UNIT– 3 Crystal Physics

What is Crystal Physics

The branch of physics which deals with the structure, properties, external
or internal symmetries in a crystal is known as crystal physics.

Crystal Structure
A crystal is a 3D solid which consists of a
periodic arrangement of atoms.
Ex. Mn3O4

Determination of their actual structure

By using X-rays, neutron and electron
beams
INTRODUCTION TO CRYSTAL PHYSICS

2
 CLASSIFICATION OF SOLIDS

SOLID MATERIALS

AMORPHOUS
CRYSTALLINE POLYCRYSTALLINE
(Non-crystalline)

3
 CRYSTALLINE SOLIDS

• arrangement of units of matter is regular and periodic.

• anisotropic substance (dependent directions)

• sharp melting point and

a definite melting temperature

• possesses a regular shape

Ex: Iron, Copper, Carbon, Germanium

4
 NON CRYSTALLINE SOLIDS

• amorphous solids

• particles are randomly distributed.

• `isotropic’ substances (independent different directions)

• not have a sharp melting point but melts

over a range of temperatures

Examples: Glass, Plastics,

Rubber etc.,

5
 POLYCRYSTALLINE SOLIDS
 Polycrystalline materials are made up of an
aggregate of many small single crystals (also
called as crystallite or grains)
 high degree of order over many atomic or
molecular dimensions.
 Grain (domains) are separated by grain
boundaries.
 The grains are usually 100 nm – 100 microns in
diameter.
 The grains are < and > 10 nm in diameter are
quantum dot and nanocrystalline.

Examples : Inorganic solids, Most of the metals and

Ceramics

6
CRYSTALLOGRAPHIC TERMS

 SPACE LATTICE

 LATTICE POINTS

 LATTICE LINES

 LATTICE PLANES

 BASIS

 CRYSTAL STRUCTURE

 UNIT CELL

 LATTICE PARAMETERS
 Space lattice - regular and periodic arrangement of points in
three dimension.
identical surroundings to that of every
other point in the array (periodic order).

lattice points - Points in a

space lattice

Lattice lines – Lattice points

are joined with lines d

Lattice plane – A collection of a set of parallel planes passing

through lattice points.

Inside the crystal, there exists certain directions along which

large concentration of atoms exists. These directions are called
crystal directions.
8
 BASIS
A structural unit which an atom or a group of atoms, which has to
be repeated at each and every lattice point of a given lattice structure
to get corresponding crystal structure is called basis.

A set of atoms associated with each lattice point.

The crystal structure is real, while the lattice is imaginary.

9
 UNIT CELL

• ‘The unit cell defined as the smallest geometric figure which

is repeated in 3Ds to derive the actual crystal structure’
• repeating its own dimensions in various directions gives
crystal structure

10
 Lattice parameters

x, y and z are crystallographic axes

Length of the unit cell along the x, y,

and z direction are a, b, and c

Interaxial angles:

α = the angle between a and b

β = the angle between b and c

γ = the angle between c and a

a, b, c, α, β, γ are collectively known as the lattice parameters

Seven crystal systems and its lattice Parameters
BRAVAIS LATTICE
Bravais in 1948 showed that 14 types of unit cells under seven crystal systems are possible.
 MILLER INDICES

Miller indices (hkl) is defined as the reciprocals of the intercepts

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

15
 illustrates a unit cell for a crystalline structure

Uses of Miller Indices

To detect direction or distance of lattice point in a crystal.
To find orientation of plane.
 MILLER INDICES
Method of finding Miller Indices:

Step 1: Determine the intercepts of the plane along the axes

X,Y and Z in terms of the lattice constants a, b & c.
Step 2: Determine the reciprocals of these numbers.

Step 3: Find the least common Multiplier (lcM)

and multiply each numerator by this lcM.
Step 4:The result is written in paranthesis. This is
called the `Miller Indices’ of the plane in
the form (h k l).

17
 IILLUSTRATION: PLANES IN A CRYSTAL

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

3 units along Y-axis and 2 units along Z-axis.

DETERMINATION OF ‘MILLER INDICES’

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

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

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

each reciprocal by lCM. The result will be 3, 2 & 3.

Step 4: Hence Miller indices for the plane ABC is (3 2 3) 18

 MILLER INDICES
THE SIGNIFICANT FEATURES OF MILLER INDICES
For the cubic crystal, the significant features of Miller indices are:
A plane, parallel to any one of the co-ordinate axes has an intercept of infinity ().
Thus, the Miller index for the axis is zero; i.e. for an intercept at infinity, the
corresponding index is zero. A plane passing through the origin is also defined in
terms of a parallel plane having non zero intercepts.
All equally spaced parallel planes have same ‘Miller indices’ i.e. The Miller indices
do not only define a particular plane but also a set of parallel planes. Thus, the planes
whose intercepts are 1, 1,1; 2,2,2; -3,-3,-3 etc., are all represented by the same set of
Miller indices.
It is only the ratio of the indices which is important in this notation. The (6 2 2)
planes are the same as (3 1 1) planes.
If a plane cuts an axis on the negative side of the origin, the corresponding index
is negative. It is represented by a bar, like (It is only the ratio of the indices which is
important in this notation. The (6 2 2) planes are the same as (3 1 1) planes.
If a plane cuts an axis on the negative side of the origin, corresponding index
is negative. It is represented by a bar, like (ī 0 0).i.e. Miller indices (ī 0 0)
indicates that the plane has an intercept in the –ve X –axis..
 INTERPLANAR DISTANCE or d-Spacing
FEATURES OF MILLER INDICES
It is the distance between adjacent planes in a family of
parallel planes labeled by Miller Indices
The relation between the interplanar distance and the
interatomic distance is ,
a
d  for cubic crystal.
h 2  k 2  l2

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

intercepts made by the plane with the crystallographic
axes are: a b c
, and
h k l

23
 Z

C’

M
’ N
d1 d2
’ ’
O

A B

A’ B’
X Y
24
 Consider a cubic crystal of side ‘a’, and a plane ABC.
This plane belongs to a family of planes whose Miller indices are
(h k l) because Miller indices represent a set of planes.
Let ON = d1, be the perpendicular distance of the plane A B C
from the origin.
Let ’, ’ and ’ (different from the interfacial angles ,  and )
are the angles between co-ordinate axes X,Y,Z with ON
respectively.
The intercepts of the plane on the three axes are:
a a a
OA  , OB  and OC  (1)
h k l

25
From the figure,
d1 d1 d1
cos  
1
, cos 
1
and cos 
1
(2)
OA OB OC

Using equation 1 in 2
d1 h dk dl
cos1  , cos1  1 , and cos1  1 (3)
a a a

From the property of direction cosines,

cos2 1  cos21  cos2 1  1 (4)

Substituting equation (3) in (4),

2 2 2
 d1h   d1k   d1l 
 a    a   a   1
     
2 2 2
d1 h 2 d1 k 2 d1 l2
2
 2  2 1
a a a
 2
d 1
2
(h 2  k 2  l2 )  1
a
2
a
d1 
2

(h 2  k 2  l2 )
a
d1  ON  (5)
h 2  k 2  l2

a
d1 
h 2  k 2  l2
Now, consider the next parallel plane.

Let OM = d2 be the perpendicular distance of this second plane from the origin.

The intercepts of this plane along the three axes are:

27
 2a 2a 2a
OA  1
, OB 
1
, OC 
1
,
h k l
2a
 OM  d 2 
h 2  k 2  l2
• Therefore, the interplanar spacing between two adjacent parallel planes of Miller
indices (h k l ) is NM = OM – ON

i.e. Interplanar spacing

a
d   d 2  d1   (6)
h 2  k 2  l2

28
 CHARACTERISTICS OF UNIT CELL

• Number of atoms per unit cell: The number of

atoms present in the unit cell .
• Coordination number: The number of equidistant
nearest neighbouring atoms surrounding the
particular atom considered.
• Atomic Radius (r) : It is defined as half the distance
between the nearest neighbouring atoms in a crystal.
• Atomic Packing factor or Packing Density (v/V): It is
the ratio of the volume occupied by the atoms in an
unit cell (v) to the volume of the unit cell (V).

29
CALCULATION OF STRUCTURE PARAMETERS OF UNIT
CELLS

SIMPLE CUBIC CELL STRUCTURE (SCC)

BODY CENTRED CUBIC STRUCTURE (BCC)
FACE CENTERED CUBIC STRUCTURE (FCC)
HEXAGONAL CLOSED PACKED STRUCTURE (HCP)

30
 SIMPLE CUBIC CELL (SCC) STRUCTURE

Each and every corner atom is shared by eight adjacent unit cells.

Therefore each and every corner atom contributes 1/8 of its part
to one unit cell.

So the total number of atoms contributed by

the corner atoms is 8.

Number of atoms per unit cell 1/8 x 8 = 1

Coordination No. = 6
(Number of nearest neighbors)
ONE ATOM PER UNIT CELL

2r = a
r=a/2
Atomic Packing Factor  APF  of SCC :
No. of atoms per unit cell  1
4
Vol. of one atom assuming spherical structure   r3
3
The radius  r   a / 2
3
4 a
Volume occupied by the atoms per unit cell  v   1*   
3 2
Volume of the unit cell (V)  a* a* a  a 3
APF  v / V
4 a3
1* 

 3 3 8   0.52.
a 6

Thus, 52% of volume of the unit cell in SCC is occupied by atom and remaining 48%
volume is vacant.

Examples : Only one element Polonium Po  at certain temperature range exhibits
this crystal structure. 33
 BODY CENTERED CUBIC CELL (BCC)STRUCTURE
Each corner atom contributes 1/8 of it to its nearest neighbour
atom.
Number of atoms per unit cell = 1/8 * 8 = 1 atom.
There is 1 atom at the Body Centered of each unit cell.

No. of atoms/unit cell = 1+1 = 2 atoms

All the eight corner atoms touch the body centre atom along the
body diagonal. Thus, for body centre atom ‘X’, there are 8 nearest
neighbour atoms.

Therefore, Coordination number = 8

 BODY CENTERED CUBIC (BCC) STRUCTURE
Atomic Radius  r  :
From Fig ,
AB  4r; BC  CD  AD  a
Consider,  ACB B

AB 2  AC 2  BC 2
Consider,  ADC
AC 2  CD 2  AD 2 A
C
 a  a  2a
2 2 2

AB 2  AC 2  BC 2 D

AB 2  2a 2  a 2  3a 2
( 4r )2  3a 2 ; 16r 2  3a 2
3a 2
3a
r2  , r=
16 4 35
APF of BCC
No.of atoms per unit cell  2
4 8
Volume of 2 atoms in theunit cell,v  2   r 3   r 3
3 3
3a
Atomic radius,r 
4
Volume of unit cell,V  a 3
v
Packing factor 
V
3
8  3a 
 
3  4  8 3 3  3
PF  3
      0.68.
a 3  64  8
Packing factor is 68% of the volume of unit cell is occupied by atoms
and the remaining 32% volume is vacant.

Examples : •Exhibited by Cr, Fe,Mo, W etc.

 FACE CENTERED CUBIC (FCC) STRUCTURE

• 4 atoms/unit cell
• Coordination number = 12
• Close packed directions are face diagonals
Example: Al, Cu, Au, Ag, Ni, Pt

All atoms are identical

6 x (1/2 face) + 8 x 1/8 (corner) = 1+3 = 4 atoms/unit cell

37
FACE CENTERED CUBIC (FCC)STRUCTURE

No. of atoms per unit cell in FCC:

The atoms in a FCC unit cell touches along
the face diagonal.

Each and every corner atom is shared by

eight adjacent unit cells.

Therefore each and every corner atom

contributes 1/8 of its part to one unit cell.

So the total number of atoms contributed by

the corner atoms is  1   8 = 1.
 
8

38
FACE CENTERED CUBIC (FCC)STRUCTURE

No. of atoms per unit cell in FCC:

Two unit cells share each and every face centered

atom.

Therefore, the contribution of a face centered atom

to unit cell is 1/2.

So, the total number of atoms contributed by the

face centred atoms = 1/2  6 = 3.

The total number of atoms present in a FCC unit

cell = 1+3 = 4.
39
 FACE CENTERED CUBIC (FCC) STRUCTURE

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

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

has four more face centered atoms as nearest neighbours.

Similarly, in a plane, which lies just below this corner atom it has
yet four more face centered atoms as its nearest neighbours.

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

number for FCC unit cell = 4 + 4 + 4 = 12
40
Atomic Radius of FCC :
Consider the fig , AC  4r; AB  BC  a
From the triangle,  ABC,
AC 2  AB 2  BC 2
AC 2  a 2  a 2 B
C
AC  2a
2 2

a 4r
AC  2a
A
a D
i.e., 4r  2a
2a
r=
4
41
APF of FCC
No of atoms per unit cell  4
4 3
Volume of 4 atoms,v  4*  r
3
2a
Atomic redius,r 
4
Volume of unit cell,V  a 3
APF  v / V

4 *
4 

 
 2 3 a3 

4 3
4*  r  3 
3  4  16  2 2 2 
 3    
 
a3 a3 3  64 
 2 2 2 2
      0.74
3  4  3* 2 6
Thus 74 % of the volume of the FCC unit cell is occupied by atoms and
42
the remaining 26 percent volume of the unit cell is vacant or void space.
 HEXAGONAL CLOSED PACKED STRUCTURE

1. No. of atoms per unit cell

It consists of three layers of atoms.

The bottom layer has six corner atoms
and one face centred atom.
The middle layer has three full atoms.
The upper layer has six corner atoms
and one face centred atom.
Each and every corner atom
contributes 1/6 of its part to one unit cell.
The number of total atoms contributed
by the corner atoms of both top and
bottom layers is 1/6  12 = 2.
The face centred atom contributes 1/2 of its part to one unit
cell.
Since there are 2 face centred atoms, one in the top and the
other in the bottom layers, the number of atoms contributed
by face centred atoms is 1/2 2 = 1.
Besides these atoms, there are 3 full atoms in the middle
layer.
Total number of atoms present in an HCP unit cell is
2+1+3 = 6.
2. CO-ORDINATION NUMBER 3. ATOMIC RADIUS
The face centered atom touches Consider any two corner
6 corner atoms in its plane. atoms.
The middle layer has 3 atoms. Each and every corner
There are three more atoms, atom touches each other.
which are in the middle layer of Therefore a = 2r.
the unit cell. i.e., The atomic radius,
Therefore the total number of r = a/2
nearest neighbours is 6+3+3=12.

a
4. ATOMIC PACKING FACTOR :

v
APF 
V
4 3
v  6*  r
3
3
4 a
v  6*   
3 2
v a 3
To find the Volume of HCP structure

AB = AC = BO = ‘a’. CX = c/2
where c  height of the HCP unit cell.
Area of the base = 6  area of the triangle ABO
= 6  1/2  AB  OO
= 6 1/2 a  OO
In triangle O’OB O 'OB  30
OO ' OO '

cos30º = BO a 3
 OO = a cos 30º = a 2
Now, substituting the value of OO, 2
Area of the base = 6   a  a =
1 3 3 3a
2 2 2
O
V = Area of the base × height A

B 47
a/c = ?
CALCULATION OF c/a RATIO

In the triangle ABA,

A ' AB  30

Cos 30º = AA '

AB
3
AA = AB cos 30º = a
2
2 2 3 Formula for Centroid of a triangle
But AX = AA = a
3 3 2
i.e. AX = a
3

49
CALCULATION OF c/a RATIO
In the triangle AXC,

AC2 = AX2 + CX2

Substituting the values of AC, AX and CX,
2
 a 
2
c
a =  
2    c2 2
 3 2  4*
a2 3
2 2
a2 
a

c c2 8

3 4 a 2
3
c2 a2
 a 
2
c 8
4 3 
a 3
c2 2  1
 a 1   Now substituting the value of to calculate APF
4  3 of an HCP unit cell.

50
HEXAGONAL CLOSED PACKED STRUCTURE

2 3
APF =
3 3 8
2 3
=
3 3 2 2

 APF =  0.74
3 2

Packing Fraction of HCP = 0.74 (74%)

51
 DIAMOND CUBIC STRUCTURE (DC)
Qualitative topic
•Exhibited by Carbon (C), Silicon (Si) and Germanium
(Ge).
•Consists of two interpenetrating FCC lattices, displaced
along the body diagonal of the cubic cell by 1/4 the
length of the diagonal.
• Also regarded as an FCC lattice with two atoms per
lattice site: one centered on the lattice site, and the other
at a distance of a/4 along all axes, ie an FCC lattice with
the two-point basis.

52
DIAMOND STRUCTURE
Qualitative topic

a = lattice constant

53
 Qualitative topic

Y(a/4,a/4,a/4)

X(0,0,0) 54
8 atoms at each corner, 6 atoms on each face, 4 atoms
entirely inside the cell
Qualitative topic

55
 STRUCTURE PARAMETERS
1. Number of atoms per unit cell: Qualitative topic
 Total number of atoms per unit cell = 1 + 3 + 4 = 8
2. Atomic radius :
Distance formula :
XY  (x 2
 x )1
2
 (y 2
 y )
1
2
 (z 2
 z )
1
2

a  a  a 
2 2 2

XY    0   0   0
4  4  4 
2 2 2 2
a a a 3a 3a
2r     
16 16 16 16 4
a 3
r 
8
3. Coordination number:
The coordination number of diamond is 4.
4. Packing factor:
Since the packing density is very low, it is termed as loosely packed
structure.  
3
4 a 3
8*   
v 3  8  3
APF  = 3
  0.34 56
V a 16
XZ2

Qualitative topic
Crystal Imperfections or Crystal defects:
The disturbance occurred in the regular orientation of atoms is called
crystal defect or imperfection.
They are different types as follows,
1. Point Defects  i. Vacancies ii. Interstitials iii. Impurities
2. Line Defects  i. Edge dislocation ii. Screw dislocation
3. Surface Defects  i. Grain boundaries ii. Tilt boundaries iii. Twin
boundaries (Qualitative topic) iv. Stacking faults
4. Volume Defects  Cracks (Qualitative topic)

1. Point Defects
i. Vacancies
A vacancy is a type of point defect in
a crystal where an atom is missing
from one of the lattice sites.
Vacancies are different types,
i. Schottky defect
The crystal defect where an equal number of cationic and anionic (Both
+ve and –ve ions) vacancies are present is called the Schottky defect.
ii. Frenkel defect
The crystal defect where some ions are displaced from normal lattice
sites to the interstitial sites is called the Frenkel defect.
ii. Interstitials
When an extra atom occupies interstitial space within the crystal
structures without removing parent atom.

There are two types,

i. Self Interstitials - If an atom from same crystal occupies
Interstitial site.
ii. Foreign Interstitials - If an impurity atom occupies Interstitial
site.
iii. Impurities
When the foreign atoms are added to crystal lattices.

There are two types,

i. Substitutional impurity defect - Substitutional impurity refers to
foreign atom that replace a parent atom in the lattice.

ii. Interstitial impurity – An interstitial impurity is a small size atom

occupying the empty space in the parent crystal.
2. Line Defects: There are two types,
1. Edge Dislocation
An edge dislocation arises when of the atomic planes forms only partially
and does not extended through the entire crystal. The edge of such a
plane forms a line defect ( or edge dislocation).
Classifications:
a. Positive edge dislocation
The extra plane of atoms is above the slip plane of the crystal than the edge
dislocation is +ve.

b. Negative edge dislocation

The extra plane of atoms is below the slip plane of the crystal than the edge
dislocation is –ve.
2. Screw dislocation

A displacement of atoms in one part of a crystal relative to rest of the

crystal. The row of atoms marking the termination of the dislocation is the
screw dislocation.
 BURGERS CIRCUIT &VECTOR
• The magnitude and the direction of the displacement are defined by a
vector, called the Burgers Vector.
• In figure (a) is a perfect crystal, starting from the point P, we go up by 6
steps, then move towards right by 5 steps, move down by 6 steps and
finally move towards left by 5 steps to reach the origin P. Now the
Burgers circuit or Burger loop gets closed.
• When the same operation is performed on the defect crystal (figure (b))
that end up at Q instead of the origin P.
 BURGERS VECTOR
So, we have to move an extra step to return to P, in order to close the
Burgers circuit.

The magnitude and the direction of the step defines the Burgers
Vector (BV).

BV = QP = b

The Burgers Vector is perpendicular to the edge dislocation line.

 STACKING FAULTS
Whenever the stacking of atomic planes is not in a proper sequence
throughout the crystal, the fault caused is known as stacking fault.

For example, the stacking sequence in an ideal FCC crystal may be

described as A-B-C-A-B-C- A-B-C-……. But the stacking fault may
change the sequence to A-B-C-A-B-A-B-A-B-C. The region in which
the stacking fault occurs (A-B-A-B) forms a thin region and it becomes
HCP.

This thin region is a surface imperfection and is called a stacking

fault.
 SURFACE IMPERFECTIONS

(Qualitative topic) not in syllabus

Surface imperfections arise from a change in the stacking

of atomic planes on or across a boundary.
The change may be one of the orientations or of the
stacking sequence of atomic planes.
In geometric concept, surface imperfections are two-
dimensional. They are of two types external and internal
surface imperfections.
 (Qualitative topic) not in syllabus

EXTERNAL SURFACE IMPERFECTIONS

They are the imperfections represented by a boundary.At the

boundary the atomic bonds are terminated.
The atoms on the surface cannot be compared with the atoms
within the crystal.The reason is that the surface atoms have
neighbours on one side only. Where as the atoms inside the
crystal have neighbours on either sides. Since these surface
atoms are not surrounded by others, they possess higher energy
than that of internal atoms.
For most metals, the energy of the surface atoms is of the
order of 1J/m2.
 (Qualitative topic) not in syllabus

INTERNAL SURFACE IMPERFECTIONS

Internal surface imperfections are the imperfections

which occurred inside a crystal.
It is caused by the defects such as, grain boundaries.
tilt boundaries, twin boundaries and stacking faults.
 GRAIN BOUNDARIES
They are the imperfections which separate crystals or grains of
different orientation in a poly crystalline solid during nucleation or
crystallization.
It is a two dimensional imperfection. During crystallization, new
crystals form in different parts and they are randomly oriented with
respect to one another.
They grow and impinge on each other.
The atoms held in between are attracted by crystals on either side
and depending on the forces, the atoms occupy equilibrium
positions.

(Qualitative topic) not in syllabus

 GRAIN BOUNDARIES
These positions at the boundary region between two crystals are
Distorted. As a result, a region of transition exists in which the
atomic packing is imperfect.
The thickness of this region is 2 to 10 or more atomic
diameters. (Qualitative topic) not in syllabus
The boundary region is called a crystal boundary or a grain
boundary .
The boundary between two crystals which have different
crystalline arrangements or different compositions, is called as
interphase boundary or commonly an interface.
 TILT BOUNDARIES
This is called low-angle boundary as the
orientation difference between two neighbouring
crystals is less than 10°.
The disruption in the boundary is not so severe as
in the high-angle boundary. In general low-angle
boundaries can be described by suitable arrays of
dislocation.
Actually a low-angle tilt boundary is composed of
edge dislocation lying one above the other
The angle or tilt will be b

D
where b = Length of Burgers vector and D = the
average vertical distance between dislocations
spacing.
(Qualitative topic) not in syllabus
 TWIN BOUNDARIES
If the atomic arrangement on one side of a boundary is a mirror
reflection of the arrangement on the other side, then it is called as
twin boundary. (Qualitative topic) not in syllabus
As they occur in pair, they are called twin boundaries. At one
boundary, orientation of atomic arrangement changes.
At another boundary, it is restored back. The region between the
pair of boundaries is called the twinned region.
These boundaries are easily identified under an optical microscope.
 VOLUME IMPERFECTIONS

Volume defects such as cracks may arise in crystals when there is

only small electrostatic dissimilarity between the stacking sequences
of close packed planes in metals. Presence of a large vacancy or void
space, when cluster of atoms are missed is also considered as a
volume imperfection. (Qualitative topic) not in syllabus
Foreign particle inclusions and non crystalline regions which have
the dimensions of the order of 0.20 nm are also called as volume
imperfections.
Pores – affect optical, thermal and mechanical properties
Cracks – affect mechanical properties
Foreign inclusions – affect electrical, mechanical, optical properties