Chapter

CRYSTAL
PHYSICS 5
KEYNOTES
Crystalline and Non-crystalline Solids |Terminologies | Lattice
Constant | Seven Crystal Systems | Bravais Space Lattices |
Miller Indices | Atomic packing factor | Closed Packed Strutcure |
Defects in Crystal | Electronic Defects
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5.1 INTRODUCTION
Crystallography is a branch of physics that deals with the study of inter-
nal structures, physical properties and imperfections of the crystalline solids by
using x-rays, electron beams and neutron beams. Generally solids are classified
into crystalline and non-crystalline or amorphous based on the arrangement of
atoms or molecules.

5.2 CRYSTALLINE SOLIDS

In crystalline solids, the atoms or molecules are arranged in a regular

and ordered fashion in a three dimensional pattern. Each and every atom has
identical environment. The crystal exhibits a definite melting point.
In crystals, the atoms or molecules are more closely packed and they are
held together by strong cohesive forces and cannot move in random manner.
Crystals possess internal symmetry.
The crystalline solids are anisotropic. i.e., the physical properties are
different in different directions.

The anisotropy of crystalline solids is a strong evidence for the existence

of orderly arrangement of atoms or molecules. The crystalline solids may be
classified into four types depending upon the nature of bonds present in them.

1. Molecular crystals
In molecular crystals, the constituent particles are molecules. These
molecules are held together by weak forces known as vander Walls’ forces.
Molecular crystals are generally soft and good insulators. They have low melting
point and low heats of vapourisation.
Example: Solid CO2, ice, iodine
 Crystal Physics 143

2. Ionic crystals
In ionic crystals, positive and negative ions are arranged in a regular
fashion throughout the crystal. These are held together by strong electrostatic
forces. These crystals are very hard and brittle and poor conductors of electricity.
They have very high melting and boiling points and high heats of vapourisation.
Example: salts like NaCl, KNO3 , LiF

3. Metallic crystals
Metallic crystals have metallic bonding. i.e., positive metallic ions are
surrounded by a sea of mobile electrons. Metallic crystals may be hard as well as
soft. These are good conductors of heat and electricity. They have moderate heats
of fusion and melting points from moderate to high. The metallic crystals are
widely used in engineering field due to their favorable properties like strength,
conductivity, reflectivity, malleability, ductility, elasticity, reflection, etc.
Example: Ni, Cu, Fe, and their alloys.

4. Covalent or non-metallic crystals

In covalent crystals, atoms are the constituent particles and they are linked
to one another by covalent bonds. Covalent crystals are very hard and non-
conductors. They have very high melting point and high heats of fusion.
Example: Diamond, Silicon, Germanium, Caroborundum (SiC).

5.3 NON-CRYSTALLINE SOLIDS

Non-crystalline solids are called amorphous solids. In amorphous

solids, the atoms or molecules do not have regular arrangement. They
are arranged in an irregular fashion and do not have identical
environment.
They do not exhibit definite melting point. The amorphous solids are
isotropic. i.e. the physical properties are same in all directions. They do not possess
internal symmetry.
Example: glass, plastics, rubber etc.
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5.4 TERMS USED IN CRYSTALLOGRAPHY

1. Space lattice
In crystalline solids, the atoms or molecules are arranged in a regular
and ordered fashion in space. The position of atoms or molecules in a crystal,
relative to one another are usually shown by points.

2. Lattice point:
An imaginary point in space, where an atom or a molecule is assumed to
be located.

3. Lattice plane:
Arrangement of lattice points in a two dimensional plane is called lattice
plane.
A space lattice may be defined as an infinite three dimensional arrange-
ment of lattice points in space in which the environment about each point
is same.

4. Lattice points

The position of atoms or molecules in space denoted by points is called

lattice points or lattice sites.

Let us consider the case of two-dimensional array of points in space as

shown in Figure 5.1.

Figure 5.1 A two-dimensional array of points

 Crystal Physics 145

From the figure, it is clear that each and every point of the space has
identical environment. Let us choose any point A as origin and consider any two
axes AB and AD, then we can draw a square. By repeating this diagram, in all the
three dimensions, the entire lattice points of the space in three dimensions can be
obtained. This three dimensional periodic arrangement of lattice points in space
is called space lattice.
Here it should be remembered that a space lattice refers to the idealized
geometrical concept whereas the structure of crystals refers to the actual arrange-
ment of atoms or molecules of the crystals in the space.
5. Space lattice:
Arrangement of lattice points in a three dimensional space is called space
lattice.

Lattice Basis Crystal structure

Figure 5.2 Basics of patterns

Figure 5.2 shows the basis associated with the space lattice. The figure
shows the basis or pattern representing each lattice point. It is observed from the
figure that the basis has identical environment. In some crystals like Al and Ba,
the basis is a single atom. But in the case of NaCl and KCl crystals, the basis is
diatomic and in CaF2, the basis is tri-atomic.

6. Basis of the crystal structure

A crystal structure is represented by associating every lattice point with
one or more atoms (or an unit assembly of atoms or molecules) identical
in composition, arrangement and orientation. This arrangement of atoms
with lattice point is called the basis or pattern.
146 Engineering Physics - I

When the basis is repeated with correct periodicity in all directions, we

can get the actual crystal structure. To generate a crystal structure, space lattice
is combined with a basis.

Space lattice + basis → crystal structure

7. Unit cell

Figure 5.3 Unit cell in two dimension

To understand the concept of unit cell, let us consider a two-dimensional

crystal lattice as shown in Figure 5.3. First we draw a parallelogram ABCD.
By rotating this parallelogram repeatedly in both directions, the whole crystal
structure may be obtained. This small region ABCD is called an unit cell. This
same procedure is extended for a three-dimensional case also.
Figure 5.4 shows the three-dimensional space lattice and a unit cell.

Figure 5.4 Space lattice and a limit cell Watch Animation in the CD-ROM

A unit cell is defined as the smallest geometrical volume of a solid and the
translational repetition of which in three-dimension, the actual crystal
structure can be obtained.
 Crystal Physics 147

This unit cell may be considered, as brick of a wall.

This unit cell may also be defined as the fundamental unit or elementary
pattern or building block.

To understand the structure of a single unit cell of the given crystal, study
of that crystal is enough so that the unit cell reflects all the properties of the
whole crystal.

Primitives
The intercepts a, b and c give the dimensions of a unit cell and are known
as primitives.

8. Primitive cell
Primitive cell is a unit cell which is formed by the primitives a, b and c
and the primitive cell will have only one lattice point.

In other words, a unit cell is a primitive cell, if all the lattice points in it are at
vertices. If a unit cell has two or more lattice points, it is not a primitive cell
(non-primitive cell). For example, simple cubic unit cell is said to be a primitive
cell. But a body centered cubic unit cell is not a primitive cell.
The unit cell differs from the primitive cell in that it is not restricted to
being the equivalent of one lattice point. In some cases, these two cells coincide.
Thus, unit cells may be also primitive cells, but all the primitive cells need not be
unit cells.

5.5 LATTICE PARAMETERS OF A UNIT CELL

A unit cell is characterized by three inter facial angles and corresponding

intercepts. These six parameters are called as lattice parameters.

Let us consider a unit cell shown in Figure 5.5. Three lines are drawn
parallel to the lines of intersection of any three faces, which do not lie in the
same plane. These lines are called crystallographic axes and are marked as x, y
and z. The intercepts of the unit cell along the three axes x, y and z are a, b and c
respectively. The angles α, β and γ between these three crystallographic axis are
148 Engineering Physics - I

Figure 5.5 Lattice parameters of a unit cell

called interfacial angles. Thus, the intercepts a, b, and c and the interfacial angles
α (between b and c), β (between a and c) and γ (between a and b) are called lattice
parameters of a unit cell. By knowing these six parameters, the structure and
actual size of the unit cell can be determined easily.

5.6 CALCULATION OF LATTICE CONSTANT

A relation between lattice constant of the cubic crystals and the density of
the crystal can be obtained in the following way. Let ‘a’ be the lattice constant
and ‘ρ’ be the density of the cubic crystal.
 Crystal Physics 149

5.7 CRYSTAL SYSTEM

The six lattice parameters (the three interfaced angles and the correspond-
ing intercepts a, b and c) are used to construct a unit cell with exact shape and
size. On the basis of shape of the unit cell crystals are classified into seven crystal
systems.
The seven crystal systems are cubic, tetragonal, orthorhombic,
monoclinic, triclinic, rhombohedral and hexagonal

1. Cubic system
In this system, all the three axes are of equal length at right angels to each
other.
i.e. a = b = c and α = β = γ = 90°
NaCl, CaF2 are examples of this system.

2. Tetragonal system
In this system, all the three axes are at right angles to each other and two
axes are equal in length but third one is different.
i.e. a = b ≠ c and α = β = γ = 90°
NiSO4, SnO2, white tin, indium, are examples of this type.

3. Orthorhombic system
In this system, all three axes are at right angles to each other and these
axes are all of different length.
i.e. a ≠ b ≠ c and α = β = γ = 90°
KNO3, BaSO4, sulphur, topaz, etc. are examples of this type.
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Cubic Tetragonal Orthorhombic

Monoclinic Triclinic Rhombohedral

4. Monoclinic system
In this system, all the three axes are of different lengths and two axes are
at right angles to each other but third is obliquely inclined.
i.e. a ≠ b ≠ c and α = β = 90°; γ ≠ 90°
Na2 SO3, FeSO4, BaSO4 are examples of this system.

5. Triclinic system
In this system, all the three axes are of different lengths and all are oblique
to the each other.
i.e. a ≠ b ≠ c and α ≠ β ≠ γ ≠ 90°
CuSO4, K2Cr2O7, etc. are examples of this system.
 Crystal Physics 151

Hexagonal

Figure 5.6 Seven crystal system Watch Animation in the CD-ROM

6. Rhombohedral system (Trigonal)

In this system, all the three axes are of equal length and are inclined to
each other at an angle other than 90°.
i.e. a = b = c and α = β = γ ≠ 90°
CaSO4, calcite are examples of this system.

7. Hexagonal system
In this system, two axes of one plane are of equal length and at 120° with
each other and third axis is different and perpendicular to this plane.
i.e. a = b ≠ c and α = β = 90°; γ =120°
Quartz, Tourmaline, SiO2 are examples of this system.
Table 5.1 gives the seven crystal systems and relation between primitives and
angles
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Table 5.1 Seven crystal systems

Relation between Relation between

S.No Name of crystal system
primitives angles
1 Cubic a=b=c α = β = γ = 90°
2 Tetragonal a=b≠c α = β = γ = 90°
3 Orthorhombic a≠b≠c α = β = γ = 90°
4 Monoclinic a≠b≠c α = β = 90°; γ ≠ 90°
5 Triclinic 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°

5.8 BRAVAIS SPACE LATTICES

In 1848, Auguste Bravias showed that the only fourteen ways of arrange-
ment of lattice points in space, so that the environment looks the same from each
point.
The fourteen possible ways of arranging lattices points in seven
crystal systems in space are called the Bravais lattices named after
the discoverer.

The fourteen types of Bravais lattices are illustrated in Figure 5.7

1. Cubic system
The cubic system has the following three Bravais lattices.

i) Simple Cubic (SC)

This system has one lattice point at each of the eight corners of the unit
cell. No other lattices point presents inside the units cell. This system is denoted
by the symbol P.

ii) Body Centered Cubic (BCC)

This system has one lattice point at each of the eight corners and one lat-
tice point at the center of the unit cell. This system is denoted by the symbol I.
 Crystal Physics 153

iii) Face Centered Cubic (FCC)

This system has one lattice point at each of eight corners and one lattice
point at the centers of each of six faces of the unit cell. This system is denoted by
the symbol F.
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Figure 5.7 Three-dimensional 14 Bravai’s lattices Watch Animation in the CD-ROM

2. Tetragonal system
The tetragonal system has the following two Bravias lattices.
i) Simple tetragonal (P)
ii) Body-centered tetragonal (I)

3. Orthorhombic system
Orthorhombic system has the following four Bravias lattices
i) Simple orthorhombic (P)
ii) Body centered orthorhombic (I)
iii) Face centered orthorhombic (F)
iv) Base centered orthorhombic (C)
Base-centered orthorhombic system
The base centered system has one lattice point at each of the eight corners
and one lattice point at the center of each of two faces opposite to each other. This
is denoted by the symbol C.

4. Monoclinic system
The monoclinic system has the following two Bravais lattices
i. Simple monoclinic (P)
ii. Base centered monoclinic (C)
 Crystal Physics 155

5. Triclinic system
This system has only the simple triclinic system (P)

6. Rhombohedral system
This system has only the simple rhombohedral system (R)

7. Hexagonal system
This system has only the simple hexagonal system (P).

5.9 LATTICE PLANES

In a crystal lattice, the lattice planes may be defined as an aggregate of
a set of equidistant parallel planes and passing through the lattice points. In a
particular lattice, we can choose different set of lattice planes. Figure 5.8 shows
different set of lattice planes in a particular lattice.

Figure 5.8 Different set of lattice planes

5.10 MILLER INDICES

In a crystal atoms are arranged in the form of layers or planes called
crystallographic planes. To designate a lattice plane, which consists of a set of
three numbers. These set of three numbers are called Miller indices. In a crystal,
the intercepts of a plane on the crystallographic axes are used to describe the
orientations of the lattice planes.
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Miller indices are the three smallest possible integers which have the
same ratios as the reciprocals of the intercepts of concerned plane.

Procedure of finding Miller Indices

1. Find the intercepts made by the plane
on the three reference axes. For
example, assume that these are x’, y’
and z’.
2. Convert these intercepts interms of
the axial units. Let them be pa, qb, rc.
3. Take the numerical parameters of
the plane, i.e., p, q and r.
4. Find the reciprocals of the numerical
parameters. In the above case, they Figure 5.9 Miller indices
will be 1/p, 1/q and 1/r.
5. Convert these reciprocals into whole numbers by multiplying each of them
with their least common multiple (LCM). Let us represent these numbers as
h, k and l.
6. Enclose these numbers in brackets as (h k l) which represents the Miller
indices of the plane under consideration.
A set of planes, which are parallel in the crystal, is called as family of planes and
is designated as {h k l}.

Miller indices of a given lattice plane

For example; let us consider a lattice plane ABC as shown in Figure 5.10.
1. The plane ABC has 2 axial units on x-axis, l axial unit along y-axis and 2
axial units along z-axis.
2. The intercepts of the plane are 2a, 1b, 2c.
3. Numerical parameters of this intercepts are 2,1, 2.
4. Then the ratio of the reciprocals of the intercepts are 1/2 : 1/1 : 1/2
 Crystal Physics 157

Figure 5.10 Miller indices of a lattice plane ABC

5. These reciprocals are converted into whole numbers by multiplying each by

their LCM.
6. Now we get three smallest whole numbers 2,1,2.
7. These numbers are enclosed in parentheses i.e. (2,1, 2)

Therefore (2,1,2) is the Miller is the Miller indices of the plane ABC.

Conditions for finding Miller Indices

While determining the Miller indices of a lattice plane, we have to follow
the following two conditions.
1. If the assumed lattice plane is parallel to any one of the coordinate axes, the
intercepts on that axis is ∞ and the Miller index for that axis is zero.
2. If the assumed lattice plane is on the negative side of any of the coordinate
axes, the Miller index for that axis is expressed by putting minus sign directly
over it such as (1 0 0).

Representation of crystal planes in a cubic unit cell

A few important planes in a cubic cell is discussed below. Crystal planes
of the family {100} are illustrated in Figure 5.11.
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Figure 5.11 Family of {100}

Similarly the crystal planes of the family are obtained by changing the location of
the origin is shown in Figures 5.12.

Figure 5.12 Family of{100}

For a cubic unit cell, {110} represents the set of six planes (110), (101),
(011), (110), (101) and (011) which is illustrated in Figure 5.13.
 Crystal Physics 159

Figure 5.13 Family of {110}

Similarly, a set triangular planes (111), (111), (111) and (111) represented by
{111} is shown in Figure 5.14.

Figure 5.14 Family of {111} Watch Animation in the CD-ROM

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5.10.1 RELATION BETWEEN INTERPLANAR DISTANCE AND CUBE EDGE

Consider a lattice plane ABC in a cubic
crystal as shown in Figure 5.15. This plane
is one of the lattice plane of the family of
planes whose Miller indices are (h k ℓ).
A normal OP is drawn to the plane
ABC from the origin O of the cube. Let OP
be the interplaner distance ‘d’ of this family
of planes.
Let OA, OB and OC are the intercepts
of the plane on the crystallographic axis x,
Figure 5.15
y and z respectively and α, β, and γ are the
angles between the crystallographic axis x,
y, z and the normal OP.
We know that the Miller indices of
a plane are of the smallest integers of the
reciprocals of the intercepts of the plane on
the crystallographic axis. But here, we can
express the intercepts as the reciprocals of
the Miller indices of the plane.

Figure 5.16
 Crystal Physics 161

5.11 IMPORTANT PARAMETERS IN CRYSTAL STRUCTURES

Some of the important fundamental parameters, which are used to describe
the crystal structures, are discussed below.

i) Number of atoms per unit cell (n)

The total share of atoms possessed by a given unit cell in a crystal system
is known as number of atoms per unit cell.

ii) Co-ordination number (CN)

In a crystal system, each atom is surrounded by other atoms.

Co-ordination number is the number of nearest equidistant, neighbour-

ing atoms which are directly surrounding a given atom.

iii) Atomic radius (r)

The atomic radius is defined as half of the distance between two nearest
neighbours in a crystal of pure element.
162 Engineering Physics - I

To calculate the atomic radius of the atom, it is assumed that the atoms are
spheres in contact in a crystal. It is usually expressed in terms of cube edge ‘a’.
iv) Atomic Packing Factor (APF) or Packing Density

It is the ratio of volume occupied by atoms in a unit cell to the total

volume of the unit cell.

5.12 CUBIC AND HEXAGONAL CRYSTAL SYSTEMS

Almost three-quarters of the elements are metals and most of the impor-
tant metals crystalline in either the cubic or hexagonal systems. They are Body
Centered Cubic (BCC), Face Centered Cubic (FCC) and Hexagonal Close Packed
(HCP). The above factors for cubic system and hexagonal system are discussed
below.

1. Simple cubic system (SC)

Figure 5.17 (a) Simple cubic lattice point representation (b) Hard sphere model
Watch Animation in the CD-ROM

This is a simplest crystal structure. A simple cubic unit cell has atoms
that are located at each of the eight corners of the unit cell. A lattice point
representation is shown in Figure 5.17 (a) and the hard sphere representation of
SC structure is shown in Figure 5.17 (b). The radioactive metal polonium (Po)
exhibits this structure.
 Crystal Physics 163

i) Number of atoms per unit cell

Figure 5.17(a) shows that the unit cell of simple cubic crystal system in
which the atoms are located at each of the eight corners of the unit cell. The eight
adjoining cubes share each corner atom. So, the effective number of atoms per
unit cell is one for SC structure. Each of the eight corner atoms contributes 1/8th
of an atom to the interior cell.
A unit cell of this type is a primitive cell.
The effective number of atom in a SC unit cell = (8 atoms at the corner × 1/8)
= 1 atom.
ii) Co-ordination number
Number of closest neighbors to an
atom is called co-ordination number of
the unit cell. From the Figure 5.18, each
corner atom has four nearest neighbours
in the same plane, one exactly above this
plane and one atom exactly below this
plane. Totally it has 6 nearest neighbour-
ing atoms. So the co-ordination number
of SC structure is 6.
Figure 5.18 Co-ordination number for
simple cubic structure is six
iii) Atomic radius Watch Animation in the CD-ROM
The atoms of this unit cell touch
each other along the cube edge. If ‘a’ is
the cube edge of the unit cell and r is
the atomic radius, the distance between
nearest neighbours is obtained from
Figure 5.19.

Figure 5.19 Atomic radius of SC

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iv) Atomic Packing Factor (APF)

The volume occupied by atoms in a simple cubic unit cell divided by
volume of a simple cubic unit cell is called the atomic packing factor. For a SC
unit cell,

i.e. 52% of the simple cubic unit cell is occupied by one atom. This is a
loosely packed structure.

2. Body-centered Cubic Crystal structure (BCC)

In this unit cell, atoms are located at each corner of a cube and a single
atom at the cube center. A lattice point representation of BCC is shown in
Figure 5.20 (a). The hard sphere representation of BCC structure is shown in
Figure 5.20 (b).

Figure 5.20 (a) Body centered (b) Hard sphere model

cubic lattice point representation

Watch Animation in the CD-ROM

 Crystal Physics 165

i) Number of atoms per unit cell

The central atom touches each corner atom but the corner atoms do not
touch each other as shown in Figure 5.20 (b). Since each corner atom is shared by
eight adjoin cubes and any other cube cannot share the center atom. So, number
of atoms (n) per unit cell of the BCC unit cell is
8 atoms at the corners × 1/8 = 1 atom
1 center atom = 1 atom
Making it a total of 2 atoms

ii) Co-ordination number

For calculating the co-ordination
number, if a central atom is considered, it
is surrounded by eight nearest neighbors.
If a corner atom is considered, the body-
centered atoms are the nearest neighbors
not the other corner atoms as shown in
Figure 5.21. So, co-ordination number of
BCC unit cell is 8.
Figure 5.21 BCC co-ordination
iii) Atomic radius
Watch Animation in the CD-ROM
In the BCC system, the corner
atoms of a unit cell do not touch each
other along the cube edge. But the body
centered atom touches the corner atoms
of the unit cell along the body diagonal as
shown in the Figure 5.22.

Figure 5.22 Atomic radius of BCC

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iv) Atomic Packing Factor (APF)

The BCC system has two atoms per unit cell.

i.e. 68% of the BCC unit cell is occupied by two atoms. Tungsten, sodium,
iron, chromium, molybdenum exhibit the BCC structure.

3. Face-centered cubic crystal structure (FCC)

In FCC structure, the atoms are located at each of the eight corners and
at the centers of all cube faces of the unit cell. Each face centred atom touches its
nearest neighbour corner atoms. Figure 5.23 (a) and (b) show the arrangement
of lattice points for an FCC unit cell and the actual packing of atoms within the
unit cell. This face-centered lattice is also called as cubic closed packed (CCP)
structure.
 Crystal Physics 167

Figure 5.23 (a) Face-centered cubic (b) Hard sphere model

lattice point representation
Watch Animation in the CD-ROM

i) Number of atoms per unit cell

In FCC crystal structure, each corner atom is shared by eight adjoining
unit cells. Therefore, each and every atom contributes 1/8 of its part to one unit
cell. Each face centered atom is shared by two adjoining unit cells. Hence 1/2 of
each face centered atom contributes 3 atoms per unit cell. So, number of atoms
per FCC unit cell is
8 atoms at the corners × 1/8 = 1 atom
6 face-centered atoms × 1/2 = 3 atoms
Making it a total of 4 atoms

ii) Co-ordination number

If we consider the corner atom
the face-centered atoms are the near-
est nieghbours. A corner atom has four
face-centered atoms in its own plane,
four in a plane above and four in a plane
below it as shown in Figure 5.24. Hence the
co-ordination number is 12. Due to its
highest co-ordination number, this is a
closed packed structure. Figure 5.24 FCC co-ordination number

Watch Animation in the CD-ROM

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iii) Atomic radius

The corner atoms of this unit cell do
not touch each other along the cube edge
but they touch each other along the diago-
nal of any face of the unit cell. Consider a
cube face as shown in Figure 5.25.
From the ∆ABC,

Figure 5.25 Atomic radius of FCC structure

iv) Atomic packing factor

FCC structure has 4 atoms per unit cell. Atomic packing factor of a FCC
unit cell can be calculated as
 Crystal Physics 169

i.e. 74% of the unit cell is occupied by 4 atoms. When we compare this
system with SC, BCC systems, it has high packing factor and hence this is a
closely packed system. Most of the metals like copper, lead, aluminium and
silver exhibit FCC structure.

4. Hexagonal Closed Packed Structure (HCP)

The unit cell of HCP system has 12 corner atoms, one at each and
every corner of the hexagon with two base centered atom, one at the top face
of the hexagon and another at the bottom face of the hexagon as shown in the
Figure 5.26 (a).
In addition to corner and base atoms, there are three symmetrically
arranged atoms in between the top and bottom face of the hexagon. Three addi-
tional atoms are located between top and bottom planes, which are illustrated in
hard sphere model as shown in Figure 5.26 (b).

Figure 5.26 (a) Lattice point representation of HCP (b) Hard sphere model
Watch Animation in the CD-ROM

i) Number of atoms per unit cell

One half of the each of the 2 base centered atoms, one six of the each of
the 12 corner atoms, and all the 3 mid plane interior atoms contribute to the HCP
unit cell. Thus, the effective number of atom per unit cell of HCP is 6.
1/6 of the 12 top and bottom layer corner atoms = 12 × 1/6 = 2 atoms
1/2 of the each of 2 center atom = 2 × 1/2 = 1 atom
3 midline interior atoms = 3 atoms
Making it a total of 6 atoms
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ii) Co-ordination number

In HCP unit cell, if we consider the
base centered atom, each atom touches
six corner atoms in the same plane and
three more atoms in a plane above and
three more in a plane below it as shown in
Figure 5.27. Thus, each atom has 12 nearest
neighbours. So, the co-ordination number of
HCP unit cell is 12.
Figure 5.27 HCP co-ordination number

iii) Atomic radius Watch Animation in the CD-ROM

In a hexagonal face of the unit cell,

the corner atoms touch each along the edge of the hexagon. From Figure 5.28

Figure 5.28 Hexagonal face of a HCP structure

iv) Calculation of c/a ratio

To calculate c/a ratio, let us consider the triangle in the bottom layer of
the HCP unit cell. Let ‘c’ be the height of the unit cell and ‘a’ be the distance
between two nearest neighboring atoms.
Consider the triangle ABO which is shown Figure 5.29(a). Here A, B and
O are the atoms of the bottom layer and y is the next layer atom which lies exactly
above this plane at a distance c/2 .
 Crystal Physics 171

Figure 5.29 (a) Bottom layer of HCP structure (b) Triangle ABO

Watch Animation in the CD-ROM

From the triangle ABA′

From the triangle Axy,

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iv) Atomic Packing Factor for HCP

The HCP structure has 6 atoms per unit cell.
 Crystal Physics 173

i.e. 74%of the HCP unit cell is occupied by 6 atoms. When we compare
this structure with other structures, it has high packing factor and hence it is a
closely packed structure. Magnesium, zinc, titanium, zirconium are common
examples of HCP structure.

5.13 CLOSE PACKED STRUCTURE

The co-ordination number and atomic packing factor are the same for
both face centered cubic and hexagonal closed pack crystal structures. These two
structures may be generated by the stacking of close packed planes of atoms in
different packing sequence. If equal size spheres are packed together as closely
as possible in a plane, then the arrangement of sphere is as shown in Figure 5.30.
174 Engineering Physics - I

The co-ordination number of each

sphere in this arrangement is six.
Consider a layer A where the
atoms are arranged in a close-packed
hexagonal array. The atoms of the next
layer B will sit in the hollows or voids Figure 5.30 Hexagonal array arrangement
of first layer A.
Now a third layer can be positioned in two ways. If the third layer is
positioned exactly identical to the first layer A, the sequence results as ABAB….
This arrangement is called Hexagonal Closest Packing (HCP) as shown in Figure
5.31.
Another way of stacking the third layer is laterally offset from those in
both layers A and B. This layer is type C and the fourth layer will correspond to
those in the first layer A. This gives the ABCABC…… type of arrangement. This
arrangement is known as Cubic Closest Packing (CCP) as shown in Figure 5.32.

Figure 5.31 Hexagonal closest packed structure Figure 5.32 Cubic closest packed structure

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5.14 COMPARISON OF SOME CRYSTAL STRUCTURES

Table 5.2 gives the comparison of properties of some crystal structures
discussed earlier.
 Crystal Physics 175

Table 5.2 Comparison of crystal structures

Hexagonal
Simple Body centered Face centered
S.No Properties closed packed
Cubic (SC) cubic (BCC) cubic (FCC)
(HCP)
Volume of
1 unit cell a3 a3 a3

No of atoms
2 1 2 4 6
per unit cell
Co-ordination
3 6 8 12 12
number
Atomic radius
4 (r)

5 Packing factor 0.52 0.68 0.74 0.74

Polonium Iron, Barium Copper, Magnesium,
6 Examples Tungsten Aluminum, Zinc, Tita-
Nickel nium
5.15 SOME CHARACTERISTIC STRUCTURES OF CRYSTALS
Several elements and all compounds will have any one of the structures
like Zinc blend cubic structure, sodium chloride structure, cesium chloride
structure and fluorite structure. Some of these structures are derivatives from or
combination of the fundamental structures described above.

1. Diamond cubic structure

Diamond cubic structure is a combination of two interpenetrating FCC
sub-lattices. Germanium, silicon and diamond possess this structure. Figure
5.33(a) shows the unit cell of diamond structure. This structure has two
sub-lattices A and B. The sub-lattice A has its origin at (0,0,0) and sub-lattice B
has its origin at the quarter of the way along the body diagonal i.e. at the point
(a/4, a/4, a/4).
Figure 5.33(b) shows the basic diamond lattice and the atomic positions in
the cubic cell of diamond projected on a cube face.
In this structure, each carbon atom forms covalent bonds with the four
nearest corner carbon atoms.
176 Engineering Physics - I

Figure 5.33(a) Unit cell of diamond Figure 5.33(b) Atomic positions on a

cubic structure cube face
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i. Number of atoms per unit cell

This structure has eight corner atoms and six face centered atoms. In
addition to that, there are four atoms inside the unit cell.

ii. Coordination number

In this unit cell, there are four nearest neigh-
boring atoms for each atom. Each atom is covalently
bonded by sharing of electrons to four other atoms
and each atom is surrounded by four others at the
corners of the regular tetrahedron. Thus, the coordina-
tion number of diamond cubic structure is 4.
Figure 5.34
 Crystal Physics 177

iii. Atomic radius

Let ‘a’ be the side of cube in an unit cell.

iv. Packing factor

178 Engineering Physics - I

i.e. 34% of the unit cell of diamond structure is occupied by 8 atoms. This
structure has low packing fraction. This is a loosely packed structure.

2. Rock salt (NaCl Crystal Structure)

Sodium chloride furnishes a good
example of rock salt structure. Figure 5.35
shows its structure, which is simple cubic
with alternate lattice positions, occupied by
positive sodium ions and negative chloride
ions. From the diagram it is evident that each
ion is surrounded by six oppositely charged
ions i.e., each Cl– ion is surrounded by 6 Na+
ions and similarly each Na+ ion is surrounded Figure 5.35 NaCl crystal structure
by 6 Cl– ions.
e.g. NaCl, LiCl, KBr, AgCl, AgBr, MgO and CaO
3. Cesium chloride
The cesium chloride structure is much
less common than the rock salt structure and
is shown in Figure 5.36. This structure has a
unit cell with each lattice point occupied by a
halide ion and a metal cation at the cell centre
or vice versa. CsCl, CsBr and CsI are good
examples of this type of structure.
Figure 5.36 CsCl crystal structure

4. Zinc blende
Zinc blende (ZnS) occurs in two polymorphic forms: the sphalerite-type
and the wurtzite-type structures. In both the sphalerite and wurtzite structures
zinc is surrounded by four sulpurs in tetrahedral coordination, but in sphalerite
the zinc atoms are arranged in a face-centered cubic lattice, whereas in wurtzite
they are approximately in positions of hexagonal closest packing.

Sphalerite (face-centered cubic ZnS)

The atomic arrangement in sphalerite is like that in diamond in which the
carbon has been replaced by equal amounts of Zn and S. In ZnS, anions (Zn2+)
 Crystal Physics 179

occupy the FCC unit cell atom positions and

cations (S2–) occupy the tetrahedral intersti-
tial positions of the FCC unit cell as shown
in Figure 5.37. Semiconductor materials like
CdS, InAs and InSb are the examples of this
type.

Wurtzite (hexagonal ZnS) Figure 5.37 Sphalerite crystal structure

Wurtzite structure is shown in Figure

5.38. The sulphide ions lie in a hexagonal
close-packed arrangement. The insertion of
zinc ions into the tetrahedral holes causes the
structure to expand so that the sulphide ions
are not in contact with each other.
e.g. ZnO, BeO, MnS and AgI

5. Fluorite and antifluorite

The fluortie and antifluorite structures
Figure 5.38 Wurtzite crystal structure
are both based on expanded FCC lattices.
CaF2 , UO2 and PbO2 are the examples for flu-
ortie structure. It has the cations forming the
lattice with the anions occupying both types
of tetrahedral hole.
The antifluorite structure is the inverse
of the fluorite structure with the anions form-
ing the lattice and the cations occupying the
tetrahedral holes. K2O, Li2O, Na2O, and Na2S
are the examples for anti-fluortie structure

Figure 5.39 Fluorite crystal structure

180 Engineering Physics - I

Comparison of some crystal structures

Table 5.3 gives the comparison of properties of some crystal structures discussed
earlier.
Table 5.3 Comparison of crystal structures

Body Hexago-
Simple Face cen-
centered nal closed Diamond
S.No Properties cubic tered cubic
cubic packed cube (DC)
(SC) (FCC)
(BCC) (HCP)
Volume of
1 a3 a3 a3 a3
unit cell
No. of atoms
2 1 2 4 6 14
per unit cell
Co-ordination
3 6 8 12 12 4
number
Atomic radius
4
(r)
5 Packing factor 0.52 0.68 0.74 0.74 0.34
Iron, Copper, Magne- Germa-
Polo- Barium, Alumi- sium, nium,
6 Examples
nium Tung- num, Zinc, Silicon,
sten Nickel Titanium Carbon

5.16 GRAPHITE STRUCTURE

The mineral graphite is one of the
allotropes of carbon. Unlike diamond,
graphite is an electrical conductor, and can
be used, for instance, in the electrodes of
an arc lamp. Graphite holds the distinction
of being the most stable form of carbon
under standard condition. Therefore, it is
used in thermo chemistry as the standard
state for defining the heat of formation of
carbon compounds.
Figure 5.40 shows the graphite
structure. The carbon atoms are arranged Figure 5.40
 Crystal Physics 181

in layer or sheet molecular structure. Graphite is formed when carbon atoms use
only three of their possible covalent bonds. Thus they leave one valence electron
helps to form metallic type bond which holds the sheets together with a spacing
of about 3.4 A.U. but the carbon atoms in the layers are covalent bonded and the
spacing between the atoms in the each layer is about 1.42 A.U.

5.17 POLYMORPHISM AND ALLOTROPY

1. A change in temperature or pressure, if not accompanied by melting or
vapourisation, may cause a solid to change its internal arrangement of
atoms.
2. The ability of a material to have more than one structure is called
polymorphism
3. If the change in structure is reversible, then the polymorphic change is
known as Allotrophy.
4. So Allotrophy is a phenomenon by which an element can have more than one
structure and in all structures there is no change in the chemical properties
but there are changes in the physical properties.
Example
Table 5.4 Comparison of crystal structures

Metal Temperature Range °C Crystal structure

Iron Upto 910 °C BCC, a - phase
910 - 1400 °Cv FCC, g - phase
1400 - 1539 °C (M.Pt) BCC, d - phase
Cobalt Room temperature HCP structure
Above 477 °C FCC structure

5. Another example, consider the allotrophic forms of carbon. Diamond and

Graphite are the two allotrophic forms of carbon. Diamond has a structure
which is a combination of two inter penetrating FCC sub lattices. The
atoms of the diamond are united by covalent bonds. Thus it acts as a
good electrical insulator and it is a hard one.
182 Engineering Physics - I

But in graphite, carbon atoms are arranged in regular hexagons in flat

parallel layers such that each atom is linked by the neighbouring atoms.
However there is no strong bonding between different layers which are
easily separable from each other. This is the reason for softness and
lubricating action of graphite. Meanwhile in each hexagonal layer, the
carbon atoms are united by covalent bonds or by metallic bonds by
loosing one valence electron. Due to the presence of metallic bonds, the
graphite acts as a good electrical conductor.
6. Other examples: Ti, Li, etc,…. Also exhibit polymorphic or allotropic
changes.

5.18 IMPERFECTIONS IN CRYSTAL

The properties such as mechanical strength, ductility, crystal growth,
magnetic hysteresis, condition in semiconductors, dielectric strength are affected
by the imperfections present in crystal. Hence these properties are said to be
structure sensitive whereas some properties of materials such as density, electri-
cal conductivity, stiffness are said to be structure insensitive.
Crystallographic defects are
1. Lattice vibrations (or) phonons
2. Points defects
a. Vacancies
i. Schottky defect
b. Interstitial defects
i. Frenkel defect
c. Compositional defects
i. Substitutional impurity
ii. Interstitial impurity
d. Electronic defects
3. Line defects
a. Edge dislocation
b. Screw dislocation
 Crystal Physics 183

4. Surface defects
a. Grain boundaries
b. Twin boundaries
c. Tilt boundaries
d. Stacking fault
5. Volume defects

1. Lattice vibrations
Atoms do not remain stationary in their designated lattice positions but
they vibrate about their mean positions. Their frequency of vibration depends on
the temperature. These vibrations of atoms play a fundamental role in affecting
certain properties such as specific heat and electrical resistance of materials.

2. Point defects
In a solid, all the atoms have vibrational energy and at all temperatures above
absolute zero, there will be a finite number of atoms which have sufficient energy
to break the bonds which hold them in their equilibrium position. When the
atoms become free from their lattice sites, they give rise to point defects. The
point defects arise due to the presence of impurity atoms also.

Figure 5.41 Point defects in metallic crystals

184 Engineering Physics - I

The most common imperfections in impure metallic crystals are illustrated

in Figure 5.41. If an atom is missing from its regular site, the defect produced is
called vacancy. If the matrix atom occupies its own interstitial site, the defect is
called self-interstitial.
If a foreign atom occupies the position of matrix atom, it is called substitu-
tional impurity atom. If the foreign atom occupies the interstitial position of the
matrix atoms, it is called interstitial impurity atom. In addition to these defects,
divacancies and trivacancies may exist in the crystals.

Point defects in ionic solids

For ionic solids, Frenkel and Schottky defects are likely to form. An atom
may leave its regular site and may occupy nearby interstitial site of the matrix
giving rise to two defects simultaneously i.e. one vacancy and other self-intersti-
tial. These two defects together is called Frenkel defect. This defect occurs only
for cations because of their smaller size as compared to the size of anions.

Figure 5.42 Points defects in ionic solids

When cation vacancy is associated with an anion vacancy the defect is

called Schottky defect. This defect is more common in ionic solids because the
lattice has to maintain electrical neutrality. The effect of these defects on some of
the properties is as below:
1. They increase the electrical resistivity.
 Crystal Physics 185

2. They increase the hardness and tensile strength due to distortion of the
lattice.
3. Vacancies increase the kinetics of diffusion and phase transformation.
Vacancies and self-interstitials are produced during the plastic
deformation of metals and alloys and by high-energy particle irradiation. As the
temperature increases, the vacancy concentration also increases and the same
can be retained by rapid cooling from high temperature to low temperature. The
equilibrium vacancy concentration at any temperature is given by:
nv = nt e(-E/kT)
nv = Equilibrium number of vacancies.
nt = Total number of atomic sites
E = Energy of formation of a vacancy
k = Boltzmann’s constant
T = Absolute Temperature in Kelvin

Problem
The fraction of vacancy sites in a metal is 1 × 10–10 at 500° C. What will be the frac-
tion of vacancy sites at 1000°C.
186 Engineering Physics - I

5.19 ELECTRONIC DEFECTS

This arises due to errors in charge distribution in solids. Due to electric
field, these defects are free to move in the crystal. Therefore electronic conductiv-
ity of certain solids occur and their reactivity increases.

3. Line defects
A part of a line of atoms will be missing from its regular side and this
missing row of atoms is called as dislocation. As the plane of atoms lie only partway
through a crystal, the edge of such a plane is a defect in the form of a line and
hence it is called as line defect. The movement of dislocation is necessary for
plastic deformation. These defects are responsible for the useful property of
ductility in metals, ceramics and crystalline polymers.

Types of dislocations
1. Edge dislocation
2. Screw dislocation
 Crystal Physics 187

Edge dislocation
This dislocation line can be considered as the defect due to the
insertion of an extra half plane of atoms. If this extra half plane of atoms is above,
the line defect is called as positive dislocation and it is denoted by the symbol
^. If this extra half plane of atoms is below, the defect is negative dislocation
which denoted as T. The lattice will be in distorted state above and below the
dislocation line. For positive dislocation, the lattice above the line is in
compression while it is in tension below the line. The reverse will be the case for
negative dislocation. The more inter-atomic spacing below the extra half plane
of atoms for positive dislocation and above the extra half plane of atoms for
negative dislocation favours segregation of interstitial atoms and impurities. The
dislocation lines can also be described by Burgers vector (b).

Figure 5.43 Burger vector and Burgers circuit for an edge dislocation

The dislocation can be completely described if the Burgers vector and the
orientation of the dislocation line are known. The Burgers vector indicates how
much and in what direction the lattice above the slip plane appears to have been
shifted with respect to the lattice below the slip plane.
188 Engineering Physics - I

Burgers vector of a dislocation line can be found out by using Burgers loop
or circuit method. Burger circuit or loop is formed by taking equal integral
lattice translations in each pair of parallel sides in the region of interest.
Such a circuit would close itself in a perfect region of the crystal i.e. a region
with no dislocations will form a closed circuit. The circuit fails to close itself
in the region containing a dislocation. The closer failure distance i.e. the vector
necessary to close the circuit is called Burgers vector of the dislocation line.
Burgers vector is perpendicular to the dislocation line. An incomplete plane in a
crystal results in an edge dislocation.

Screw dislocation
In screw dislocation, atoms are displaced in two separate planes
perpendicular to each other. It can be imagined as being produced by cutting the
crystal partway through with a knife and then shearing one part of the crystal
with respect to the other part parallel to the cut. The name screw dislocation is
given because it transforms successive atomic planes into the surface of a helix
around the dislocation line. The Burgers vector is parallel to the dislocation line.
Such a dislocation has neither tensile nor compressive stresses but has shear
stresses.

Figure 5.44 Screw dislocation

Dislocations come into the materials during the solidification or by

mechanical processing of metals. The number of dislocation is expressed by
 Crystal Physics 189

dislocation density. Dislocation density is the number of dislocations intersect-

ing a unit cross-sectional area in lines/cm2.
The dislocation density of well annealed material is approximately 104 to
106 line/cm2. If the annealing is done more carefully, the dislocation density reduces
to 102 lines/cm2. It increases with the degree of cold work and can be
approximately 5 × 1011 lines/cm2 for heavily cold worked materials.
Dislocation lines can end at the surface of a crystal and at grain boundaries,
but never inside a crystal. Therefore, it clearly indicates that dislocation must either
form closed loops or branch into other dislocations. Dislocations have a strong
effect on deformation characteristics and mechanical properties. They also
influence the recrystallisation temperature, phase transformation
characteristics, electrical properties and corrosion resistance of materials. The
designation ‘Screw’ for this lattice defect is derived from the fact that the lattice
planes of the crystal spiral the dislocation line.

4. Planar defects or surface imperfections

It arises due to change in the stacking of atomic planes during solidifica-
tion or mechanical and thermal treatments. The change may be of the orientation
of the planes or of the stacking sequence of the planes. They are of two types:
External surface imperfections and Internal surface imperfections.

External Surface Imperfections

The atoms present in the surface possess higher energy than the
interior atoms since they are surrounded by atoms on one side only. This external
surface imperfections represent the defects present on the boundary or the external
surface.
Internal surface imperfections
1. Grain boundaries
2. Tilt boundaries
3. Twin boundaries
4. Stacking faults
190 Engineering Physics - I

Grain boundaries
These are the defects, which sepa-
rate grains of different orientation from
each other in a polycrystalline material
during nucleation or crystallization. The
following Figure 5.45 shows the grain
boundary in a polycrystalline material in
which two randomly oriented grains have Figure 5.45 Grain boundary
a region of transition at the grain boundary
where the atomic packing is imperfect.
Grain boundaries are observed during the solidification of polycrystalline
materials. Area of the grain boundary depends on the grain size of the material,
and increases with decrease in grain size.

Tilt boundary or Low angle boundary

It is composed of edge dislocation lying one above the other in boundary.
The angle of tilt will be

b - magnitude of the Burger’s vector

h - average vertical distance between
dislocations
It consists of edge dislocations
lying one above the other in the boundary.
These defects affect the deformation behaviour,
mechanical properties and recrystallisation
temperature of materials. It also influence the
electrical properties and corrosion resistance of
materials.
Figure 5.46
Twin boundaries
These are the boundaries in the grains at which the atomic arrangement
on one side of a twin boundary is the mirror reflection of the atoms on the other
side. The region between the pair of boundaries is called the twinned region. The
 Crystal Physics 191

volume of the material, which has an orientation similar to the mirror image of
the matrix orientation, is called a twin. Twins which form during the process of
recrystallisation are called annealing twins and those which form during plastic
deformation of the materials are known as deformation twins.

Figure 5.47

Stacking faults
A stacking fault, which is a surface imperfection, arises from the stacking
of one atomic plane out of sequence on another while the lattice on either side of
the fault is perfect. Hexagonally close packed and face centred cubic structures
are described by stacking of identical close packed planes one over the other.
HCP structure is produced by the stacking sequence of the type ABABAB.
In which any one atom from the second plane occupies any one interstitial site of
the first plane. Third plane is stacked similar to first and fourth similar to second
and so on. For FCC structures, the stacking sequence is ABCABCABC… First
two planes are stacked in a similar way to HCP and third plane C is stacked
in a different manner than the first two. Stacking of the third plane is in such a
manner that any one atom from the third plane occupies a common interstitial
void of the first two planes. Fourth plane is stacked similar to first, fifth plane is
stacked similar to second and sixth plane similar to third and so on.
The stacking fault may change the sequence of FCC crystal i.e. ABCAB-
CABC … to ABCABCABABCABC … The stacking fault is due to the missing of C
plane of atoms after the eighth plane. This defect can be regarded as a thin region
of HCP stacking in a basically FCC crystal.
192 Engineering Physics - I

Intrinsic fault results in one break whereas extrinsic fault results in two
breaks in the stacking sequence. The stacking faults may occur during crystal
growth.

Figure 5.48

5. Volume Defects
When there is only small electrostatic dissimilarity between the stacking
sequences of close packed planes in metals, these volume defects arise. Volume
imperfection are cracks, when clusters of atoms are missing, a large vacancy
 Crystal Physics 193

or void is obtained. Foreign particle inclusions, large voids or non-crystalline

regions which have the dimensions of the order of 20 A° are also called as volume
imperfections.

Review Questions

Short questions
1. What is crystal?
2. State the differences between crystalline and non crystalline solids.
3. Define space lattice
4. Define basis of a crystal structure
5. Define unit cell of a crystal
6. What are the lattice parameters of a crystal?
7. Define the term primitive cell
8. What are the classifications of crystal systems?
9. What are Bravais lattices?
10. Define the term co-ordination number of a crystal.
11. Define the term atomic radius and packing factor
12. What are Miller indices?
13. What are point defects? (or) Zero dimensional defects?
14. What are Frankel and Schottky defects?
15. What is a line defect (or) a one dimensional defect?
16. What is edge dislocation?
17. What is screw dislocation?
18. What is meant by stacking fault?
19. What are the difference between edge and screw dislocation?
194 Engineering Physics - I

20. What is meant by polymorphism and allotropy?

21. Define Burger vector.

Descriptive questions
1. Explain the various types of crystal systems with examples
2. Describe the Bravais lattices of seven crystals systems with neat sketches
3. Explain the structure of simple cubic system
4. Explain the characteristics of a unit cell of BCC structure
5. Explain the characteristics of a unit cell of FCC structure
6. Explain the structure of HCP structure. Derive the relation between c and
a and also calculate the atomic packing factor of HCP structure
7. Define the terms ‘co-ordination number’, ‘atomic radius’ and ‘packing
factor’. Calculate the above for SC, BCC and FCC structures.
8. What are Miller indices? How are they determined?
9. Show that for a cubic lattice the distance between two successive plane
(h k l) is given by

10. Explain the following

a. NaCl structure b. ZnS structure
c. Diamond structure d. Graphite structure
11. Explain the various types of crystal defects.