
ON d hd
cos '   
OA a a
h
Fig. 5. 10 (a)
From the  OBN
ON d kd
cos  '   
OB a a
k
From the  OCN
ON d ld
cos  '   
OC a a
l
The law of direction cosines is
cos 2  ' cos 2  ' cos 2  '  1
2 2 2
 hd   kd   ld 
      1
 a   a  a


d2 2
2
h  k2  l2 1 
a
a2
d2 

h2  k 2  l 2  Fig. 5. 10 (b)
a
d 
h 2
 k2  l2 

MILLER INDICES FOR DIFFERENT

PLANES

Fig. 5. 11
 CRYSTAL IMPERFECTIONS
If atoms in the solid are not arranged in a perfectly regular manner, it is called
defects (or) imperfections in crystals. It is observed that the crystals are rarely found to be
perfect.
The effect of imperfections is found to be very important in understanding the
properties of crystals. This is because, structure insensitive properties like stiffness,
density and electrical conductivity are not affected much by the presence of imperfections
of defects in the crystals.
Structure sensitive properties such as, mechanical strength, ductility, crystal
growth, magnetic hysteresis, dielectric strength which are of greatest technical
importance are found to be greatly affected by the presence of imperfections.

Various types of crystal Imperfections

1. Lattice vibrations or Phonons

2. Point defects or zero dimensional defects
a) Vacancies
b) Interstitial defects
c) Self-interstitial defects
d) Schottky defect
e) Frankel defect
3. Line defects or one dimensional defects or dislocations
a) Edge dislocation
b) Screw dislocation
c) Dislocation climb
d) Dislocation slip.
4. Surface defects or plane defects or two dimensional defects
a) Grain boundaries
b) Twin boundaries
c) Tilt boundaries
d) Stacking faults
5. Volume defects of three dimensional defects or bulk defects.

Lattice vibrations or Thermal Vibrations or Phonons-

Mathematically, atoms in a perfect lattice should occupy exactly the sites to which
they are attached. No crystal is perfectly rigid, since it can be deformed by finite forces. It
is possible to displace the atoms from their ideal sites with a finite expenditure of energy
due to lattice vibrations (thermal vibrations). The frequency of vibration is almost
independent of temperature, but the amplitude increases with increasing temperature.
When the vibrations become strong enough the atoms may break the bonds between
them. Since the atoms interact with one another they tend to vibrate in synchronism. The
thermal vibration of atoms of a solid does not seriously disturb the perfect structure of the
crystal.
CRYSTAL IMPERFECTIONS
The disturbance occurred in the regular orientation of atoms is called crystal defect or
imperfection.
Classification of crystal defects
 Point defect – Zero dimensional
 Line defect – One dimensional
 Surface defect – Two dimensional
 Volume defect – Three dimensional Fig. 5. 12 (a)
1) Point defect:
Point defects are crystalline irregularities in one or two atomic dimension. There are three types
of point defects.
a) Vacancies
One or more atoms are missing from a normal occupied position is known as vacancy. There
are different kinds of vacancies like Frenkel defect, Schottky defect etc.
i) Schottky defect
Two oppositely charged ions are missing from an ionic crystal. This is known as Schottky
defect. Since a pair is missing, electrical neutrality is maintained.
ii) Frenkel Defect
A vacancy associated with interstitial impurity is called Frenkel
defect. Frenkel defect does not change the overall electrical neutrality.
b) Interstitial defect
When an extra atom occupied interstitial space within the crystal
structure without removing parent atom, the defect is called interstitial defect.
There are two types namely self and foreign interstitial.
i) Self Interstitial
If an atom from same crystal occupies interstitial site, then it is called
self Interstitial.
Fig. 5. 12 (b)
ii) Foreign Interstitial
If an impure atom occupies interstitial site, then it called foreign interstitial.
c) Impurities
When the foreign atoms are added to crystal lattice, they are known as impurities. The defect
is called impurity defect.
i) Substitution impurity
A substitutional impurity refers to foreign atoms that replace a parent atom in the lattice.
ii) Interstitial impurity
An interstitial impurity is a small size atom occupying the empty space in the parent crystal,
without dislodging any of the parent atoms from their sites.
2) Line defects
The defects due to dislocation or distortion of atoms along a line are known as line defects.
These defects are also called dislocation.
Types of dislocations
i) Edge dislocation
An edge dislocation arises when one of the atomic
planes forms only partially and does not extend
throughout the lattice. The atomic plane AB terminates at
B. It is viewed as an extra plane inserted in between a set
of parallel planes. This is called edge dislocation.
There are two types of edge dislocations namely
Positive edge dislocation () & Negative edge
dislocation (T). If the extra plane of atoms above the slip
Fig. 5. 12 (c)
plane than that edge dislocation is called positive. If the
extra plane of atom below the slip plane than that edge
dislocation is called negative.
i) Screw dislocation
Screw dislocation is due to a displacement of
atoms in one part of a crystal relative to rest of the
crystal. This dislocation forms a spiral ramp around
dislocation line.If spiral motion of one part of the crystal
is in clockwise direction then dislocation is right handed,
on the other hand, spiral motion is in anti-clockwise
directions then the dislocation is left handed. Fig. 5. 12 (d)

3) Surface defects
The defects on the surface of material are
called surface defects.The surface defects are
Grain boundaries, Tilt & twist boundaries, and
Twin boundaries, Stacking fault
i) Grain boundaries
Whenever the grains of different
orientations separate the general pattern of atoms
and exhibit a boundary, the defect caused is called
grain boundary.
A grain boundary is formed when two
growing grain surfaces meet. The shape of the
grain is usually influenced by the presence of
Fig. 5. 12 (e)
surrounding grains.
i) Tilt and twist boundaries
Tilt boundaries are an array of parallel edge dislocation of
same sign arranged one above other in an array or series. Twist
boundaries consists of atleast two set of parallel screw dislocation
lying in the boundary.

ii) Twin boundaries

If the boundaries in which the atomic arrangement on one Fig. 5. 12 (f)
side of the boundary is somewhat a mirror image of the other side,
then that defect is called twin boundary.

3. Stacking faults
Whenever the stacking of atoms is not in proper sequence
throughout the crystal, defect caused is called stacking fault.
Fig. 5. 12 (g)

Fig. 5. 12 (h)
ROLE OF IMPERFECTIONS IN PLASTIC DEFORMATION
Plastic deformation is defined has the process of permanent deformation which exists in a
metal even after the removal of the stress. This occurs due to rolling, forging, drawing, spinning etc.,
The plastic deformation in crystalline materials occurs at low temperature where the application of
stress is very small. Plastic deformation usually occur under the tensile, compressive or torsional
stresses. There are two basic modes of plastic deformation namely slip or gliding and twinning. The
slip mode is commonly found in many crystals at elevated temperature where the twinning at occurs
at lower temperature.
Modes of Plastic deformation:
1. Slip or gliding
The shear deformation in which the atom moves in one crystal plane over the atom of another
crystal plane by inter atomic distance relative to its initial position. Lower stresses is enough to produce
slip. It occurs due to the movement of dislocation. The orientation of the crystal above and below the
slip plane is same before and after deformation. Slip band is formed after several milli seconds.
2. Twinning
The shear deformation in which a portion of the crystal takes up another portion as a mirror image.
Higher stresses is required. It occurs due to mechanical deformation. Twinning results in an orientation
difference across twin plane. Twins can be formed in few micro seconds.
 CRYSTAL GROWTH - SOLUTION GROWTH
It is a simplest method to grow many crystalline materials which are highly soluble.
Low temperature solution growth:
The low temperature solution growth is suitable for materials which decompose at high
temperature and undergo phase transformation below the melting point. There are two methods of low
temperature solution growth. They are
 Slow cooling method
 Slow evaporation method
SLOW COOLING METHOD
Slow cooling is the easiest method to grow bulk single crystals from solution. This technique
needs only a vessel for the solution, in which the crystals grow.
The temperature at which crystallization begin is in the range of 45 ◦C to 75 ◦C and the lower limit of
the cooling is the room temperature.
SLOW EVAPORATION METHOD
In this method, the saturated solution is kept at a particular
temperature and provision is made for evaporation. This is simple
and convenient method of growing single crystals of large size.
 Growth of strain and dislocation free crystals.
 Permits the growth of prismatic crystals by varying the
growth conditions
 Only method which can be used for substances that
undergo decomposition before melting.
 A variable rate of evaporation may affect the quality of the crystal. Fig. 5. 13 (a)
Vapour growth technique
The crystalline material to be grown is vaporized and condensed to form crystal on a seed
crystal or substrate. The methods of growth of crystal form vapour phase are broadly classified into
two types.
i) Physical vapour deposition (PVD)
The solid material is converted into gaseous phase by physical process of heating. The
evaporated materials is passed through a low pressure inert gas atmosphere chamber. The vapour
condenses through collision with inert gas species and becomes super saturated homogenously.
ii) Chemical vapour deposition (CVD)
CVD involves the reaction of vapour phase material followed by decomposition to form solid
phase singale crystal.
 In this method, both carrier gas and the reactive gas are taken into two cylinders.
 The carrier gas carries the reactive gas into the inlet port of the evacuated reactive
chamber. A substrate is placed inside the reactive chamber near to outlet port on which required
crystal will be grown.
 Both reactive and carrier gases are allowed into the reactive chamber and heated to a
suitable temperature, so that reaction can take place at high temperature. During the
reaction, the atoms/molecules of the reactive gas will fall on the substrate
Advantages: It is used for the crystalline materials having high
melting point, less solubility in solvents and also it enables the
production of high purity crystals.

CRYSTAL GROWTH - CZOCHRALSKI METHOD

Principle
It is a crystal pulling technique of growth of crystal by a
gradual layer by layer condensation of melt.
Construction & Working
 The pure material which is to be grown in the form of a
single crystal is taken in the crucible.
 The material is heated above the melting point by using
induction heater. Thus the melt is obtained in the crucible.
 A small defect free single crystal, called seed crystal is
introduced into the melt by means of a crystal holder.
 A small portion of seed crystal is initially melted. The Fig. 5. 13 (b)
temperature is adjusted for the growth of seed crystal by the solidification of melt into a thin
layer of crystal.
 The seed crystal is rotated and gradually pulled out of the melt by maintaining the grown crystal
and melt interface near the surface of the melt.
 Thus a single crystal grown is on the seed crystal. The diameter of the grown crystal is
controlled by the temperature of the melt and rate of pulling.
Advantages
1. It will produce strain free surface
2. It can produce large single crystal called ingot.
Limitations
1. High vapour pressure of the materials can be produced.
2. It may produce contamination of melt by the crucible.
CRYSTAL GROWTH - BRIDGMANN TECHNIQUE
Principle
The selective cooling of the molten material to form
single crystal by solidification along a particular direction is
the principle of Bridgmann Technique.
Construction & Working
 In this method the material to be grown in the form of
single crystal is taken in a cylindrical crucible.
 The crucible is made of platinum and tapered
conically with pointed tip at the bottom.
 The crucible is suspended in the upper furnace until
the material in the crucible is completely melted. Fig. 5. 13 (c)
 The crucible is then slowly lowered from upper furnace into lower furnace with help of an
electric motor.
 The temperature of the lower furnace is maintained below the melting temperature of the melt.
 Since the pointed tip enters the lower furnace first, the melt at this point starts to solidify to
form crystal.
 As the crucible is continuously lowered, the solidification of melt continues to form crystal
until all the melt become a solid crystal.
Advantages
1. It is a simple technique.
2. It enables easy stabilization of temperature gradients.
3. Crucible can be evacuated and sealed. Hence oxidation of melt is prevented.
Limitations
1. Confinement of crystal may occur.
2. No visibility of material during growth.
X- RAY DIFFRACTION
Max von Laue, in 1912, discovered that crystalline substances act as three-dimensional
diffraction gratings for X-ray wavelengths similar to the spacing of planes in a crystal lattice. X-
ray diffraction is now a common technique for the study of crystal structures and atomic spacing.

Laue diffraction
Laue diffraction, first detected by Max von Laue, a German physicist, is invaluable for
crystal analysis. Laue diffraction, in X-rays, produces a regular array of spots on a photographic
emulsion resulting from X-rays scattered by certain groups of parallel atomic planes within
a crystal.
When a thin, pencil-like beam of X-rays of wavelengths ranging from 0.2 Å to 2 Å is
allowed to impinge on a crystal of dimension 1 mm * 1mm * 1mm, certain wavelengths will be
oriented at just the proper angle to a group of atomic planes so that they will combine in phase to
produce intense, regularly spaced spots on a film or plate centred around the central image from
the beam, which passes through undeviated. The symmetry of the spot pattern reflects the
symmetry of the crystal when viewed along the direction of the incident beam. Laue method is
often used to determine the orientation of single crystals by means of illuminating the crystal with
a continuous spectrum of X-rays.
Although the Laue method can also be used to determine the crystal structure, several
wavelengths can reflect in different orders from the same set of planes, with the different order
reflections superimposed on the same spot in the film. This makes crystal structure determination
by spot intensity difficult. Powder diffraction method overcomes this difficulty.
X-ray Powder Diffraction (XRD)
X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase
identification of a crystalline material and can provide information on unit cell dimensions. The
analyzed material is finely ground, homogenized, and average bulk composition is determined.

Fundamental Principles of X-ray Powder Diffraction (XRD)

X-ray diffraction is based on constructive interference of monochromatic X-rays and a
crystalline sample. These X-rays are generated by a cathode ray tube, filtered to produce
monochromatic radiation, collimated to concentrate, and directed toward the sample. The
interaction of the incident rays with the sample produces constructive interference when conditions
satisfy Bragg's Law (nλ=2d sin θ). This law relates the wavelength of electromagnetic radiation to
the diffraction angle and the lattice spacing in a crystalline sample.

X-ray diffractometers consist of three basic elements:

 X-ray tube,
 Sample holder, and
 X-ray detector.

X-rays are generated in a cathode ray tube by heating a filament to produce electrons. The
electrons are accelerated toward a target by applying a voltage, and bombarding the target material
with electrons. When electrons have sufficient energy to dislodge inner shell electrons of the target
material, characteristic X-ray spectra are produced. These X-rays are collimated and directed onto
the sample. As the sample and detector are rotated, the intensity of the reflected X-rays is recorded.

The geometry of an X-ray diffractometer is such that the sample rotates in the path of the
collimated X-ray beam at an angle θ, while the X-ray detector is mounted on an arm to collect the
diffracted X-rays and rotates at an angle of 2θ. The instrument used to maintain the angle and
rotate the sample is termed a goniometer. For typical powder patterns, data is collected at 2θ from
~5° to 70°, angles that are preset in the X-ray scan.

Applications
X-ray powder diffraction is most widely used for
 the identification and characterization of unknown crystalline materials

 identification of fine-grained minerals such as clays and mixed layer clays that are
difficult to determine optically
 determination of unit cell dimensions
 measurement of sample purity

Strengths
 Powerful and rapid (< 20 min) technique for identification of an unknown mineral
 Minimal sample preparation is required
 XRD units are widely available
 Data interpretation is relatively straight forward

Limitations
 Must have access to a standard reference file of inorganic compounds (d-spacings, hkls)
 Requires tenths of a gram of material which must be ground into a powder
 For mixed materials, detection limit is ~ 2% of sample
GRAPHITE STRUCTURE
v Graphite, one of the allotropic forms of carbon.
v Carbon atoms arranged in regular hexagons in flat parallel layers such that each carbon
atom is linked by the neighboring atoms.
v When each carbon atom forms three covalent bonds with three other carbon atoms in the
same plane with bond length 1.42 Ȧ, sheets of graphite are produced.
v The sheets are held together in a crystal by Vander walls force with spacing about 3.4 Ȧ.
v It shows that there is no strong binding between different layers.
v Therefore layers are easily separable from each other.
v The weak intersheet bonding explains the softness of graphite and hence it used as a
lubricant.
v The fourth bonding electron of carbon is delocalized and resonates between three
covalent bonds due to this graphite have good electrical and thermal conductivities.

Fig. 5. 12
PROPERTIES
v High thermal conductivity
v High thermal shock resistance
v High melting temperature
v Low density
v Low hardness
v High electrical conductivity

APPLICATIONS
v As a lubricant at higher temperature
v For manufacturing lead pencils and stove paints
v It is a component of printer’ ink

15
Epitaxial growth
Epitaxy refers to the method of depositing a mono-crystalline film on a mono-
crystalline substrate. The deposited film denoted as epitaxial film or epitaxial layer. Epitaxial
films may be grown from gaseous or liquid precursors. The substrate acts as a seed crystal, the
deposited film takes on a lattice structure and orientation identical to those of the substrate.
Hence the quality of single crystalline growth depends on the crystallinity of substrate.

TYPES OF EPITAXIAL GROWTH

a) Liquid Phase Epitaxy
The film grown using liquid solutions over a substrate termed as liquid phase epitaxy
(LPE).
b) Vapour Phase Epitaxy
The film grown by depositing vapour of materials over a substrate is termed as vapour
phase epitaxy.

LIQUID PHASE EPITAXY (LPE)

Liquid phase epitaxy is a method to grow semiconductor crystal layers from the melt
on solid substrates. Basically, it is a high temperature solution growth technique in which a
thin layer of the required material is deposited onto a suitable substrate. Liquid Phase Epitaxy
method characterized as a near equilibrium growth process, when compared to the various
vapour phase epitaxy techniques.

The semiconductor dissolved in the melt of another material. At conditions that are
close to the equilibrium between dissolution and deposition of the semiconductor,
crystallization takes place on the substrate slowly and uniformly. The equilibrium conditions
depend very much on the temperature and on the concentration of the dissolved semiconductor
in the melt.

A crystalline layer of material is grown from a saturated liquid solution. The process
takes place in a high-purity carbon boat, which contains the substrate in the lower part and a
series of bins with melted materials in each bin. For example, one bin might hold gallium (Ga),
another aluminium (Al), and another gallium arsenide (GaAs). The substrate is placed in
contact with each bin in turn, the temperature is reduced, and an exact thickness of material is
crystallized. Thus mono-crystalline solid can be produced by liquid phase epitaxy. Generally
the growth takes place in the presence of hydrogen atmosphere to achieve oxide free crystals.
Crystallization takes place on the substrate slowly and uniformly. The equilibrium conditions
depend very much on the temperature and on the concentration of the dissolved semiconductor
in the melt.