DEPARTMENT OF PHYSICS

NAME OF THE SUBJECT : ENGINEERING PHYSICS

SUBJECT CODE : PH8151

REGULATION : 2017

UNIT – V :CRYSTAL PHYSICS

 UNIT – V (CRYSTAL PHYSICS)
5. Introduction
Many of the properties of solid materials depend mainly on their crystal structures. Based on
the arrangement of atoms and molecules, the solid material classified as follows

Solid Material

Crystalline Non-Crystalline
Material Material (Amorphous)

5.1. Crystalline Material

The periodic arrangement of atoms in all three dimensions space is called crystal. It has
regular shape and when it is broken, all broken pieces have the same regular shape. It has sharp
melting point. The physical properties of the crystal vary with direction and therefore they are called
anisotropic substances. It may be made up of metallic crystals or non-metallic crystals.
Examples: Cu, Al, W, Mg, Carbon, crystalized polymer and plastics.
5.2. Non-Crystalline Material
Random arrangement of atoms in all three dimensions space is called non-crystalline
material or amorphous. They have no directional properties and therefore they are called isotropic
substances. They do not possess any regular shape and they have a wide range of melting points.
Examples: Glass and Rubber.
5.3. Fundamental Definitions
5.3.1. Space Lattice
A regular and periodic arrangement of infinite number of points in three dimensions space is
known as space lattice. Every point in this arrangement is identical to that of every other point.

5.3.2. Basis (Motif)

A group of atoms in every lattice point is called basis or motif.

5.3.3. Crystal
A crystal is defined as regular and periodic arrangements of atoms or molecule in three
dimensional spaces.
Crystal = Space lattice + Basis

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It can be classified into two types. They are,
1. Single Crystal
2. Polycrystalline Material
1. Single Crystal
The entire crystalline material consists of only one crystal is known as single crystal.
Example: KDP, ADP.
2. Polycrystalline Material
A collection of many small crystals are separated by well-defined boundaries is called
polycrystalline materials.
Example: GaP, GaAs, ZnO and ZnS.
5.3.4. Fundamental translation vector
Mathematical representation of position vector in the space lattice is called fundamental
translation vector.
In two dimension R = n1a + n2b

In three dimension R = n1a+ n2b + n3c

Where, a, b and c are the fundamental translation vectors and n1, n2 and n3 are the integers.
5.3.5. Interfacial angle
The angles between the three crystallographic axes are known as interfacial angles.
Generally it’s are represented as α, β and γ respectively.

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5.3.6. Unit Cell
The unit cell is a smallest geometric volume containing one or more atoms arranged in three
dimension. And also, it is called fundamental building block of a crystal structure.

5.3.7. Primitive cell

Primitive cell is the smallest volume unit cell which contains the lattice points at the corner
only.

5.3.8. Lattice Constant

The distance between any two successive lattice points along any three dimensional directions
is called lattice constant.
5.4. Parameters determining the Crystal structure of Materials
Let us discuss some of the important parameters which are used to describe the crystal
structure.
5.4.1. Number of atoms per unit cell or Effective number
The total number of atoms present in or shared by a unit cell is known as number of atoms per unit
cell.
5.4.2. Atomic radius
Atomic radius is defined as half of the distance between any two nearest neighbour atoms which
have direct contact with each other, in a crystal of a pure element. It is usually expressed in terms of
cube edge a.
5.4.3. Co-ordination number
Co-ordination number is the number of nearest neighbouring atoms to a particular atom. Or Co-
ordination number is the number of nearest neighbours directly surrounding a given atom.
5.4.4. Atomic packing factor or packing density or density of packing
Atomic packing factor is defined as the ratio between the volumes occupied by the total
number of atoms per unit cell (u) to the total volume of the unit cell (v).
𝑢
APF =
𝑣
Where,
u = Total number of atoms per unit cell X volume of one atom
v = Total volume of the unit cell

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5.5. Seven Crystal Systems
Based on the fundamental translation vector and interfacial angle, the crystal classified in to
seven types. They are,
1. Cubic; 2. Triclinic; 3. Monoclinic; 4. Orthorhombic; 5.Tetragonal;
6. Rhombohedral; 7. Hexagonal.

5.6. Bravais Space Lattice

A three dimensional space lattice is generated by repeated translation of three non-coplanar
vectors a, b and c. There are only fourteen distinguishable ways of arranging points in three
dimensional spaces. These fourteen space lattices are known as Bravais space lattices. The different
Bravais space lattices and their crystal systems are listed in given table.
Crystal Bravais Space Symbols
System Lattices
Simple P
Cubic Body Centred I 3
Face Centred F
Triclinic Simple P 1
Simple P
Monoclinic Base Centred C 2
Simple P
Base Centred C
Orthorhombic Body Centred I 4
Face Centred F
Simple P
Tetragonal Body Centred I 2
Rhombohedral Simple P 1
Hexagonal Simple P 1
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5.7. STRUCTURE OF CUBIC
Cubic system
The cubic crystal structure is the simplest type and the atoms can take positions at the corners,
faces and also at the centre of the cube. Based on the positions of the atom in the cubic system, it can
be classified in to three types. They are,
1. Simple Cubic (SC) or Primitive(P)
2. Body Centred Cubic (BCC) and
3. Face Centred Cubic (FCC)
5.7.1. Simple Cubic Structure (SC)
A simple cubic unit cell consists of eight corner atoms as shown in given figure. Example:
polonium

Number of Atoms per unit cell

In actual crystal, each and every corner atom touches with each other and is shared by eight
adjacent unit cells. Therefore, one corner atom contributes 1/8 of its part to one unit cell. Hence,
Total number of atoms per unit cell is
1
= × (total number of corner atoms)
8
1
= ×8=1
8
In other words, the effective number of lattice points in a simple cubic structure is one. Thus,
simple cubic is a primitive cell.
Atomic Radius
In simple cubic (SC) structure the corner atoms touch each other along the edges. Let us
consider one face (front face) of the simple cubic structure as shown in figure.
Here, the nearest neighbour distance is the lattice constant
a = 2r.
Atomic radius r = a/2

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Co-ordination Number
Simple cubic unit cell consists of eight corner atoms. Let us consider any one corner atom say
X, shared by 8 unit cells as shown in figure.

For this particular atom ‘X’ there are four nearest neighbour atoms, shown as 2, 3, 4 and 5 in its
own plane (horizontal plane) and there are two more nearest atoms, one directly above (atom 1) and
the other one directly below (Atom 6). All the atoms, other than these six atoms lie at greater
distances from the X atom. The total number of nearest neighbours for X-atom is 4+2= 6. Hence, the
coordination number for simple cubic is six.
Packing factor
𝑢
APF = ……….. (1)
𝑣
Where,
u = Total number of atoms per unit cell X volume of one atom
v = Total volume of the unit cell
The number of atoms per unit cell =1
4 3
Volume of one atom (spherical) is = πr
…… (2)
3
We know that, the radius of atom in simple cubic is
r = a/2 ……. (3)
Volume occupied by the total number of atoms per unit cell is
4
𝑢 = 1 × 3 π 𝑟3 ……… (4)

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

4 𝑎 3
𝑢 = 1× 𝜋� �
3 2
4𝜋𝑎3
=
24
𝜋𝑎3
𝑢= …….. (5)
6
Volume of the unit cell (v) = length x breadth x height
We know that for a cubic system,
length = breath = height = a
v=axaxa
v = a3 ………. (6)
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Substitute equation (5) and (6) in equation (1) we get, atomic packing factor (APF) is,
𝜋𝑎3 ⁄6
APF =
𝑎3
APF = π/6
Or APF = 0.52 ………… (7)
Therefore, we can say that 52% volume of the unit cell of SC is occupied by atoms and
remaining 48% volume is vacant. Thus, the packing density is 52%. Since the packing density is very
low, SC has loosely packed structure.
5.7.2. Body Centre Cubic Structure (BCC)
A body centred cubic structure has eight corner atoms and one body centred atom. The
diagrammatic representation of a body centred cubic structure is shown in given figure.
Examples: Tungsten, Chromium, Molybdenum, etc.

Number of Atoms per unit cell

In a body centred crystal structure, the body centred atom touch along the diagonal of the body.
In bcc unit cell, each and every corner atom is shared by eight adjacent unit cells.
The total number of corner atoms per unit cell is
1
= ×8=1
8
The number of body centred atoms per unit cell is
1
= ×1=1
1
Total number of atoms per unit cell in BCC is
=1+1=2
Atomic Radius
In BCC structure, the corner atoms do not touch each other. But each corner atom touches the
body centred atom along the body diagonal as shown in figure. Therefore the two corner atoms (A and
D) situated at the opposite ends can be joined by drawing a diagonal as shown in figure.
D

C
A B

From the geometry of the figure, we can write

(AD) 2 = (AC) 2 + (CD) 2
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 = (AB) 2 + (BC) 2 + (CD) 2
(AD)2 = a2 + a2 +a2 = 3a2
AD = a √3 ............... (1)
From figure,
The diagonal of the cube AD = 4r .............. (2)
From equation (1) and (2) we can write
4r = a√3
√3
Atomic radius r = a ……….. (3)
4
Co-Ordination Number
In BCC structure, there will be one body centred atom at the centre of the unit cell and eight
atoms at the 8 corners of the unit cell as shown in figure.

The corner atoms do not touch each other. But each corner atom touches the body centred
atom along the body diagonal. Thus, the body centre atom has eight nearest neighbour atoms (corner
atoms). Hence, the co-ordination number body centred cubic structure is eight.

Packing Factor
𝑢
APF = …………. (1)
𝑣
Where,
u = Total number of atoms per unit cell X volume
of one atom
v = Total volume of the unit cell
In body-centred cubic structure,
The number of atoms per unit cell = 2
4
Volume of an atom (spherical) is = πr
3 ……… (2)
3
We know that, the atomic radius of BCC is
𝑎√3
r= ……….. (3)
4
Volume occupied by the total number of atoms per unit cell is
4
𝑢 = 2 × 𝜋𝑟 3 …………….. (4)
3
Substitute equation (3) in (4) we get,
3
8𝜋 𝑎√3
u= � �
3 4
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 8𝜋 𝑎3 3√3
u= � �
3 4𝑋4𝑋4
√3
u =π𝑎3 ……… (5)
8
Volume of the unit cell for a cubic system is
v = a3 ………….. (6)
Substitute equation (5) and (6) in equation (1) we get,
√3
π𝑎3 8
Atomic pacing factor (APF) =
a3
√3
APF = π
8
APF = 0.68 ……….. (7)
Therefore, we can say that 68% volume of the unit cell of BCC is occupied by atoms and
remaining 32% volume is vacant. Thus the packing density is 68%. Since the packing density is
greater than simple cubic, it has tightly packed structure, when compared to SC.
5.7.3. Face Centred Cubic Structure (FCC)
A face centred cubic (FCC) structure unit cell consists of eight corner atoms and six face
centred atoms. A face centred cubic unit cell is shown in given figure.

Number of atoms per unit cell

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 unit cell.
1
Hence, the total number of atoms contributed by the corner atom is = × 8 = 1
8
Each and every face centred atom is shared by two unit cells. Therefore, a face centred atom
contributes half of its part to one unit cell.
1
Hence, the total number of atoms contributed by the face centred atom is = × 6 = 3
2
Total number of atoms per unit cell in FCC is = 1 + 3
=4
Atomic Radius
In FCC structure, the corner atoms do not touch each other. But each corner atom touches the
face centred atoms along the diagonal of the face of the cube as shown in figure.

99
 C

A B

Therefore, the two corner atoms (A and C) situated at the opposite ends of the same face can be
joined by drawing a diagonal as shown in above figure.
From the geometry of the figure, we can write
(AC) 2 = (AB) 2 + (BC) 2
= a2 + a2
(AC) 2 = 2a2
AC = a√2 .............. (1)
But from figure, the diagonal of the cube is
AC = 4r ....... (2)
From equation (1) and (2) we can write
4r = a √2
𝑎√2
Atomic radius r = ……… (3)
4
Co-Ordination Number
In this system, there are eight corner atoms, and six face centred atoms, one at the centre of
each face. To calculate the coordination number, for FCC, let us consider a corner atom (X) as shown
in figure.

In its own plane it has four face centred atoms (1, 2, 3 and 4) as nearest neighbours. In a plane
which lies just above this corner atom, it has four more face centred atoms (5, 6, 7 and 8) as nearest
neighbours. And, similarly in a plane which lies just below this corner atom it has four more face
centred atoms, (9, 10, 11 and 12) as nearest neighbours. The total number of nearest atoms to any
corner atom is 4+4+4+4= 12. Hence, the coordination number is 12.

100
Packing Factor
𝑢
APF = ……….. (1)
𝑣
Where,
u = Total number of atoms per unit cell X volume
of one atom
v = Total volume of the unit cell
In face-centred cubic structure,
The number atoms per unit cell = 4
4 3
Volume of atoms is = πr ………… (2)
3

We know that, the atomic radius of FCC is

𝑎 √2
r= ……….. (3)
4
Volume occupied by the atoms per unit cell is
4
𝑢 = 4 × 𝜋𝑟 3 ………… (4)
3
Substitute equation (3) in (4) we get,
3
16𝜋 𝑎 √2
u= � �
3 4
16𝜋 𝑎3 2√2
u= � �
3 4𝑋4𝑋4
√2
u = π𝑎3 …….. (5)
6
Volume of the unit cell for a cubic system is
v = a3 …………… (6)
Substitute equation (5) and (6) in equation (1) we get,
√2
π𝑎3 6
Atomic packing factor (APF) =
a3
√2
APF = π
6
APF = 0.74 ...…. (7)
Therefore, we can say that 74% volume of the unit cell of FCC is occupied by atoms and
remaining 26% volume is vacant. Thus, the packing density is 74%. Since the packing density is very
high, the FCC structure has closely or tightly packed structure.
5.8. Hexagonal Closed Packed Structure (HCP)
The hexagonal closed packed (HCP) structure 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.

101
Number of atoms per unit cell
In order to calculate the total number of atoms in the hcp structure, let us consider the bottom
layer of atoms. The bottom layer consists of six corner atoms and one face centred atom. Each and
every corner atom contributes 1/6 of its part to one unit cell. Thus,
1
The total number of atoms contributed by the corner atom is = 6 × 6 = 1

The face centred atom contributes ½ of its part to one unit cell. Therefore, the total number of atoms
1 3
present in the case of the bottom layer is = 1 + =
2 2

Similarly, the upper layer also has 3/2 number of atoms. The middle layer has three full atoms.
3 3
Therefore, the total number of atoms present in a unit cell is = + +3=6
2 2

The total number of atoms present in the case of hcp crystal structure is six.
Atomic Radius
To find the atomic radius of HCP structure, consider any two corner atoms. It has to be noted
that, each and every corner atom touches each other; therefore they are the nearest neighbours.

r r
From figure,
We can write a = 2r
The atomic radius is r = a/2
Co-Ordination Number
The HCP structure is considered to have three layers via. (i) Bottom layer (BL), (ii) Top layer
(TL), (iii) Middle layer (ML) as shown in figure.

102
 In the top and bottom layers, the base centred atom is surrounded by six corner atoms. In the
middle layer we have 3 atoms stacked inside the unit cell as shown in figure. Let us consider two unit
cells as shown in figure. Let ‘X’ be the reference atom taken in the bottom layer (BL1) of unit cell – I
(or top layer [TL2] of unit cell 2). This atom has 6 neighbouring atom in its own plane. Further at a
distance of c/2 it has 3 atoms in the middle layer (ML1) of unit cell-I and 3 more atoms in the middle
layer (ML2) of unit cell-2. Therefore, the total numbers of neighbouring atoms are 6+3+3=12.

Relation between ‘c’ and ‘a’ [c/a ratio]

In hexagonal system, ‘c’ is the height Cof the unit cell of HCP structure and ‘a’ is the distance
between two neighbouring atoms. Now consider the triangle ABO in the bottom layer. Here A, B and
O are the lattice points and exactly above these atoms at a perpendicular distance ‘c/2’ the next layer
atom lies at C.

In ΔABY,
𝐴𝑌
Cos 300 = (or) AY = AB Cos 300
𝐴𝐵
√3
Since, AB = a and Cos 300 = we can write
2
√3
AY = 𝑎 ............... (1)
2

103
 2
But from figure, 𝐴𝑋 = 𝐴𝑌
3
Substituting the AY value in the above equation, we get
2 𝑎√3
𝐴𝑋 =×
3 2
2 𝑎√3
𝐴𝑋 = ×
√3 × √3 2
𝑎
𝐴𝑋 = ………. (2)
√3
In ΔAXC,
𝐴𝐶 2 = 𝐴𝑋 2 + 𝐶𝑋 2
Substituting the given values in the above equation we get,
𝑎 𝑐
AC = a; = ; and 𝐶𝑋 = , we get
√3 2
𝑎𝑐 22
2
𝑎 =� � +� �
√3 2
2
2
𝑎 𝑐2
𝑎 = 2+ 2
�√3� 𝑎

2
𝑎2 𝑐 2
𝑎 = +
3 4
𝑐2 𝑎2
= 𝑎2 −
4 3
𝑐 2 3𝑎2 − 𝑎2
=
4 3
𝑐 2 2𝑎2
=
4 3
𝑐2 2 × 4
=
𝑎2 3
𝑐2 8
= ………. (3)
𝑎2 3
Taking square root on both sides of equation (3) we get,

𝑐2 8
� = �
𝑎2 3

𝑐 8
= � = 1.633
𝑎 3
𝑐
= 1.633 ………… (4)
𝑎
Atomic Packing Factor (APF)
We know that,

104
 𝑢
Atomic Packing Factor (APF) = ……….. (5)
𝑣
Where,
u = Total number of atoms per unit cell X volume
of one atom
v = Total volume of the unit cell
Number of atoms per unit cell in HCP structure = 6.
4
Volume of one atom (spherical) = πr
3
3
We know that,
Radius of atom in HCP is r =a/2 ……. (6)
Therefore, volume occupied by the total number of atoms per unit cell is,
4
𝑢 = 6 × 𝜋𝑟 3 ………… (7)
3
Substitute equation (6) in (7) we get,
24 𝑎 3
u= π� �
3 2
24𝜋𝑎 3
𝑢=
24
u= πa 3
............. (8)
For HCP,
The volume of the unit cell is
𝑣 = 𝐴𝑟𝑒𝑎 𝑜𝑓 𝑡ℎ𝑒 𝑏𝑎𝑠𝑒 × 𝐻𝑒𝑖𝑔ℎ𝑡 …....... (9)
Area of the base = Area of six triangles
Area of the base = 6 × area of the one triangle (AOB)
From figure,
1
The area of the triangle AOB = (𝐵𝑂) × (𝐴𝑌)
2
𝑎 √3
Substituting the value of BO = a and 𝐴𝑌 = we have
2
1 𝑎 √3
Area of triangle AOB = a
2 2

𝑎2 √3
=
4
𝑎2 √3
Area of the base = 6 ×
4
3√3𝑎2
𝐴𝑟𝑒𝑎 𝑜𝑓 𝑡ℎ𝑒 𝑏𝑎𝑠𝑒 = ............ (10)
2
We know that,
The height of the hcp structure = c ............. (11)
Substituting equations (10) and (11) in equation (9) we get
3√3 2
Volume of the unit cell is (v) = 𝑎 x c ......... (12)
2
Substituting equations (8) and (12) in equation (5), we get

105
 𝜋𝑎3
Atomic packing factor = 3
√3 2
2
𝑎 𝑐

2𝜋 𝑎
= � �
3√3 𝑐

𝑎 3 1/2
Since =� � , we get
𝑐 8

2𝜋 3 1/2
Atomic packing factor = � �
3√3 8

2𝜋√3
=
3√32√2
𝜋
=
3√2
Atomic packing factor = 0.74
Therefore we can say that 74% volume of the unit cell of HCP is occupied by atoms and
remaining 26% volume is vacant. Thus, the packing density is 74%, which is the same as that of FCC
structure. Hence, HCP structure is also termed as tightly or closely packed structure.
5.9. DIAMOND CUBIC STRUCTURE
Diamond has Face Centred Cubic (FCC) structure with the basis of two carbon atoms, via, ‘X’
and ‘Z’. The ‘X’ atom is located with an origin of (0 0 0) and the ‘Z’ atom is located with an origin
𝑎 𝑎 𝑎
of �4 4 4
� (i.e.) one quarter of the way along the body diagonal as shown in figure.

Thus, from figure, we can see that the diamond structure is formed due to the combination of
two interpenetrating FCC sub lattices, having the origin (0 0 0) and (1/4 ¼ ¼) along the body
diagonal. Let us now discuss some of the important parameters of the diamond.
Number of atoms per unit cell
In diamond we have 3 types of atoms via,
(i) Corner atoms, represented by ‘C’ in figure
(ii) Face centred atoms, represented by ‘F’ in figure
(iii) Four atoms present inside the unit cell represented as 1, 2, 3 and 4, in figure.

106
 Each corner atom is shared by 8 unit cells. Similarly we have 8 corner atoms in a unit cell.
1
The number of corner atoms per unit cell is = x8
8
= 1 atom
Each face centred atom is shared by 2 unit cells. Similarly, we have 6 face centred atoms. The
number of face centred atom per unit cell is
1
= x 6 = 3 atoms
2
Inside the unit cell we have 4 atoms, represented by 1, 2, 3, and 4 in figure, which is shared by
that particular unit cell alone.
Total number of atoms per unit cell = 1+3+4= 8
Atomic radius
Atomic radius is defined as half the distance between any two nearest neighbour atoms, which
have direct contact with each other. Here, the corner atoms do not have contact with each other and
the face centred atoms also do not have contact with the corner atoms. But, both face centred atoms
and the corner atoms are contact with the four atoms (1, 2, 3 and 4) situated inside the unit cell as
shown in figure. From figure, we can see that the nearest two neighbours which have direct contact
(shown by double line) are atoms ‘X’ and ‘Z’.
Let us draw perpendicular to the ‘Z’ atom, which meets the unit cell at a point ‘Y’ as shown in
figure, which is at a distance of a/4.

From figure, we can write

(XZ) 2 = (XY) 2 + (ZY) 2
(XZ) 2 = [(XW) 2 + (WY) 2] + (ZY) 2
𝑎 2 𝑎 2 𝑎 2
=� � +� � +� �
4 4 4
𝑎2 𝑎2 𝑎2
= + +
16 16 16
3𝑎2
(XZ) 2 =
16

107
Since XZ = 2r, we can write
3𝑎2
(2r) 2 =
16
3𝑎2
4r2 =
16
3𝑎2
r2 =
16

𝑎 √3
Atomic radius (r) =
8
8𝑟
The lattice constant a =
√3
Coordination number
We know the coordination number is the number of nearest neighbouring atoms to a particular
atom. From figure the number of nearest atoms (shown by double line) for Y atom is 4. Therefore, the
coordination number of diamond is 4.

Atomic packing factor

𝑢
Atomic Packing Factor (APF) = ……….. (1)
𝑣
Where,
u = Total number of atoms per unit cell X volume
of one atom
v = Total volume of the unit cell
Volume of an atom (spherical) is = 4/3 πr
3

In diamond, we have 8 atoms per unit cell

We know that the atomic radius of diamond structure is
𝑎√3
r= ……… (2)
8
Volume occupied by the total number of atoms per unit cell is
4
𝑢 = 8 × 𝜋𝑟 3 …………. (3)
3
Substitute equation (2) in (3) we get,
3
32𝜋 𝑎√3
𝑢= � �
3 8
32𝜋𝑎3 3√3
𝑢=
3×8×8×8
𝑎 3 √3
𝑢=𝜋 …………. (4)
16
Since diamond has cubic structure, the volume of the unit cell is
v = a3 ........... (5)
Substitute equation (4) and (5) in equation (1) we get,
𝑎3 √3
Atomic Packing Factor = 𝜋
16𝑎3

108
 𝜋� 3
= 16
Atomic packing factor = 0.34 …… (6)
Packing density = 34%
Thus we can say that 34% volume of the unit cell in diamond cubic structure is occupied by
atoms and the remaining 66% volume is vacant. Since the packing density is very low, it is termed as
very loosely packed structure.
5.10. Graphite Structure
Graphite is an allotropic form of carbon, which has distinct crystal structures and properties. It
has properties of both a metal and a non-metal. It is flexible but not elastic, has a high thermal and
electrical conductivity, and is highly refractory and chemically inert. Graphite has a low adsorption of
X-rays and neutrons making it a particularly useful material in nuclear applications. These unusual
combinations of properties are due to its crystal structure, which is shown in given figure.
The carbon atoms are arranged hexagonally in a planar condensed ring system. The layers are
stacked parallel to each other. The atoms within the rings are bonded covalently with bond length 0.14
nm, whilst the layers are loosely bonded together by van der Waals forces with the distance about 0.34
nm. The high degree of anisotropy in graphite results from these two types of bonding acting in
different crystallographic directions.

Now let us remember that carbon has a valence of 4 and can make four bonds. Therefore, as
carbon had only made 3 bonds and the other is free, which is floats freely between two layers of
carbon. This free carbon is delocalised and mobile thus can conduct electricity and makes graphite as
an electric conductor despite being a non-metal.
Uses
1. It is used in internal combustion engines in the form of oildag (graphite mixed in oil).
2. It is used an oil free lubricant in food-stuff industry in the form of aquadag (graphite mixed in
water).
3. It is used as a lubricant in lathe, open gears, cast iron bearing, air-compressors, and railway
truck-joints.

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5.11. Comparison chart for SC, BCC, FCC, HCP and DIAMOND structures
The parameters determining the crystal structure of SC, BCC, FCC, HCP and diamond are
given for comparison, in table.

S.No System SC BCC FCC HCP Diamond

Atoms per unit
1 1 2 4 6 8
cell
√3 √2 𝑎 √3
2 Atomic radius a/2 a4 a4 a8
2
Coordination
3 6 8 12 12 4
number
Atomic packing 𝜋 𝜋√3 𝜋√2 𝜋 𝜋√3
4 = 0.52 = 0.68 = 0.74 = 0.74 = 0.34
factor 6 8 6 3√2 16
5 Packing density 52% 68% 74% 74% 34%
6 Examples Polonium Cr, Fe, Na Pb, Ni, Ag Mg, CO, Ti Ge, Si

5.12. Relation between lattice constant and density

Let us consider a cubic crystal of following parameters via,
(i) The lattice constant of the cell = a
(ii) The number of atoms per unit cell = n
(iii) The atomic weight of the crystalline
substance or compound = M
(iv) The density of the unit cell = ρ
(v) The Avagadro’s number = N
[Avogadro’s number gives the number of molecules per kilogram mole of the substance].
𝑀
Mass of each molecule =
𝑁

Thus the mass of n molecules or mass of an unit cell is

𝑀
= n
𝑁
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑎𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
Density of a unit cell is ρ =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
3
We know that the volume of the unit cell = a
𝑀
Density of the unit cell ρ = na3
𝑁
3 𝑀𝑛
Lattice constant a =
𝑁𝜌
𝐴𝑡𝑜𝑚𝑖𝑐 𝑤𝑒𝑖𝑔ℎ𝑡 𝑋 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 1/3
Lattice constant a = � �
𝐴𝑣𝑎𝑔𝑎𝑑𝑟𝑜 𝑁𝑢𝑚𝑏𝑒𝑟 𝑋 𝑑𝑒𝑛𝑠𝑖𝑡𝑦
Therefore, using the above equation, we can calculate the lattice constant.
5.13. Lattice planes
A crystal lattice is considered as a collection of a set of parallel equidistant planes passing
through lattice points. These planes are known as lattice planes.

110
5.14. Miller Indices
Miller indices are a symbolic vector representation for the orientation of an atomic plane in a
crystal lattice. It is defined as the reciprocal of the fractional intercepts which the plane makes with the
crystallographic axes.
5.14.1. Procedure for finding Miller indices
1. Find the intercepts of the plane along the co-ordinate axes X, Y and Z.
2. Take reciprocal of these intercepts.
3. Reduce the reciprocals into whole numbers using least common multipliers (LCM).
4. Write these integers within parentheses to get Miller indices.
For example, consider a crystal plane as shown in given figure.

1. Intercepts are 1, 3, 2.
1 1 1
2. Reciprocal of these intercepts are , ,
1 3 2
6 6 6
3. LCM of denominators 1, 3, and 2. Hence, multiplying by 6, we have , , . The Miller
1 3 2
indices of this plane is (6 2 3).

5.14.2. Features of Miller indices

1. Plane passing through the origin has non zero intercepts.
2. All equally spaced parallel planes have same Miller indices.
3. Miller indices do not define a particular plane, but it defines a set of parallel planes.
4. If the plane is parallel to any one of the coordinate axes, then its intercepts will be at infinity.
Therefore, the miller index of that particular axis is zero.
5. If a plane cuts the axis on the negative side, then the corresponding Miller indices will be
negative.
5.14.3. Points to ponder
 Miller indices should be enclosed only in parentheses.
 There should not be any commas in between the numbers.
 Putting a bar over the numbers indicate the negative Miller indices.
 If the Miller indices is say (2 6 3) means it should be read as two six three and not as two
hundred and sixty three.
Examples of common Miller indices

111
5.15. Interplanar distance (or) d spacing in cubic lattice
The distance between any two successive planes is called d spacing or interplanar distance.
Let us consider a cubic lattice of length ‘a’ with two planes ABC and Aʹ Bʹ Cʹ. Let d1 and d2 be
the distance between the origin and the first (ABC) and second plane (Aʹ Bʹ Cʹ). Let d be the distance
between the two planes ABC and Aʹ Bʹ Cʹ.

112
 A Miller index of the two planes is (hkl) and draws a perpendicular line ON from origin. Let
OA, OB and OC be the intercepts made by the plane on X, Y and Z axis respectively. Let α, β, γ
represents the angle between ON and X, Y and Z axes respectively.
Distance between the two planes is
d=d2 – d1 …….. (1)
To find d1:
The intercepts of the first plane on the three axes are,
𝑎 𝑎 𝑎
𝑂𝐴 = ; 𝑂𝐵 = ; 𝑂𝐶 =
ℎ 𝑘 𝑙
𝑎 𝑎 𝑎
𝑂𝐴: 𝑂𝐵: 𝑂𝐶: = : :
ℎ 𝑘 𝑙
From ΔONA,
𝑂𝑁 𝑑 𝑑 ℎ
𝑐𝑜𝑠 𝛼 = = ⁄1 = 1
𝑂𝐴 𝑎 ℎ 𝑎
From ΔONB,
𝑂𝑁 𝑑1 𝑑1 𝑘
𝑐𝑜𝑠 𝛽 = = =
𝑂𝐵 𝑎⁄𝑘 𝑎
From ΔONC,
𝑂𝑁 𝑑1 𝑑1 𝑙
𝑐𝑜𝑠 𝛾 = = =
𝑂𝐶 𝑎⁄𝑙 𝑎

𝑑1 ℎ 𝑑1 𝑘 𝑑1 𝑙
cos 𝛼: cos 𝛽: cos 𝛾 = : :
𝑎 𝑎 𝑎
From the law of direction cosines we can write,
𝑐𝑜𝑠 2 𝛼 + 𝑐𝑜𝑠 2 𝛽 + 𝑐𝑜𝑠 2 𝛾 = 1
𝑑1 ℎ 2 𝑑1 𝑘 2 𝑑1 𝑙 2
� � +� � +� � =1
𝑎 𝑎 𝑎
𝑑12 2
(ℎ + 𝑘 2 + 𝑙 2 ) = 1
𝑎2
𝑎2
𝑑12 = 2
ℎ + 𝑘 2 + 𝑙2
𝑎
𝑑1 = ………. (2)
√ℎ2 +𝑘 2 +𝑙 2
To find d2:
The intercepts of the second plane on the three axes are,
2𝑎 2𝑎 2𝑎
𝑂𝐴ʹ = ; 𝑂𝐵ʹ = ; 𝑂𝐶ʹ =
ℎ 𝑘 𝑙
2𝑎 2𝑎 2𝑎
𝑂𝐴ʹ: 𝑂𝐵ʹ: 𝑂𝐶ʹ: = : :
ℎ 𝑘 𝑙
From ΔOMAʹ,

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 𝑂𝑀 𝑑2 𝑑2 ℎ
𝑐𝑜𝑠 𝛼ʹ = = =
𝑂𝐴ʹ 2𝑎⁄ℎ 2𝑎
From ΔOMBʹ,
𝑂𝑀 𝑑2 𝑑2 𝑘
𝑐𝑜𝑠 𝛽ʹ = = =
𝑂𝐵ʹ 2𝑎⁄𝑘 2𝑎
From ΔOMCʹ,
𝑂𝑀 𝑑2 𝑑2 𝑙
𝑐𝑜𝑠 𝛾ʹ = = =
𝑂𝐶ʹ 2𝑎⁄𝑙 2𝑎

𝑑2 ℎ 𝑑2 𝑘 𝑑2 𝑙
cos 𝛼ʹ: cos 𝛽ʹ: cos 𝛾ʹ = : :
2𝑎 2𝑎 2𝑎
From the law of direction cosines we can write,
𝑐𝑜𝑠 2 𝛼ʹ + 𝑐𝑜𝑠 2 𝛽ʹ + 𝑐𝑜𝑠 2 𝛾ʹ = 1
𝑑2 ℎ 2 𝑑2 𝑘 2 𝑑2 𝑙 2
� � +� � +� � =1
2𝑎 2𝑎 2𝑎
𝑑22 2
2
(ℎ + 𝑘 2 + 𝑙 2 ) = 1
4𝑎
4𝑎2
𝑑22 = 2
ℎ + 𝑘 2 + 𝑙2
2𝑎
𝑑2 = ………. (3)
√ℎ2 +𝑘 2 +𝑙 2
Substitute equation (2) and (3) in equation (1) we get,
2𝑎 𝑎
𝑑= −
√ℎ2 + 𝑘 2 + 𝑙2 √ℎ2 + 𝑘 2 + 𝑙2
𝑎
𝑑= ……… (4)
√ℎ2 +𝑘 2 +𝑙 2
Equation (4) represents the interplanar distance, which is same as that of the distance between
the origin and the first plane.
5.16. Crystal Growth
Crystal growth is a major stage of a crystallization process, and consists in the addition of few
atoms, ions, or polymer strings into the characteristic arrangement of crystalline Bravais lattice. The
growth typically follows an initial stage of either homogeneous or heterogeneous nucleation, unless a
seed crystal purposely added to start the growth.

114
 5.16.1. Solidification (or) Crystallization
Solidification is the transformation of material from liquid to solid state on cooling.

When a liquid solidifies (solidification process), the energy of each atom is reduced. This
energy is given out as latent heat. For a pure metal it occurs at a fixed temperature. During
solidification, the disordered structure of the liquid transforms to the orderly arrangement depending
upon the time of solidification. This solidification process greatly influences the crystal growth.

5.16.2. Crystal Growth Techniques

Crystal can be grown using the following basic growth techniques. They are,
 Low temperature solution growth
 High temperature solution growth (Flux growth)
 Melt growth
 Hydrothermal growth
 Gel growth
 Vapour phase growth
5.17. Melt Growth
Melt technique is the process of crystallization by fusion and re-solidification of the starting
materials from the melt. The growth from melt is further sub-grouped into two techniques.
 Czochralski technique
 Bridgman technique (high temperature technique)
5.17.1. Czochralski Method or Crystal Pulling Method
Principle:
Crystals are grown by a gradual layer by layer condensation of melt. It is based on liquid-solid
phase transition initiated by a seed crystal.
Description
1. The pure material which is to be grown in the form of single crystal is taken in the crucible.
2. The material is heated above the melting point using induction heater.
3. Thus melt is obtained in the crucible. A small defect free single crystal, called seed crystal is
introduced into the melt.
4. The seed crystal is attached to a rod, which is rotated slowly.
5.
6.
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7. The temperature difference between the melt and the seed crystal establishes the desired growth
condition.
8. The seed is slowly with-drawn from the melt by pulling and rotating such that the crystal diameter
is gradually increased to the desired value.
9. The seed crystal is dipped into a melt held at a temperature slightly above the melting point.
10. The shape of the crystal is initially in the form of thin neck and then the diameter of the crystal is
increased to the required size. This is known as necking procedure.
11. By using necking procedure and pulling mechanism, bulk single crystals can be obtained by
Czochralski method.
Advantages
 It produces defect free crystal.
 It produces large single crystal.
 It allows convenient chemical composition of crystal.
 The dopant distribution in the crystal will be uniform.
Limitations
 High vapour pressure of the materials can be used.
 Possibility of liquid phase encapsulation occurs during solidification.
 It may produce contamination of melt by the crucible.
5.17.2. Bridgman Techniques
Principle
The selective cooling of the molten material is used to form single crystal by solidification
along a particular direction. It is classified into two types. They are,
 Vertical Bridgman Technique
 Horizontal Bridgman Technique
In both techniques, the melt in a sealed crucible is progressively frozen from one end to other end.
Description
1. The material to be grown in the form of a single crystal which is taken in a cylindrical crucible.
2. Crucible is made of platinum and tapered conically with pointed tip at the bottom.
3. The crucible is suspended in the upper furnace until the material in the crucible in completely
melted into molten liquid.

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 4. Crucible is then slowly lowered from upper furnace into lower furnace with the help of an
electric motor.
5. Temperature of the lower furnace is maintained below the melting point of the material inside
the crucible.
6. Thus, a bulk single pure crystal can be grown in the crucible by lowering the crucible at steady
rate (1 – 30 mm/hr.).
Advantages
 It is relatively cheaper than other pulling techniques.
 Simpler technology
 Melt composition can be controlled during the growth.
 It enables easy stabilization of temperature gradient
Disadvantages
 Growth rate is very low.
 Sometimes instead of single crystals, polycrystals may grow.
 Since the material is in contact with the walls of the container for long period, it leads to
dislocations of the nucleus.
 This technique can't be used for materials which decompose before melting.

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