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Crystallography

Applied Physics – I (University of Mumbai)

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CRYSTAL PHYSICS
Crystallography Space lattice, Unit Cell & Lattice parameters

Introduction
The matter which surround us is found to exist in three states viz, solids, liquids and gases.
All these materials are composed of atoms and molecules. The constituent particles, atoms or
molecules of matter are held together through forces of attraction. The attractive forces which hold the
constituent particles of a substance together are called bonds.
We know that, some solids are brittle, some are ductile, some are malleable, some are strong,
some are weak, some are good conductors of heat and electricity, some are bad conductors of heat and
electricity, some are magnetic, some are non-magnetic and so on. The reason for these different
properties of the solids is due to their structure. That is, the behavior of the solid materials is closely
related to the structure of the material.
Classification of Solids
If we examine the solid materials with which we daily come across, we shall find that most of them do
not have any characteristic difference in their outward appearance. But, if we examine them under a
microscope we shall find these materials have different internal atomic structures.
Based on the internal atomic structure, the solids can be classified into two categories namely
I. Crystalline
II. Non-crystalline or Amorphous solids.

Crystalline solids (Crystals)

Crystalline solids or crystals are those, in which the constituent atoms or molecules are
arranged in an orderly fashion throughout in a three dimensional pattern.
Each atom or molecule is fixed at a definite point in space at a definite distance from and in a
definite angular orientation to all other atoms or molecules surrounding it. Therefore, crystalline solids
have well defined geometrical form (pattern), i.e., they have well defined faces and angles between
them. Further when crystal breaks, the broken pieces are all having regular shape. The crystalline solids
have directional properties and therefore they are called anisotropic substances. A crystalline material
may be either in the form of a single crystal, (where the solid contains only one crystal) or an aggregate
of many small crystals or grains separated by well defined grain boundaries also known as
polycrystalline solid.
Few examples for crystalline solids: Copper, silver, Aluminium, iron etc.
Crystallography: The study of the geometric form and other physical properties of crystalline solids by
using X-rays, electron beams and neutron beams etc., is termed as the science of crystallography.

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Examples for single crystals: Sugar, common salt (NaCl), diamond etc. These single crystals are
produced artificially from their vapour or liquid state.

Amorphous solids (Non-crystalline solids)

"Amorphous" means "without form".
In amorphous solids, the constituent particles, atoms or molecules are not arranged in an orderly
fashion, i.e., the same atomic groups are arranged more randomly.
These solids have no directional properties and therefore they are called isotropic substances. These
amorphous solids do not have a sharp melting point.
Examples: Plastics, rubber and glass.
Note:
Super cooled liquids
The materials like glass, which exhibit some of the properties of a solid like hardness, definite shape
etc., but are not crystalline, are regarded as super cooled liquids.

Fig.1

Difference between crystalline and non-crystalline material

Sr.
Crystalline material Non-crystalline material
No.
They have definite and regular geometrical They do not have definite geometrical
1 shapes which extend throughout the crystal. shape.
They are anisotropic. They are isotropic.
2
3 They are most stable. They are less stable.
They have sharp melting point. Examples: They do not have sharp melting point.
4 Diamond, NaCl, KC1 Examples: Glasses, plastics, rubber

Crystal Structure
The crystal structure gives the arrangement and disposition of atoms within a crystal.
Determination of crystal structure with the help of X-rays is known as X-ray crystallography. X-rays are
most widely used to study the crystal structure because the wavelength of X-rays (10-12 to 10-10 m) is
most comparable with the inter-atomic distances.

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Fundamental crystallographic terms (definitions)

a) Lattice
Lattice is defined as an array of points such that every lattice point has got the same environment or
every point is indistinguishable from the other lattice point. It is an imaginary concept.

b) Space lattice or crystal lattice

Definition - 1: A three dimensional collection of points in space is called a space lattice or crystal
lattice. The environment about any particular point is in every way the same. That is, space lattice is an
idealized geometrical (imaginary) concept by which crystal structures can be described.

Figure 2 Figure 3

c) Lattice points
Lattice points denote the position of atoms or molecules in the crystal.
d) Basis or Motif
A crystal structure is formed by associating with every lattice point a unit assembly of atoms or
molecules (i.e., one or more atoms or molecules) identical in composition, arrangement and
orientation. This unit assembly is called the basis or pattern or motif. The logical relation is

Space lattice + Basis = Crystal structure.

(a) Lattice (b) Basis (c) Lattice + Basis

Fig.4.
The number of atoms in the basis may be as low as one. Examples are Aluminium and Barium. In NaCl
and KCl the basis is two atoms and in CaF2 the basis is three atoms. But, there are structures for which
the basis exceeds 1000 atoms.
Note: A crystal lattice refers to the geometry of a set of points in space. The crystal structure refers to
the actual arrangement of atoms or molecules in the space.

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e) Lattice planes
A set of parallel and equally spaced planes in a space lattice which include all lattice points are
called as lattice planes.
The different ways of drawing the lattice planes for the array of figure 3 are shown in figure 5.

Fig 5
f) Unit cell: The unit cell is the smallest block or geometric figure from which the entire crystal is built up
by repetition in three dimensions.
 The unit cell may be considered as the brick of a wall where the latter represents the crystal. We
know that, the shape of the wall depends upon the shape and arrangement of the brick. Similarly
the shape of the crystal will depend upon the shape of the unit cell and the arrangement of atoms
within the unit cell.
 Translation: Motion of a body in which all the points in the body follow parallel paths.
 Other terms used to represent a unit cell: The unit cell is also known as basic cell or basic unit or
fundamental unit or fundamental elementary pattern or building block or lattice unit.
g) Lattice parameters

Fig. 6. Lattice Parameters

The figure 6 shows a unit cell of a three dimensional crystal lattice. The lines drawn parallel to the lines
of intersection of any three faces of the unit cell which do not lie in the same plane are called
crystallographic axes. The intercepts a, b and c are nothing but the edges of the unit cell, (i.e., the
distance between two lattice points) which defines the dimensions of a unit cell. These intercepts are
known as its primitives or characteristic intercepts along the axes. These three quantities a, b and c are
also called the fundamental translational vectors. The angles between (a, b), (b, c) and (c, a) are
denoted by γ, α and β respectively.
The three angles (α, β and γ) are called interfacial angles. Both, the intercepts and interfacial angles
constitute the lattice parameters of the unit cell.

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The form and actual size of the unit cell can be determined if the values of intercepts and interfacial
angles are known.

h) Primitive cell P
A primitive cell is the simplest type of unit cell which contains one lattice point per unit cell (contains
lattice points at its corner only).
Example: Cubic cell.
If there is more than one lattice point it is called a non-primitive cell.
Example: BCC and FCC contain more than one lattice point per unit cell.
If the number of lattice points per unit cell is two (BCC), three and four (FCC) the unit cell is called
doubly primitive, triply primitive and quadruple primitive respectively.
Multiple Choice Questions
Q.1 A crystal Lattice refers to the geometry of a set of-----
a) Points in Space
b) Atoms in Space
c) Molecules in Space
d) Elements In space
Q.2 A unit Assembly of atoms or molecules identical in composition is called as-
a) Basis
b) Unit cell
c) Lattice
d) None
Q.3 Which one of the following crystal is a poly crystal?
a) Diamond
b) Rock Salt
c) Aluminium
d) Sugar
Q.4 Which one is the Correct Equation?
a) Lattice + Basis =Crystal
b) Lattice + unit cell =Crystal
c) Lattice + Crystal= Basis
d) Crystal + Basis = Lattice
Q.5 Which one of the following is a primitive cell?
a) SC
b) BCC
c) FCC
d) HCP

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Bravais lattices, Cubic systems: SC, BCC & FCC

Crystal System
On the basis of the lengths and directions of the axes of the symmetry, all the crystals may be classified
into seven systems.
The shapes of the unit cells are shown in Fig. Of these seven crystal systems, the cubic system is the
simplest and most symmetrical in which a = b = c and α = β = γ = 90°. It is interesting to note that
more than half of the naturally occurring crystals belong to the cubic system.
According to the different values of the lattice parameter, seven crystal systems can be formed as
follows:

S. No. Crystal System Basic Vectors Interfacial Angles

1. Cubic a=b=c α = β = γ =90°
2. Monoclinic a≠b≠c α = β = 90° ≠ γ
3. Triclinic a ≠b ≠ c α ≠ β ≠ γ ≠ 90°
4. Tetragonal a=b≠c α = β = γ = 90°
5. Orthorhombic a≠b≠c α = β = γ = 90°
6. Rhombohedral (trigonal) a=b=c α = β = γ ≠ 90°
7. Hexagonal a=b≠c α = β = 90°, γ = 120°
Bravais Space Lattice:
In 1845, Bravais showed that there are only 14 ways of arranging points in space so that the
environment looks the same from each point. These 14 lattices are called Bravais space lattices, each of
which has the same collection of symmetry elements at the lattice points. They are shown below

Fig.7. Bravais Lattices

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For cubic system, three types of Bravais lattices are possible, viz.:
(i) Simple cubic (SC) (e.g. Palladium)
(ii) Body-centered cubic (BCC) (e.g. Molybdenum)
(iii) Face-centered cubic (FCC) (e.g. Ni, Cu, NaCl)

Some Important terms:

1. Number of atoms per unit cell or Effective number
The total number of atoms present in a unit cell is known as number of atoms per unit cell.
2. Co-ordination number
Co-ordination number is the number of nearest neighbours directly surrounding a given atom.
3. Atomic radius
It is defined as half of the distance between to nearest neighbours in a crystal of a pure element.
It is usually expressed in terms of cube edge a. Any two nearest neighbouring atoms touch each
other.
4. Atomic packing factor (Packing density or Density of packing)
It is defined as the ratio of the volume of atoms per unit cell to the total volume occupied by the
unit cell.
5. Voids:
The space in the unit cell which is left unoccupied by atoms is called as the void
void = (100 − APF in %)
(a) Simple Cubic Structure:

Fig.8
In simple cubic crystal structure the atoms or molecules are located at the each corner of the cube or the
unit cell. Thus there is only one basis atom per unit cell. As it is the cubic crystal structure the lattice
constants along the crystallographic axes are equal.
Thus we have = =
Also as the for the cubic structure one should have
= = =

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i. Number of atoms per unit cell:

Fig.9
The figure 9 shows the unit cell of a simple cubic structure. In this case, there are only 8 atoms, one
at each corner of the cube or the unit cell. In actual crystals, each and every corner atom is shared by
8 adjacent unit cells. Therefore, each and every corner atom contributes 1 / 8th of its part to one unit
cell. Total number of corner atoms Nc = 8

The total share of the entire corner atoms/unit cell = 8 × 1 / 8 = 1.

Number of atoms/unit cell = 1

In other words, the effective number of lattice points in a simple cubic structure is one. Thus, simple
cubic is a primitive cell.
ii. Co-ordination Number:

Fig.10
Simple cubic unit cell consists of 8 comer atoms. Let us consider any one corner atom as shown in
figure 10. For the atom at the centre there are 4 nearest neighbours in its own plane (horizontal plane)
and there are 2 more nearest atoms, one directly above and the other one directly below. Except these
six atoms all the other atoms lie at greater distances from it. Thus, the coordination number for an atom
in simple cubic is 6.

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iii. Relation between ‘a’ and ‘r’:

Let us consider one face of the simple cubic structure, figure 11. In this structure the atoms touch each
other along the edges.

a = 2r

Fig.11: Simple cubic structure

Hence, the nearest neighbour distance is 2r = a. Therefore, r = a/2.

iv. Atomic Packing Factor (APF):
The packing factor or packing density of the simple cubic structure can be calculated as follows:
No. of atoms per unit cell x Volume of one atom
APF =
Volume of the unit cell
In simple cubic,
The number of atoms per unit cell = 1

Volume of one atom= πr = π ∵ =

Volume of the unit cell = a3

4 a
1× π
APF = 3 2
a
π
APF = = 0.52
6
52 % of the volume is occupied by atoms and remaining 48 % volume is vacant.
v. Void:
The space in the unit cell which is left unoccupied by atoms is called as the void
void = (100 − APF in %)
= (100 − 52) = 48 %

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(b) Body Centered Cubic Structure

Fig. 12

In body centered cubic structure, there are 8 atoms at each corner of the unit cell plus one atom at the
geometric centre of the unit cell. Thus the corner atom touches the body central atom through the
body diagonals. In this way there are two basis atoms, one located at the corner & the other one at
the center of the body.
i. Number of Atoms Per Unit Cell:

Fig. 13

In this case, there are 8 atoms one at each corner of the unit cell plus one atom at the centre of the unit
cell, figure 10. Each and every corner atom is shared by 8 adjacent unit cells. The atom at the body
centre is not shared by any other unit cell. Number of unshared atoms/unit cell = 1.
The total share of all the corner atoms per unit cell is 8 x 1 / 8= 1.
Hence, total number of atoms/unit cell = 1 + 1 = 2

ii. Co-ordination Number:

In this structure, there will be one atom at the body centre and eight atoms at the 8 corners of the
unit cell figure 14. Thus, for an atom at the body centre obviously, there are 8 nearest
neighbours (corner atoms). Hence, the co-ordination number of an atom in body centered cubic
structure is 8. The corner atoms do not touch each other. But, each corner atom touches the body
centre along the body diagonal.

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Fig. 14

Alternative method

The coordination number can also be determined in another way as follows.

We know that in a BCC structure, each corner atom is surrounded by eight ether body centered unit
cells. Therefore, the nearest adjacent neighbours are the body centered atoms of the eight surrounding
unit cells. Thus, the coordination number is 8.

ii. Relation between ‘a’ and ‘r’:

D

Fig.15: Body Centered Cubic structure

In this structure, the corner atoms do not touch each other. But, each corner atom touches the body
centered atom along the body diagonal, figure 15. Thus, the diagonal of the cube AD is 4r. But, from
the geometry of the cube,

( ) =( ) +( ) =( ) +( ) +( ) [∵ ( ) =( ) +( ) ]

( ) = + + = [∵ = = = ]

= √ ; =

√
∴ = √ OR =

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iii. Atomic Packing Factor (APF):

The packing factor or packing density of the body centered cubic structure can be calculated as follows:
No. of atoms per unit cell × Volume of one atom
APF =
Volume of the unit cell
The no of atoms per unit cell = 2

√ √ √
Volume of 2 atoms = 2 × πr = = ∵ =

Volume of the unit cell = a3

√3
APF = 8
a
∴ APF = 0.68

∴ 68% of the volume is occupied by atoms and remaining 32 % volume is vacant.

iv. Void:
The space in the unit cell which is left unoccupied by atoms is called as the void
void = (100 − APF in %)
= (100 − 68) = 32 %

(c) Face Centered Cubic Structure

Fig.16
In face centered cubic structure, there are 8 atoms at each corner of the unit cell. Also we have in
addition one atom at the center of the each face of the cube. Thus the corner atom touches the face
central atom along the face diagonals. In this way there are two basis atoms, one located at the corner &
the other one at the center of the face.

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i. Number of atoms per unit cell:

Fig.17
In this case, there are 8 atoms, one at each corner of the unit cell and six atoms at the centers of six faces
of unit cell figure 17.The total share of all the corner atoms per unit cell is 8x1/8=1.
Now, consider the atoms at the face centre of the unit cell. Each such atom is shared by only two unit
cells, which lie on either side of the plane in which the atom is located. The total share of all the face
centered atoms per unit cell = 6 x 1/2 = 3. Hence, the total number of atoms/unit cell is 1 + 3 = 4.
ii. Co-ordination Number:

Fig.18
In this system, there are 8 corner atoms and six face centered atoms one at the centre of each face. To
calculate the coordination number, consider any corner atom ( the blue coloured one at the center). In
its own plane it has 4 face centered atoms as nearest neighbour. In a plane which lie just above this
corner atom, it has 4 more face centre atoms as nearest neighbors’ and similarly, in a plane which lie
just below this corner atom it has 4 more face centered atoms as nearest neighbours. The total
number of nearest atoms to any corner atoms is 4 + 4 + 4 = 12. Hence, the coordination number is
12.

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iii. Relation between ‘a’ and ‘r’:

C

4r
a

a B
A

Fig.19: Face Centered Cubic structure

In face-centered cubic structure, the atoms touch each other along the diagonal of any face of the
cube. The diagonal of the cube AC is 4r.
But, from the geometry of the figure
( ) =( ) +( ) = + =2
∴ = √2 [∵ =4 ]
4 = √2

√
Hence r=
iv. Atomic Packing Factor (APF):
The packing factor or packing density of the face centered cubic structure can be calculated as
follows:
. ×
=
ℎ
The no of atoms per unit cell = 4
4 16 √2 √2 √2
∴ Volume of 4 atoms = 4 × πr = = ∵ =
3 3 4 6 4
Volume of the unit cell = a3
√
√
APF = =

∴ APF = 0.74
∴ 74% of the volume is occupied by atoms and remaining 26 % volume is vacant
v. Void:
The space in the unit cell which is left unoccupied by atoms is called as the void
void = (100 − APF in %)
= (100 − 74) = 26 %

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Multiple Choice Questions

Q1.The relation of length of axes and interfacial angle of unit cell in cubic crystal system is
a. a = b = c and α = β = γ ≠ 90°.
b. a = b = c and α ≠β = γ = 90°.
c. a = b ≠c and α = β = γ = 90°.
d. a = b = c and α = β = γ = 90°.
Q2.The co-ordination number for FCC lattice is-
a. 12
b. 8
c. 6
d. 4
Q3.The packing density for BCC lattice is-
a. 52%
b. 68%
c. 74%
d. 34%
Q4.The atomic radius for SC lattice is-
√
a.
√
b.
√
c.
d.
Q5.The atomic radius for FCC is1.278A°, then lattice constant is-
a. 3.61 A°
b. 36.1 A°
c. 3.61 cm
d. 3.61 m

University Questions
1) Describe the BCC structure with lattice parameters & characteristics.
2) Describe the FCC structure with lattice parameters & characteristics
3) What is atomic Packing Factor? Give its Significance.
4) Explain the co-ordination no for FCC crystal structure.
5) Derive the relation between ‘a’ and ‘r’ for BCC and FCC structure.

Relation between Lattice Constant and Density

Consider a cubic crystal.
Let, the lattice constant of the cell = a
The number of atoms per unit cell = n
The atomic weight of the crystalline substance or compound = A

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The density of the unit cell =ρ

The Avogadro’s number = N
[Avogadro’s number gives the number of molecules per kilogram mole of the substance]

∴ Mass of each Atom =

Hence, Mass of n Atoms (i.e., mass in each unit cell)=

∴ Density of a unit cell is

Mass of a unit cell
=
Volume of a unit cell
×
=

ℎ ×
=
×
Hence, using the above equation, we can calculate the lattice constant ‘a’.

University Questions
Derive the relation between Lattice constant (a) and Density (ρ) of the materials.
Numericals
Data:
 Avogadro’s number NA= 6.023×1023/gm mole.
NA= 6.023×1026 /kg mole.

1. The density and molecular weight of the FCC lattice are 6250 kg/m3 and 60.2 respectively. Find the
lattice constant of the crystal. [Ans: 3.99A°]
2. Cu has FCC structure and the atomic radius is 1.278 A. Calculate the density of Cu crystal. Given
atomic weight of Cu is 63.5 [Ans: 8929kg/m3]
3. Sodium crystallizes in a cubic lattice. The edge of the unit cell is 4.3 A. The density of Na is 963
kg/m3, its atomic weight is 23. How many atoms are contained in one unit cell? What type of cubic
unit cell Na form? [Ans: 2 and BCC ]
4. Ni has FCC structure, its lattice constant is 3.52 A, atomic weight of Ni is 58.71; calculate its radius,
APF and density. [Ans: 1.24 A°, 0.74 % and 8939kg/m3]
5. For NaCl structure calculate the number of molecules per unit cell and packing factor assuming
radius of Na+ ion is 0.98 A and radius of Cl- is 1.81 A. [Ans: 4 and 66% ]

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Miller Indices (hkl) & Drawing Miller Planes and Direction

Miller Indices

Miller introduced a set of three numbers to designate a plane in a crystal. This set of three numbers
is known as Miller indices of the concerned plane.
Definition - 1: Miller indices may be defined as the reciprocal of the intercepts made by the plane along
the three crystallographic axes which are reduced to smallest numbers.

Here, let us discuss briefly the method of designating a plane in crystal. This method was suggested by
William Miller.
Procedure For Finding Miller Indices (Steps in the determination of Miller indices)
The steps in the determination of Miller indices of a plane are illustrated with the aid of figure 20.
Consider the plane ABC which cuts 1 unit along the X-axis, 3 units along the Y-axis and 2 units along
the Z-axis.

Fig. 20
Step 1:
Find the intercept of the plane ABC along the three axes X, Y, and Z. Let it be OA, OB and OC.
Express the intercepts in terms of multiples of axial lengths, i.e., lattice parameters. Let them be OA =
pa, OB = qb and OC = rc where p, q and r are the intercept numerical values along the three axis.
In this example shown,p = 1, q = 3 and r = 2
Hence, OA: OB: OC = pa: qb: rc = la: 3b: 2c
∴The intercepts are la, 3b and 2c along the three axes.
Step 2:
Find the reciprocal of the numerical intercept values, i.e.
For the example shown the reciprocal of the numerical intercept values are
111
132
Step 3: Convert these reciprocals into whole numbers by multiplying each with their least common multiple
(LCM)
Here the LCM is 6

Therefore,
6× 6× 6× = 6, 2, 3

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Step 4:
Enclose these numbers in bracket. This represents the indices of the given plane, and is called the Miller
indices of the plane. For the example shown, the Miller indices are (6 2 3).

It is generally denoted by (h k l). It can also be noticed that ℎ: : = : :

Note: Negative indices are represented by putting a bar over the index.

Important features of Miller indices of crystal plane

For the cubic crystal especially, the important features of Miller indices are,
1. For an intercept at infinity, the corresponding index is zero.
[I.e. if a plane is parallel to any one of the coordinate axis, then its intercept is at infinity. Hence, the
Miller index for that axis is zero].
2. All equally spaced parallel planes have the same Miller indices (hkl) or vice versa.
[i.e., if the Miller indices of two planes have the same ratio like (844), (422) and (211) then the
planes are parallel to each other].
3. The indices (h k l) do not represent a particular plane, but a set of parallel planes.
4. It is only the ratio of the indices which is important in this notation.
5. If a plane cuts the axis on the negative side of the origin, corresponding index is negative.
Procedure for Sketching the Plane from the Given Miller Indices
The following procedure is adopted for sketching any plane when, its Miller indices are given.
As a first step, take the reciprocals of the given Miller indices.
These reciprocals represent the intercepts in terms of the axial units along the X, Y and Z axes
respectively. c

For example, Z

 Let the Miller indices be (221).

 Therefore, its reciprocals of intercepts will be or b/2

0.5, 0.5 and 1 respectively. a/2 a/2 Y
X
 Now sketch the plane with intercepts 0.5, 0.5 and 1
Fig.21
marked on the X, Y and Z axes respectively and joining
them to form the plane, as shown in fig.21

Common planes in a simple cubic structure:

Even though, there are a number of planes that can be drawn, the most common planes in a simple cubic
structure are (1 0 0), (1 1 0) and (l 1 1).

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Fig. 22
The three most important planes in a simple cubic structure are shown in figure 22 and the way of
drawing all the above planes are explained one by one.
a. Plane (100)
In this case h= 1, k = 0 and l = 0. The reciprocals of h, k and l are = 1∞∞
Now, sketch the plane with intercepts (1, ∞, ∞) along the X, Y and Z axes respectively, figure a.
b. Plane (110)
In this case h = 1, k= 1 and l = 0. The reciprocals of h, k and l are = 11∞
Now, sketch the plane with intercepts (1, 1, ∞) along the X, Y and Z axes respectively, figure b.
c. Plane (111)
In this case h = 1, k= 1 and l = 1. The reciprocals of h, k and l are = 111
Now, sketch the plane with intercepts (1, 1, 1) along the X, Y and Z axes respectively, figure c.

Directions in the unit cell:

The crystallographic direction is a vector formed by joining any two lattice points with the starting point
as the origin. It is represented by the indices [h k l] and is perpendicular to the plane given by Miller
Indices (h k l).
To find the direction when Miller Indices are given, the following steps are to be followed
 If any of the indices is greater than 1, then divide all the indices with the highest index.
 With respect to a chosen origin, draw planes represented by the indices.
 Find the point of intersection of the three planes.
 Finally draw a line from the origin passing through the point of intersection to get the direction.

For e.g. let us draw the direction of [112]

The highest index is 2. Hence dividing all indices with 2 gives [ ½ ½ 1]
Draw the plane X = 1/2
Draw the plane Y= 1/2
Draw the plane Z = 1, and find the point of intersection of the three planes
Draw line from the origin to this point to get the direction [112]
Directions are always given in Square Brackets
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[0 2 1]

Note:
If the certain Miller Index is zero, the line along that crystallographic axis should be skipped.
Let us draw the direction of [0 2 1]
The reduced intercepts 0 1 1/2
Draw the plane X = 0
Draw the plane Y=1
Draw the plane Z = - ½ , select the origin suitably to get the negative Z axis and find the point of
intersection of the three planes
Join the origin and this point to give the direction [0 2 1]
The direction drawn using certain set of Miller Indices is always perpendicular to that plane.
Multiple Choice Questions

Q1.Miller Indices of the plane are(132), then the intercept on all the three axes are
a) a, b/3,c/2
b) a,-b/3,c/2
c) -a,-b/3,c/2
d) a,-b/3,-c/2
Q2. The Miller Indices for a plane with the following set of intercepts. (a/2, b, ∞).
a) (1/210)
b) (210)
c) (211)
d) (110)
Q3. If the Miller indices of two planes have the same ratio like (844), (422) and (211) then the planes
are
a) parallel
b) Perpendicular
c) Anti parallel
d) inclined
Q4. If a plane cuts the axis on the negative side of the origin, corresponding index is
a) Negative
b) Positive
c) Zero
d) Infinite

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Q5. For an intercept at infinity, the corresponding index is

a) Negative
b) Positive
c) Zero
d) Infinity
University Questions
1. What are Miller indices? Write the procedure to obtain the same.(short note)
2. Draw the following planes for cubic structure
(200), (112), (121), (132), (121), (222), (120), (100), (101)
3. Draw the following Directions for cubic structure
[200], [112], [121], [132] [232]
4. Find the Miller Indices for a plane with the following set of intercepts. (a, 2b, 3c) and also draw the
plane for cubic structure.

Derivation for Interplanar Spacing (dhkl) & some numerical

Relation between Inter-Planar Distance and Cube Edge

Inter-planar distance is the distance between two adjacent parallel planes having Miller indices (hkl). In
the figure 23 shown below, the inter-planar distance between the planes ABC and the plane passing
through origin.

C
N
’ ’ A X
O ’

B
Fig.23
Y
Consider the plane ABC as shown in figure. The plane ABC belongs to a family of planes whose
Miller indices are (hkl). The perpendicular ON from the origin to the plane represents the inter-planar
distance. Let this distance be d = ON. The distance d of this normal from the origin to the plane will
also be the distance between adjacent planes. That is, the inter-planar distance.

Let ON make an angle ’, ’ and ’ (different from Interfacial angles) with the X, Y and Z axis
respectively.

The intercepts of the plane on the three axes are,

= , = =
ℎ

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Where, ‘a’ is the cube edge.

∴ : : = : :

From the Fig. 23

We have

ℎ
cos = = =
ℎ

cos = = =

cos = = =

By cosine rule, we have

cos + cos + cos = 1

ℎ
+ + = 1

Except for cubic and Trigonal, for all other crystal systems the relation between the inter-planar
distance d and the axial length is given by
/
dhkl = + + if a≠b≠c

Hence dhkl = for cubic a=b=c

√

This gives the relation between inter-planar distance d and cubic edge a

Interplanar Spacing for cubic System:

1. Simple Cubic (S.C) Lttice:

In this lattice, the (100) planes cut the X-axis and parallel to Y and Z axis. The (110) planes cut
obliquely across the X and Y axis but they are parallel to Z axis. Similarly the (111) plane cut obliquely
across the three axes.

Hence, Interplanar Spacing d100 = =

√

Similarly, d110 =
√
and d111 =
√

∴ : : = 1: :
√ √

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2. Face Centered Cubic (F.C.C) Lattice:

The (100), (110) and (111) planes of a face centered cubic lattices are as shown in Figure 24(a), 24(b)
and 24 (c)

Now it is clear from the fig 24(a) that additional (100) planes arise half way between (100) planes.
These planes pass through the centre of the front and back faces. Now the distance between d100 is a/2
on the basis of simple cubic lattice.

Similarly for the planes (110) it is found that,

d = (d ) simple lattice = =
√ √

But it is seen from fig 24(c) that for (111) planes no additional planes are there,
a
Hence d = (d ) simple lattice =
√3

Fig.24

: : = 1: :
√ √

3 . Body Centered Cubic (B.C.C) Lattice:

The (100), (110) and (111) planes of a body centered cubic lattices are as shown in Figure 25(a), 25(b)
and 25(c).

Now it is clear from the fig 25(a) that additional (100) planes arise half way between (100) planes. Now
the distance between d100 is a/2 on the basis of simple cubic lattice.

But it is seen from fig 25(b) that for (110) planes no additional planes are there,

∴d = (d ) simple lattice =
√

And for planes (111) there arise a plane midway between (111) plane from fig 25(c)

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d = (d ) simple lattice = =
√ √

∴ : : = 1: :
√ √

Fig.25

Numericals
√
1. In a SC cubic crystal find the ratio of spacing (110) and (111) planes. [Ans: ]
√
2. Silver has FCC structure and its atomic radius is 1.441 A. find the spacing of (111) plane.
[Ans: 2.353A°]
3. Na has BCC structure with lattice constant 4.29 A. Calculate the inter-planer spacing for (111) and
(330) planes. [Ans: 1.238A° and 1.011A° ]
4. In a BCC structure, the spacing of (121) plane is 0.1nm. Determine the atomic radius.
[Ans: 2.121A°]
5. The inter-planer spacing of (110) plane is 2Å for a FCC crystal. Find the atomic radius.
[Ans: 2 A°]

University Questions
Q.1 Show that in a crystal of cubic structure the distance between the planes with miller indices h, k and
l is equal to d = where, ‘a’ is lattice constant.

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Hexagonal Closed Packed (HCP) Structure

Hexagonal Close Packed Structure (HCP):

In the hexagonal close packed structure as shown in figure 26, the unit cell contains one atom at
each corner of the two hexagonal prisms (top and bottom), one atom each at the centre of the
hexagonal faces and three more atoms within the body of the cell. It is thus obvious that each unit
cell shares 14 atoms, and contains 3 full atoms. The common examples of this type of structure are
Magnesium, zinc, zirconium, cadmium etc

A layer

c/2

B layer
c

A layer
b
a

Fig. 26

i. Number of atoms per unit cell:

In figure 26, there are six corner atoms at each top A-layer and bottom A-layer. One face centre atom
at each top A-layer and bottom A-layer and there are three full atoms at the middle layer B-layer of
the structure.
Each corner atom is shared by six surrounding hexagon cells.

The number of corner atoms in the top layer is × 6 =1

Similarly, the number of corner atoms in the bottom layer is. × 6 =1

Each central atom at top and bottom layer is shared by two unit cells.
The number of corner atoms in the top layer is ×1=

Similarly, the number of centre atoms in the bottom layer is ×1=

But, the 3 atoms within the body of the cell are fully contributing to the cell, i.e., they are not shared
by another unit cells.

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∴ The total number of atoms per unit cell in hexagonal close packed is =
Number of corner atoms Number of centre (top and Number of middle layer
(top and bottom layer) per bottom layer) atoms per
unit cell
+ unit cell
+ atoms per unit cell

= (1 + 1) + [ + ]+3 =2+1+3=6
ii. Co-ordination Number:
With reference to the figure 26, there are three layers (A, B, A) in the hexagonal system. Consider
the bottom A-layer. In this layer, the central atom (x) has six neighbouring atoms in its own layer.
Further at a distance c/2 from the bottom A-layer, there are two layers, one is above B-layer and
another is below (not shown), containing 3 atoms in each layer. These layer atoms are also the
neighbouring atoms for the reference atom (x). Therefore, the total number of neighbouring atoms is
6 + 3 + 3. Hence, the coordination number is12.

iii. Atomic radius:

To find atomic radius of hcp structure, consider any two corner atoms. It is to be noted that, each
and every corner atom touches each other (nearest neighbours) as shown in figure 27.
∴ = 2 OR =

∴The atomic radius is =

Fig. 27

iv. Relation between ‘c’ and ‘a’ :

In hexagonal system, let the height of the unit cell be c and the distance between two neighbouring
atoms be a.
In figure 28 (a), I, J, K, L, M, N and O are the bottom layer of atoms in HCP structure and P, Q, T are
the middle layer atoms.
Consider the arrangement of atoms I, N. O and P shown in figure 28 b. I, N and O represents the bottom
layer atoms and P represent the middle layer atom. Now, let us draw the normal line OR from 0 to the
line IN, which bisects the line IN.

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Consider in triangle IOR

N M

cos 30 = = cos 30 P
O
√ I L
= [∵ OI = a] ------ (1)
Q T
If ‘S’ is orthocenter, it is found that the length
of OS is equal to (2/3) of OR. J K
Fig. 28 (a)

It means

N P

c/2

R a = 2r

S 300

I O
In triangle SOP, a

Fig. 28 (b)

2
=
3
√
= from equation (1)
=
√
------ (2)
= + ------ (3)
Substituting OP, OS and SP values in equation (3), we get;

= + …………. [∵ = , = ]
√3 2 2
On rearranging and simplifying we get,

= + − =
3 4 3 4
2 8
∵ = =
3 4 3

= ------ (4)

Equation (4) gives the axial ratio for a HCP structure

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Atomic packing factor (APF):

. ×
= --------- (1)

Number of atoms per unit cell in HCP structure = 6.

∴Volume of all the atoms in a unit cell = 6 ×

= = ∵ = ------------ (2)

The volume of the unit cell = Area of the Base × height

Area of the base = 6 × area of the triangle ONI

From fig.28b area of the triangle ONI = ( IN) ( RO)

1 √3 √3
= × =
2 2 4

√ √
Thus the area of the base = 6 × =

The height of the hcp structure = c

√
The volume of the unit cell = × ---------- (3)

Substituting equations (2) and (3) in equation (1)

3 8
= = = ∵ =
3√ 3 √ √ 8 3
×
2

√
= = .

∴74% of the volume is occupied by atoms and remaining 26 % volume is vacant

Void:
The space in the unit cell which is left unoccupied by atoms is called as the void
void = ( 100 − APF in %)
= ( 100 − 74) = 26 %

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SC BCC FCC HCP

Lattice Parameter
Lattice constant a=b≠c and
a=b=c and α=β=γ=90
α=β=90, γ=120
No. of atoms per
1 2 4 6
unit cell
Co-ordination No. 6 8 12 12
Relation between √3 √2
= = = =
‘a’ and ‘r’ 2 4 4 2
APF 0.52 0.68 0.74 0.74

Voids 0.48 0.32 0.26 0.26

Relation between
8
‘a’ and ‘c’ - - - =
3

Multiple Choice Questions

Q1.The value of c/a ratio in unit cell of HCP crystal system is
a.
√

b. √ 3/ √ 8
c. 8/ 3
d. 3/ 8
Q2.The co-ordination number for HCP lattice is-
a. 12
b. 8
c. 6
d. 4
Q3.The packing density for HCP lattice is-
a. 52%
a. 68%
b. 74%
c. 34%
Q4.The atomic radius for HCP lattice is-
√
a.
√
b.
√
c.
d.
Q5.The atomic radius for HCP is1.278A°, then lattice constant is-
a. 25.6 A°
b. 2.56 A
c. 2.56 cm
d. 2.56 m

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University Questions

1. Explain Hexagonal closed packed Structure (HCP) in detail.

2. Derive the relation between lattice constant (a) and the height (c) for the HCP unit cell.

NaCl and Diamond crystal structure

SODIUM CHLORIDE (NaCl)
NaCl is an example of ionic solid. Closed packing of the spheres can be used to describe the
ionic solids. Ionic solids are made up of atoms of different sizes.
The cations are ordinarily smaller as they looses the electron and anions form the closed packed
structure into whose void the cations get accommodated.
In NaCl, Na looses an electron and becomes Na+ ion and Cl- grabs the electron and become Cl-
ion. The Bravais lattice is FCC, the base consists of one Na ion and one Cl ion separated by one half of
the body diagonal of a unit cube i.e. the six anions surround each cation and six cations surround each
anions. Thus the cation occupies the octahedral voids formed by the anions.
Co-Ordination Number:
As the each cation is surrounded by six equidistant anions and vice-versa hence the co-
ordination number is six.
Location of ions:
The crystal structure is of FCC type, it can be considered as two interpenetrating FCC structures
with their basis ions say Na+ and Cl- located at (000) and mid way between the cube edge of sub lattice

respectively 0, , 0 , 0,0 0,0,

Thus if we consider the Na+ at the origin (000) then the location of the ions can be given as,

Na+: ( 000) , 0 , 0 , 0

Cl- : 0 0 , 00 , 00 ,

Cl- 0,0,
1
Cl- 0, ,0
+ 2
Na (000)

1
a/2
Cl- ,0,0
2

Fig.29

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No. of atoms per unit cell:

For Na+:
Considering Na+ situated at origin i.e. (000) there are 8 corner Na+ ions shared by eight unit cells
contributing 1/8th of its volume to the unit cell and six face central Na+ ions each shared by two unit
cells (adjacent) contributing 1/2 of its volume to the unit cell.
No. of Na+ ions per unit cell = 8 × + 6× = 1+ 3= 4

For Cl- :
The Cl- ions are at the center of edges of cubic unit cell. There are such 12 Cl - ions each ion is shared by
4 unit cells contributing 1/4th of its volume to the unit cell and
one Cl- ion is exclusively within the unit cell at the center of the cubic unit cell contributing whole of its
volume to the unit cell.
Thus, No. of Cl- ions per unit cell = 12 × + 1= 3+ 1= 4

Thus the total no. of ions per unit cell = 4 + 4 = 8

Total no. of NaCl molecule per unit cell = 4
As these two atoms touch along the edge of the unit cell, the distance between their centers is 1/2 of the
cube edge.
Under equilibrium condition
a
∴r + r =
2
Where, r is the radius of Na+ ion and r is the radius of the Cl- ion.

. ×
=
ℎ
4 4
× + ×
3 3
=
[2( + )]

DIAMOND STRUCTURE:

The diamond crystal structure can be considered as the two interpenetrating FCC crystal
structure with its two basis atoms both (carbon) situated at (000) and ( ) places. i.e. (

th along the body diagonal)

Although it is FCC structure, it is not as closed packed as other FCC structures since each carbon atom
is surrounded by only four other carbon atoms forming covalent bond.

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Carbon atom at
( )

Fig.30
Carbon atom at (000)

Co-ordination no:
Each carbon atom is surrounded by only four equidistant carbon atoms. Thus co-ordination no is 4.
If the atom is imagined to be at the corner of regular tetrahedron then its four nearest neighbours are at
the corner of tetrahedron.
Relation between ‘a’ and ‘r’:
To find the Relation between ‘a’ and ‘r’, let us consider the two basis atoms of diamond structure are at
(000) and ( ).

As these two atoms touch along the body diagonal, the distance between their centres is 1/4th of body
diagonal.
We know that the distance between the centers of two adjacent atoms = 2r
For cubic structure with cube edge ‘a’ the body diagonal = √ 3a
1
∴2r = √ 3a
4
√3
∴r = a
8
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No of atoms per unit cell:

There are eight corner atoms each shared by eight unit cells, contributing 1/8 th of its volume to the unit
cell.
Six atoms at the center of the faces of the cubic cell each shared by two unit cell contributing 1/2 of its
volume to the unit cell.
Four atoms which are inside the unit cell completely belong to the same unit cell contributing whole of
its volume to the unit cell.
1 1
∴No. of atoms per unit cell = 8 × + 6× + 4= 1+ 3+ 4= 8
8 2
. ×
of Diamond =
ℎ
4
8× 4 4 √3 √3 √3
= 3 = 8× = 8× == = 0.34 ∵ =
3 3 8 16 8
void = ( 100 − APF in % = ( 100 − 34) = 66 %

Multiple Choice Questions

Q1.For maximum ionic bonding energy and greatest stability the potential energy should be
a. Minimum
b. Maximum
c. Zero
d. Infinite
Q2.The co-ordination number for Diamond lattice is-
a. 12
b. 8
c. 6
d. 4
Q3.The packing density for Diamond lattice is-
a. 52%
b. 68%
c. 74%
d. 34%
Q4.The number of molecules in NaCl unit cell are-
a. 12
b. 8
c. 6
d. 4
Q5.The basis of Diamond unit cell contains…………atoms.
a. 2
b. 1
c. 4
d. 3
University Questions
1. Describe the Diamond structure with lattice parameters & characteristics. Also give other examples
of diamond structure
2. Describe the NaCl structure with lattice parameters & characteristics.
3. Calculate the distance between the atoms of a basis of the diamond structure, if lattice constant
is a = 2.4 A
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ZnS structure, Ligancy & Critical Radius Ratio

The Zinc blende (ZnS) Structure

ZnS exists in two main crystalline forms, and this dualism is often a salient example of polymorphism.
In each form, the coordination geometry at Zn and S is tetrahedral. The more stable cubic form is
known also as zinc blende or sphalerite. The hexagonal form is known as the mineral wurtzite. The
transition from the sphalerite form to the wurtzite form occurs at around 1020 celsius. The structure of
ZnS (Sphalerite) is the same as that of Diamond in which the Carbon atoms along the body diagonal are
replaced by Zn ions. The structure is shown in fig.31

Fig.31.(a) ZnS structure (b) 2-D representation of ZnS (c) Zn++ at the centre of the primitive cells

Corner ions ----S2-

Ions at 1/4th along body diagonal -------Zn+-

The two types have these features in common:

 a 1:1 stoichiometry of Zn:S

 a coordination of 4 for each ion (4:4 coordination)
 tetrahedral coordination

Zincblende (sphalerite) is based on an FCC lattice of anions whereas wurtzite is derived from an hcp
array of anions. In both structures, the cations occupy one of the two types of tetrahedral holes present.
Zincblende is best thought of as a face-centered cubic array of anions cations occupying one half of the
tetrahedral holes. Each ion is 4-coordinate and has local tetrahedral geometry. Unlike wurtzite,
zincblende is its own antitype -- you can switch the anion and cation positions in the cell and it doesn't
matter (as in NaCl). In fact, replacement of both the Zn and S with C gives the diamond structure!

No of Zn ions per unit cell = 4

No of Sulphide ions per unit cell = 4

Since the number of atoms in a single unit cell of Zn and S is the same, it is consistent with the formula
ZnS.

Coordination No = 4 (tetrahedral)

The ionic radius for Zn2+ is 74pm and for S2- is 190pm. Therefore the ratio between cationic and
anionic radii in zinc blend is 0.39 (74pm/190 pm) .This suggests a tetrahedral ion arrangement and four
nearest neighbors from standard crystal structure prediction tables. Therefore, four sulfur atoms
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surround each zinc atom and four zinc atoms surround each sulfur atom. The coordination number, the
number of electron pairs donated to a metal by its ligands, for both zinc and sulfur is four. The
difference between wurtzite and zincblende lies in the different arrangements of layers of ions.

Applications
Luminescent material: Zinc sulfide, with addition of few ppm of suitable activator, is used as
phosphor in many applications, from cathode ray tubes through X-ray screens to glow in the dark
products. Copper-doped zinc sulfide ("ZnS plus Cu") is used also in electroluminescent panels. It also
exhibits phosphorescence due to impurities on illumination with blue or ultraviolet light.

Optical material: Zinc sulfide is also used as an infrared optical material, transmitting from visible
wavelengths to just over 12 micrometers. It can be used as a planar optical window or shaped into a
lens.
Ligancy & Critical Radius Ratio
The ionic crystals are formed when metal & nonmetal ions are bound with ionic bond. And positive and
negative ions are alternately arranged. A positive ion has negative ions nearest to it and vice versa. This
alternativeness of positive and negative ions minimizes the electrostatic potential energy. Normally, the
positive ion (the cation) is smaller in size than the negative ion (the anion).

Definition: In ionic crystal co-ordination number is defined as “The number of nearest anions
surrounding a central cation.” This is called as Ligancy.

 We know, as energy given off as atoms/ions are brought closer together, until equilibrium distance
is reached.
 The solid becomes more stable if atoms/ions are closely packed and average atomic distance is
reduced.
Consider case of co-ordination number 3 (i.e. Ligancy 3)
E g. One cation (smaller size) surrounded by three anions (larger size).

(a) (b) (c)

Fig.32
Case I: fig. 32(a),

The cation is loosely fitted into the space between three anions. Here repulsive forces among the anions
are more than attractive forces between cation and anions. This makes the configuration unstable.

Case II: fig. 32(b),

In this case, anions are touching one cation and there is no enough space to fit another anion that will
touch cation. This configuration is stable but not a critical situation.

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Case III: fig. 32(c),

In this case, cation is just big enough so that it touches all three anions while allowing them to touch
each other. This is the critical position when Ligancy 3 becomes possible.
The radius ratio (rc/ra) at this position is the critical radius ratio.
The possible Ligancies, the ranges of radius ratios and associated ionic configurations are given in
following table.

Ligancy Range of radius ratio Atomic configuration

2 0.000 – 0.155 Linear

3 0.155 – 0.225 Triangular
4 0.225 – 0.414 Tetrahedral
6 o.414 – 0.732 Octahedral
8 0.732 – 1.000 Cubic
12 1 FCC monatomic or HCP

Note:
 The Ligancy 5 & 7 does not occur.
 The Ligancy 12 is the maximum possible Ligancy. But it occurs in FCC monatomic and HCP
which are mostly metals, not ionic solids.
1) Critical radius ratio for Ligancy 3.
Ligancy 3 forms a planar triangular structure as shown in
fig 33, we have
(BC) = ra

(AB) = ra+rc

∠B = 30° A

In ∆ABC
cos 30° = BC/AB
B C
0.866 = ra/ ra+rc
Fig.33
ra = 0.866 ra + 0.866 rc
rc = (1-0.866) ra/0.866
rc /ra = 0.155
2) To find ratio for Ligancy 6.

For Ligancy 6, the structure is octahedral with a cation is squeezed into the octahedral void of 6 anions
th th
(4 in a plane as shown in fig, and 5 anion is in upper layer and 6 in bottom layer).

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From fig34, we have

In ∆ BFE, ∠ = 90° & ∠ = 45°

(BF) = ra

(BE) = ra+ rc

∴cos 45 = , cos 45 =

∴ 0.7017 =

∴0.7017(ra+rc) = ra Fig.34
( . )
∴ rc = ra
.

∴ = 0.414

3) To find ratio for Ligancy 4.

Ligancy 4 forms tetrahedral structure. As shown in figure 35 a tetrahedron PQRSP can be considered to
be inscribed in a cube with P as apex of tetrahedron fig 35(a)

Fig. 35
Anions (A) are present at the opposite 3 corners of the cube at a distance √2 a. Cation is (C) at the
centre at a distance of √3 a/2(half of the body diagonal). In the critical condition, all anions are in
contact along the face diagonal and the cation centre to anion centre distance is half of the body
diagonal of the cube.
√
That is, + = and + = √2

+ √3
∴ =
√2
√3
= − 1
√2

∴ = 0.225

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4) To find ratio for Ligancy 8:

Ligancy 8 forms cubic structure. In the critical position of ligancy 8, eight anions of the crystal present
at the corners, touch along the cubic edges. Along the body diagonal, the cation and the anions are in a
position where surrounding anions touch the central cation while allowing themselves to touch each
other.
From fig36, the edge of cube a= 2 ,
Length of the body diagonal √ 3 a = 2( + ) √3a
Substituting the value of ‘a’ in the above eqn. Fig.36
2( + ) = √ 3 a
2( + ) = √3(2 ) √ 2a
( + ) = √3

= √3

1+ = 1.732

∴ = 0.732

Multiple Choice Questions

Q1. The value of critical radius ratio for Ligancy 3 is-

a. 0.124
b. 0.0414
c. 0.141
d. 0.155

Q2.The atomic configuration for ligancy 6 is-

a. Linear
b. Triangular
c. Octahedral
d. Cubic

Q3. The Ligancy……. is the maximum possible Ligancy.

a. 12
b. 7
c. 4
d. 3
University Questions
1. Define Critical Radius Ratio and ligancy, for ionic crystals.
2. Define Critical Radius Ratio and Determine the critical radius ratio for ligancy 3.
3. Describe ZnS crystal structure in short.
4. Derive the expression for critical radius ratio for ligancy 4, 6 and 8.

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X-ray Diffraction
Introduction:
X-rays are electromagnetic waves. It was discovered by “Rontgen” in 1895 during the course of cathode
ray tube experiment.
X-ray can be produced when fast moving electrons strike with high atomic number solid like
Copper or Tungsten kept in high vacuum. Most of the kinetic energy of electrons striking the target
material is converted into heat, less than 1% is being transferred into X-rays.

Properties of X-rays:
(i) X-rays are electromagnetic rays of very short wavelength (= 0.1 to 100Å).
(ii) They travel on a straight line path.
(iii) X-rays are not deflected by electric and magnetic field and hence they do not have any
charge.
Importance of X-rays in crystallography:
X-ray provides a new method for investigating the fine structure of matter.

Production of X-ray: (Coolidge tube)

Coolidge tube is a glass envelope with a very high vacuum maintained in it (Fig.37). It consists of
filament F (Cathode), target T (Anode). The filament is heated by passing an electric current to get
thermionic emission of electrons. The electrons produced are accelerated towards the Anode (Target) by
very high potential difference between Cathode and Anode.

Fig.37: Schematic Diagram of Coolidge tube (X-ray tube)

Soft X-ray: X-ray produced at low applied accelerating potential (0.12 kV to 12 kV) have long
wavelength (~10 Å) and have low penetration power.
Hard X-ray: X-ray produced at high applied accelerating potential (12 kV to 120 kV) have short
wavelength (~1 Å) and have high penetration power.
The spectrum of radiation emitted by an X-ray tube is analyzed. It shows two features, one continuous
spectra superposed by the several lines called as characteristic X-ray (Fig. 38).

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Fig.38 Continuous and Characteristic X-ray spectrum

Properties of Continuous X-rays:
(i) X-rays of different wavelengths- White X-rays.
(ii) Deceleration of electrons is responsible for Continuous X-rays.
(iii) Depends on the applied potential difference between the filament (cathode) and target
(anode).
Properties of Characteristic X-rays:
(i) X-rays of single wavelength.
(ii) Transition of electrons from the higher to lower orbit is responsible for Characteristic X-
rays.
(iii) Depends on the target material.

X-ray Diffraction and Bragg’s Law

Diffraction: Diffraction is the slight bending of wave as it passes around the edge of an object.
Diffraction occurs when the size of object is about the same as the wavelength of incident wave. Hence
X-ray diffraction: bending of X-rays around the edge of the object.
X-ray diffraction occurs, when X-rays having wavelength (in the order of few Å) of the order of
inter atomic distance made incident on the crystalline solid. Crystals can also be called as 3-D grating.
Bragg’s Law:

2d Sin  n
English physicists Sir W.H. Bragg and his son Sir W.L. Bragg developed a relationship in 1913 to
explain why the cleavage faces of crystals appear to reflect X-ray beams at certain angles of incidence
(theta, θ). The variable d is the distance between atomic layers in a crystal, and the variable lambda,, is
the wavelength of the incident X-ray beam; n is an integer. This observation is an example of X-ray
wave interference, commonly known as X-ray diffraction (XRD), and was direct evidence for the
periodic atomic structure of crystals.
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X-ray diffraction: The atomic planes of a crystal cause an incident beam of X-rays to interfere with one
another as they leave the crystal. The phenomenon is called X-ray diffraction.
The following figures 39 (a) and 39 (b) shows the interference of X-rays .

Fig.39(a). Constructive Interference of reflected X-rays

Fig.39(b). Destructive Interference of reflected X-rays

Derivation of Bragg’s Law:

Consider a crystal in which atoms are arranged in a periodic manner with inter atomic spacing
‘d’. A narrow beam of monochromatic X-ray of wavelength λ is allowed to fall on a crystal at a
glancing angle θ (Figure 40). The crystal acts as a diffracting grating with atoms as the opaque part and
the spacing between them as the transparent part.

Figure 40
Let AB and DE be the incident rays and BC and EF be the corresponding reflected rays the path
difference between the rays ABC and DEF is (GE+EH) therefore the path difference is given by

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Δ = GE + EH = d sinθ + d sinθ = 2 d sinθ

Constructive interference takes place only when the path difference is equal to nλ that is when the

following condition is satisfied

Multiple Choice Questions

Q1. To have constructive interference path difference should be.

(a) Odd multiple of λ/2
(b) Integral multiple of wavelength
(c) Both (a) and (b)
(d) None of these
Q2. In X-ray diffraction which of the following is correct.
(a) X-rays reflected from atomic plans does not interfere
(b) X-rays reflected from atomic plans do interfere
(c) Both (a) and (b)
(d) None of these
Q3. Which of the following is the correct form of Bragg’s law?
(a) d Sin = n λ
(b) 2d Sin = n λ
(c) 2 Sin = n λ
(d) 2 n Sin = d λ
Q4. In the Bragg’s law (2d Sin  = n λ), n is
(a) Rational number
(b) Non-integer
(c) Integer
(d) Irrational number
Q5. In the Bragg’s law (2d Sin  = n λ), d stands for
(a) Inter planar spacing
(b) Radius of atom
(c) Lattice constant
(d) None of above
Numerical Problems

1. Bragg’s reflection of the first order was observed at 21.70 for (111) planes of cubic crystal. If
wavelength of X-rays were 1.54 Å, find lattice constant.(Ans: 3.606 Å)
2. Electrons are accelerated through a potential difference of 60 kV in X-rays tube. The X-ray
beam then strikes a NaCl crystal for which the lattice spacing is 2.82 Å. Calculate the angle of
first order diffraction.(Ans: 2.100.)
3. A beam of X-rays is incident on a NaCl crystal with lattice spacing 0.282 nm. Calculate the
wavelength of X-rays if the first order Bragg reflection takes place at a glancing angle of 8.580.
(Ans: 0.8414 Å)
4. Calculate glancing angle on cube (100) having lattice constant 2.814 Å corresponding to first
order diffraction for X-rays of wavelength 1.541 Å. (Ans: 15.890)
5. Calculate the wavelength of X-rays reflected from the face of FCC crystal with lattice constant
2.82 Å if the second order Bragg’s reflection occurs at a glancing angle of 17.160.(Ans: λ=0.83Å)

University Questions

Q. 1. Explain and deduce Bragg’s law for X-ray Diffraction.

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Q.2. Derive the Bragg’s law of X-ray Diffraction. State one of the applications of X-ray diffraction
technique.
Q.3. A monochromatic beam of X-ray is made incident at a glancing angle ‘’on a single crystal having
interplanner spacing‘d’. Prove that the X-rays reflected from the atomic plans satisfy 2d Sin = nλ)
Q.4. Obtain an expression relating the wavelength of the X-ray to the angular positions of the scattered
beams and the separation of atomic planes in the crystals.
Q.5. Explain how crystal can act as three dimensional grating for X-ray diffraction

Crystal structure determination

X-ray diffraction techniques:

X-Ray Diffraction Method

Laue Method Rotating Crystal Method Powder Method

Orientation Lattice constant Lattice Parameters

Single Crystal Single Crystal Polycrystal (powdered)
Polychromatic Beam Monochromatic Beam Monochromatic Beam
Fixed Angle Variable Angle Variable Angle

Laue Method:
 The Laue method is mainly used to determine the orientation of large single crystals while
radiation is reflected from, or transmitted through a fixed crystal.
 The diffracted beams form arrays of spots that lie on curves on the film. The Bragg angle is
fixed for every set of planes in the crystal.
 Each set of planes picks out and diffracts the particular wavelength from the white radiation
that satisfies the Bragg law for the values of d and θ involved.
Back-reflection Laue Method:
In the back-reflection method, the film is placed between the x-ray source and the crystal. The beams
which are diffracted in a backward direction are recorded. The film intersects the cone, with the
diffraction spots generally lying on a hyperbola.

Single
Crystal Fig. 41
X-ray Film

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Transmission Laue Method:

In the transmission Laue method, the film is placed behind the crystal to record beams which are
transmitted through the crystal. The film intersects the cone, with the diffraction spots generally
lying on an ellipse.

X-ray Single Film

Crystal

Fig 42: Laue Pattern

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 continuos spectrum of X-rays.

The Powder Method:

• If a powdered specimen is used, instead of a single crystal, then there is no need to rotate the
specimen, because there will always be some crystals at an orientation for which diffraction is
permitted.
• In this method monochromatic X-ray beam is incident on a powdered or polycrystalline sample.
• This method is useful for samples that are difficult to obtain in single crystal form. The powder
method is used to determine the value of the lattice parameters accurately. Lattice parameters are
the magnitudes of the unit vectors a, b and c which define the unit cell for the crystal.
• For every set of crystal planes, by chance, one or more crystals will be in the correct
orientation to give the correct Bragg angle to satisfy Bragg's equation.
• Every crystal plane is thus capable of diffraction.

Debye Scherrer Camera:

A very small amount of powdered material is sealed into a fine capillary tube made from glass that
does not diffract X-rays. The specimen is placed in the Debye Scherrer camera and is accurately
aligned to be in the centre of the camera. X-rays enter the camera through a collimator.

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Fig. 43: Debye Scherrer camera with Diffraction pattern

The powder diffracts the x-rays in accordance with Bragg’s law to produce cones of diffracted
beams. These cones intersect a strip of photographic film located in the cylindrical camera to
produce a characteristic set of arcs on the film. When the film is removed from the camera, flattened
and processed, it shows the diffraction lines and the holes for the incident and transmitted beams as
shown in Fig. The diameter of diffracted beam cone ‘L’ is measured on the film and the incident
angle is calculated by using following formula

90 0 L

D
Where,
L= Diameter of cone on photographic film
D=Diameter of cylinder

Fig.44: Diffraction pattern obtained with Debye Scherrer camera

Application of XRD:
• Differentiation between crystalline and amorphous materials.
• Determination of the structure of crystalline materials.
• Determination of the orientation of single crystals.
• Measurement of strain and small grain size…..etc

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Bragg’s spectrometer:

Fig.45: Schematic Diagram of Bragg’s spectrometer

Bragg’s spectrometer consists of i) X-ray tube: Which produces X-rays, ii) Sample holder: Place where
crystal can be kept and iii) Detector: Which collects the diffracted X-ray photons. The diffraction
pattern is obtained from the Diffractometer as shown below. By measuring the angle of diffraction, type
of the cell and dimensions can be determined.
For example if θ1, θ2 and θ3 are the angle of diffraction from (100), (110) and (111) set of
planes, then we have,

1 1 1
d100 : d110 : d111  : :
Sin1 Sin 2 Sin 3

Fig.46: X-ray Diffraction Spectra obtained from X-ray Diffractometer

For Simple Cube (SC),

1 1
d100 : d110 : d111  1 : :
2 3
For Body Centered Cube (BCC),

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1
d100 : d110 : d111  1 : 2 :
3
For Face Centered Cube (FCC),

1 2
d100 : d110 : d111  1 : :
2 3

Multiple Choice Questions

Q1. For Laue Method which of the followings are correct

(a) Orientation of crystal can be determined.

(b) Applicable to single crystal.
(c) Polychromatic X-ray beam is used.
(d) Angle of X-ray incident is fixed.
(e) All of above.

Q2. For Rotating Crystal Method which of the followings are correct

(a) Lattice constant can be determined.

(b) Applicable to single crystal.
(c) Monochromatic X-ray beam is used.
(d) Angle of X-ray incident is variable.
(e) All of above.

Q3. For Powder Method which of the followings are correct

(a) Lattice parameters can be determined.

(b) Applicable to polycrystal (powdered sample).
(c) Monochromatic X-ray beam is used
(d) Angle of X-ray incident is variable
(e) All of above

Q4. Which of the followings are the three standard planes whose d-values is used to determine the unit
cell type for cubic system

(a) (100), (110) and (111) planes.

(b) (120), (123) and (111) planes.
(c) (100), (110) and (123) planes.
(d) (100), (112) and (110) planes.

Q5. Which of the followings is correct for SC CELL?

1 2
(a) d100 : d110 : d111  1: :
2 3
1 1
(b) d100 : d110 : d111  1: :
2 3
1 1
(c) d100 : d110 : d111  1: :
2 3

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1
(d) d100 : d110 : d111  1: 2 :
3

Q6. Which of the following is correct for BCC CELL?

1 2
(a) d100 : d110 : d111  1: :
2 3
1 1
(b) d100 : d110 : d111  1: :
2 3
1 1
(c) d100 : d110 : d111  1: :
2 3
1
(d) d100 : d110 : d111  1: 2 :
3

Q7. Which of the following is correct for FCC CELL?

1 2
(a) d100 : d110 : d111  1: :
2 3
1 1
(b) d100 : d110 : d111  1: :
2 3
1 1
(c) d100 : d110 : d111  1: :
2 3
1 1
(d) d100 : d110 : d111  2 : :
2 3

Numerical Problems

1. The glancing angle of reflection for first order K X-rays from Palladium are 5.40 from (100) planes,
7.60 from (110) planes and 9.40 from (111) planes. From the above mentioned data determine the
cubic lattice structure of crystal.(Ans: Simple Cubic)
2. The glancing angles for X-rays reflected are 5.220, 7.40 and 9.060 from (100), (110) and (111) planes
of polonium. Determine the type to which it belongs.(Ans: Simple Cubic)

University Questions

Q.1. Explain the construction and working of Bragg’s spectrometer.

Q.2. Explain crystal rotating method for determining crystal structure using X-rays.

Q.3. Explain powder method for determining crystal structure using X-rays.

Q.4. What is the difference between crystal rotating method and powder method?

Q.5. Write a short note on determination of crystal structure using X-rays.

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Liquid Crystals
Introduction:
Liquid crystals are a phase of matter that has properties between those of a conventional liquid and
those of a solid crystal. . It's a substance that behaves something like a liquid and something like a solid.
If you were to touch the stuff, it would feel gooey and soapy--in fact, the slimy mess you find at the
bottom of a soap dish is a genuine liquid crystal, not much different from the material in a laptop screen.
For instance, a Liquid Crystal may flow like a liquid, but its molecules may be oriented in a crystal-like
way. This phenomenon was discovered by an Austrian scientist Friedrich Reinitzer.
Liquid crystals are formed by a systematic phase transition with respect to temperature. At higher
temperature, they have conventional liquid phase characterized by a random molecular ordering. At
lower temperature, they exhibit significant short range orientation order while still having the ability to
flow.

As we heat, matter changes from solid to liquid after passing through an intermediate phase known as
liquid crystal phase or mesomorphic phase :

SOLID LIQUID LIQUID

CRYSTAL

Liquid crystals can be classified into thermotropic and lyotropic Liquid crystals.

Thermo tropic liquid crystal exhibit a phase transition into the Liquid crystal phase as temperature is
changed.
Lyotropic Liquid crystals exhibit phase transitions that depend on the concentration of the mesogen in a
solvent and temperature.
The phases of liquid crystals
Liquid crystals can be divided into different phases by the type of ordering.

1. Nematic or thread like Phase:

 When isotropic liquid is cooled, the first phase that condenses is Nematic, in which long
molecules are aligned so that they are on an average parallel to a direction specified by a vector
called director.
 This phase has high degree of orientation order but no long range of translational order.
 These liquid crystals can be easily aligned by an external magnetic or electric field. Aligned
molecules of nematic liquid crystals have the optical properties of crystals and this makes them
extremely useful in liquid crystal display

Fig 47.
2. Smectic or Soap like Phase:

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As temperature is further reduced, molecules begin to segregate into planes (layers) giving rise to
Smectic phase. This phase is more solid like. The molecules are aligned along the director in one
direction. .
 They form well defined layers that can slide over one another in a manner similar to that of soap.
Hence they are also called as soap like phases.
 The smectic liquid crystals have positional order along one direction, Thus they are more crystal
like than nematic phases.
 Smectic phase are typically classified as A phase and C phase. In the Smectic A phase, the
molecules are oriented along the layer normal, while in the Smectic C phase they are tilted away
from the layer normal

Smectic A phase, the Smectic C phase, the

molecules organized into molecules are tilted
layers Inside the layers
Fig. 48
3. Chiral Nematic or the Cholesteric Phase

 The cholestric phase exhibits chirality.It is is often called cholestric because it was first
discovered for cholesterol derivatives.
 This phase is exhibited by chiral molecules i.e. molecules having no internal planes of
symmetry.
 The molecules have positional ordering in a layered structure, molecules tilted by a finite angle
with respect to the normal to the layer.
 Due to chirality, a finite twist from one layer to the nest is introduced ,producing a spiral
twisting of the molecular axis along the perpendicular direction to the layers.
 An important characteristic of Cholesteric phase is the pitch. The pitch ‘p’ is defined as the
distance it takes for the director to rotate one full tern in the helix (Fig. b).
 Cholesteric phase molecules in bulk change the polarization angle.
 These molecules are wavelength dependent.

Fig.49

Properties of Liquid Crystals:

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 Liquid crystal can be considered as consisting of molecular electric dipole many of which tend
to be along a vector called the director.
 The colour of Cholesteric material can change drastically over a short interval of temperature.
 Nematic and Cholesteric materials are sensitive to external electric and magnetic field.
 They can be stimulated by low voltage and electric power.
 They are sensitive to pressure and chemical contaminations.
Questions.:
1. What are liquid crystals? How are they produced? State its different phases.
2. State the properties of liquid crystal
3. Explain the different phases of liquid crystals.
Write a short note on liquid crystals.
Crystal Defects
Imperfections or defects: Any deviation from the perfect atomic arrangement in a crystal is said to
contain imperfections or defects. Adding alloying elements to a metal is one way of introducing a
crystal defect. Crystal imperfections have strong influence upon many properties of crystals, such as
strength, electrical conductivity and hysteresis loss of ferromagnets. Thus some important properties of
crystals are controlled by as much as by imperfections and by the nature of the host crystals.
Imperfections in crystalline solids are normally classified according to their dimension as follows
1. Point imperfections (Zero dimensional defects)
2. Line imperfections (one dimensional defect)
3. Plane or surface imperfections (Two dimensional defects)
4. Volume imperfections (three dimensional defects)
Point Defects: Point defects are where an atom is missing or is in an irregular place in the lattice
structure. Point defects include
1) Self interstitial atoms
2) Impurity defect a) interstitial impurity b) substitutional impurity
3) Substitutional atoms
4) Vacancies.

1) A self interstitial atom is an extra atom that has crowded its way into an interstitial void in the
crystal structure. Self interstitial atoms occur only in low concentrations in metals because they
distort and highly stress the tightly packed lattice structure.

Fig.50

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2) A substitutional impurity atom is an atom of a different type than the bulk atoms, which has
replaced one of the bulk atoms in the lattice. Substitutional impurity atoms are usually close in
size(within approximately 15%) to the bulk atom. An example of substitutional impurity atoms
is the zinc atoms in brass. In brass, zinc atoms with a radius of 0.133 nm have replaced some of
the copper atoms,which have a radius of 0.128 nm.

Fig.51
3) Interstitial impurity atoms are much smaller than the atoms in the bulk matrix. Interstitial
impurity atoms fit into the open space between the bulk atoms of the lattice structure. An
example of interstitial impurity atoms is the carbon atoms that are added to iron to make steel.

Fig.52
4) Vacancies are empty spaces where an atom should be, but is missing. They are common,
especially at high temperatures when atoms are frequently and randomly change their positions
leaving behind empty lattice sites. In most cases diffusion (mass transport by atomic motion) can
only occur because of vacancies.

Fig.53

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5) Schottky imperfection is a type of vacancy in which an atom being free from regular site
migrates through successive steps and eventually settles at the crystal surface. In an ionic
crystal, however a vacancy on either a cation or anion site must be electrically balanced by some
means. This may be achieved if there is an equal number of a cation and anion vacancy, or if for
every ionic crystal vacancy a similar charged interstitial appears. The concentration of Frenkel
defect changes the density.

Fig.54

6) Frenkel defect For ionic crystal when a negative ion vacancy is associated with an interstitial
negative ion or a positive ion vacancy is associated with an interstitial positive ion . Since
cations are smaller in size compare to anion and a cation may occupy the void between the
anions

This defect can occur in ionic crystal when,

a) The anion is much larger than cation.

b) The ion has low co- ordination number

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The concentration of frenkel defect does not change the density.

Fig.55
Comparison between Frenkel and Schottky Defects
S.No Schottky Defect Frenkel Defect
It is produced because of missing atoms or It is produced when some atoms or ions are
1 ions from their normal crystal sites displaced from their normal sites and
occupy interstitial sites
The presence of Schottky defect lowers It does not affect the density of the crystal
2
the density of the crystal
It is generally shown by ionic solids It is generally shown by ionic solids having
3
having high coordination number low coordination number
In this cations and anions are of equal In this anions are larger in size than cations
4
sizes

Numericals
1. Calculate the ratio of the number of vacancies to the number of atoms when the average energy
required to create a vacancy is 1.95 eV at 500° K.(Ans: 2.3 x 10-20)

2. The average energy required to create a vacancy is 1 eV, calculate the ratio of vacancies at 500 ° K
and 1000° K.(Ans: 1.08 x 105)

3. Estimate the ratio of vacancies at i) -119 ° C ii) 80 ° C. Where average energy to create vacancy is
1.8 eV.(Ans: (i) 1.4 x 10-59 and (ii) 2.11 x 10-26)

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Multiple Choice Questions

1. In case of schottky defect the density of the compound
a) Decrease b) Increase c) Doubles d) Remains constant
2. Schottky defect occurs when
a) Cation moves from the lattice point
b) Anion moves from the lattice point
c) A pair of cation and anion moves
d) When an electron moves
3. Defects in which impurities which fit into the open space between the bulk atoms of the lattice
structure.
a) Vacancies b) Interstitials c) Schottky defect d) Frenkel Defect
4. In case of Frenkel defect
i. An ion moves to an interstitial site
ii. A vacancy is created
a) Only a correct b) Only b correct c) Both a & b false d) Both a & b correct
5. Vacancy is
a) Absence of atom at lattice point
b) Presence of atom at lattice point
c) Presence of atom at interstitial point
d) Absence of atom at lattice point

University Questions
1. Write a short note on point defects

2. Differentiate between Schottky & Frenkel defect

3. Describe significance of knowing about imperfections in crystal.

4. What are photonic crystals?

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