SOLID STATE PHYSICS

UNIT IV
CHAPTER

CRYSTAL STRUCTURE
1.1 INTRODUCTION
When two atoms are brought together, two kinds of forces: attraction and repulsion come into play.
The force of attraction increases rapidly as the separation between atoms, decreases. At small distances
the force of repulsion comes into being and increases more rapidly with further decrease in inter-
atomic distance. At distance r = r
0
, attractive force becomes equal to the repulsive force and at this
distance the interaction energy acquires minimum value and the atoms form a bound state. The
minimum energy corresponds to the equilibrium-state. When a large number of atoms are brought
together, the atoms in equilibrium-state, arrange themselves to form a closed pack structure, called
solid. Thus, the forces of interaction between the structural particles (atoms, ions, group of atoms)
are responsible for the existence of solids. The force of attraction between the particles prevents them
from flying apart and the force of repulsion prevents them from merging.
Fig. 1.1.1 Variation of inter-atomic force and potential energy with distance
Solids occur in two forms: Crystalline and amorphous. A crystalline solid is one in which atoms
or other structural units are arranged in an orderly repetitive array. That is, a crystalline solid exhibits
long-range orders.
Amorphous (non-crystalline) solids do not show long range periodicity. An amorphous substance,
such as glass, is actually regarded as a super-cooled liquid that differs from ordinary liquid in its
physical properties. Usually viscosity is used to differentiate a liquid from amorphous solid. If the
coefficient of viscosity is less than 10
15
poise, it is called liquid, if it is greater than this, it is a
solid. The transition from liquid to amorphous-state and vice-versa is gradual whereas the transition
between a liquid and crystalline solid is sharp.
1.2 SPACE LATTICE OR CRYSTAL LATTICE
Space lattice is a geometrical abstraction. To have its meaning, imagine a network of straight lines
constructed in such a way that it divides the entire space into identical volumes. The points of
intersection of these lines are called lattice points. The network of points in three dimensions, in which
the surrounding of each point is identical with the surrounding of other points, is called space lattice.
By associating each lattice point with a single atom or group of atoms, called basis, crystal structure
results. Thus, for every crystal there is a network of lattice points, which are occupied by either a
single atom or group of atoms.
Fig. 1.2.1 Space lattice and fundamental vectors a, b and c
In 1848, a Russian mathematician Bravais showed that there are just 14 ways of arranging points
in space lattice such that all the lattice points have exactly the same surroundings. Such lattices are
called Bravais lattices. From these 14 space lattices, an unlimited number of different crystal structures
can be made.
Fig. 1.2.2 Two dimensional space lattice spanned by basis vectors a and b
For any type of lattice, there exists three fundamental translation vectors a, b, and c, not lying
in a plane, in terms of which any lattice point can be specified. A translation operation T is defined
by
T = n
1
a + n
2
b + n
3
c ...(1.2.1)
where n
1
, n
2
, n
3
are integers. Thus means that by applying the operation T to a point r we reach
another point r', which has the same environment as point r.
r' = r + T = r + n
1
a + n
2
b + n
3
c ...(1.2.2)
The set of points r' given by Eqn. (2) for all possible values the integers n
1
, n
2
, and n
3
defines
the space lattice.
1.3 UNIT CELL
A parallelepiped formed by fundamental vectors a, b and c of space lattice is called unit cell. Each
crystal is built up of a repetitive stacking of unit cells each identical in size, shape and orientation.
The unit cell with basis is thus the fundamental building block of the crystal. A unit cell is always
drawn with lattice point at each corner, but there may also be lattice points at the center of some of
the faces or at the body center of the cell. Although there are infinite number of ways of choosing
the unit cell, but the simplest way is conventionally accepted.
Primitive Cell
A unit cell with lattice points at its corners only is called primitive cell. Thus, there is only one lattice
point to each primitive cell. It is also defined as the smallest unit cell in volume of space lattice.
Basis vectors: A set of linearly independent vectors a, b, c, which can be used to define a unit
cell, are called basis vectors.
Primitive basis vectors: A set of linearly independent vectors that define a primitive cell is
called primitive basis vectors.
1.4 PARAMETER OF A UNIT CELL
A unit cell is specified by six quantities: three edges a,
b, c and three angles o, , defined in the figure. These
quantities are termed the parameters of the unit cell. In
crystallography, the distances are expressed in terms of
a, b, c.
The 14 space lattices with conventional unit cell,
some by their primitive cells and others by non-primitive
cells are shown in the Fig. (1.4.2). The 14 lattices may
be grouped into 7 crystal systems, each of which has in
common certain characteristic symmetry elements.
Fig. 1.4.1 Parameters of a unit cell
Fig. 1.4.2 14 Bravais space lattices with conventional unit cell
Table 1.4.1: Seven Crystal Systems
System Bravais lattice Symbol Unit cell characteristics
1 Triclinic Simple P a b c, o 90
2 Monoclinic Simple P a b c, o = 90
0

Base centered C
3 Orthorhombic Simple P a b c, o = = 90
Base centered C
Body centered I
Face centered F
4 Tetragonal Simple P a = b c, o = = 90
Body centered I
5 Cubic Simple P a = b = c, o = = 90
Body centered I
Face centered F
6 Hexagonal Simple P a = b c, o = 120, = = 90
7 Trigonal Simple P a = b = c, o = = 90
(Rhombohedral)
Fig. 1.4.3 Primitive (rhombohedral) and non-primitive (cubic) unit cells for f.c.c. lattice
The crystallographic description of crystal requires specification of shape and size of unit cell
and distribution of matter in it. The choice of unit cell is not unique. While choosing the unit cell,
emphasis is given on the symmetry exhibited by it. If a non-primitive cell exhibits more symmetry
than a primitive cell, the former is preferred. For example, in F.C.C. lattice the simplest primitive
cell is rhombohedral with three fundamental translation vectors, each of length L/2, which make
angles of 60 with respect to each other Fig. (1.4.3). A non-primitive cubic unit cell of length L
exhibits strong symmetry and therefore, it preferred to primitive cell. The rhombohedral unit cell
has volume (L
3
)/4 whereas the cubic unit cell has volume L
3
.
Fig. 1.4.4 Primitive and non-primitive (conventional) unit cell for b.c.c. lattice
Similarly for B.C.C. lattice, because of strong symmetry shown by cubic unit cell, it is
conventionally accepted in comparison to primitive rhombohedral unit cell, which can be constructed
with primitive vectors of length ( L3)/2, The primitive cell has volume (L
3
)/2 and non-primitive
cubic unit cell has volume L
3
.
1.5 SYMMETRY
An object is said to have symmetry if it coincides with itself as a result of some kinds of its spatial
movement or rotation through some angle about an axis. The larger the number of ways by which
the object can be made to coincide with itself, the more symmetric it is said to be.
By symmetry element we mean an operation by which equivalent points of the object or space
lattice are brought into coincidence. All the possible symmetry operations on an object can be expressed
as a linear combination of following four symmetry elements.
(i) n-fold rotation axis (Symmetry axes): If a rotation of a lattice about an axis through an
angle 2r/n brings a lattice into a position indistinguishable from its initial position, then
the axis is a n-fold rotation symmetry axis. The possible values of n are 1, 2, 3, 4 and 6.
Five-fold rotational symmetry in a crystal lattice is impossible. Obviously any axis of a
lattice is a one-fold symmetry axis.
(ii) Plane of symmetry: This type of symmetry exists if one half of the lattice coincides with
itself as a result of the mirror reflection of its points in a certain plane. This plane is
called the symmetry plane of the lattice.
(iii) Inversion center (center of symmetry): A crystal lattice is said to possess the center of
symmetry if it coincides with itself upon inversion through a certain point. This point is
called the center of symmetry. By inversion operation the position vector r of a lattice
point is converted into r.
(iv) Rotation-inversion axis: If a lattice remains unchanged upon rotation about an axis through
angle 2r/n, n = 1, 2, 3, 4 and 6, followed by inversion about a lattice point through which
the rotation axis passes, it is said to have rotation-inversion axis. This kind of symmetry
is indicated in the figure.
The point A takes the position A' upon rotation through angle r. Upon inversion about point
O, the point A' goes to A". Thus, A and A'' are related by two-fold rotation-inversion axis.
Fig. 1.5.1 Two-fold rotation-inversion axis
1.6 MILLER INDICES
A plane in a crystal is specified in terms of Miller indices. To find the Miller indices of a plane,
following procedure is used.
(i) Determine the intercepts of the plane on crystal axes in terms of fundamental vectors a, b
and c.
(ii) Take the reciprocal of these numbers in order. Reduce them to three smallest integers having
the same ratio.
(iii) Enclose these numbers in parentheses as (h k l).
The Miller indices (h k l) denote a set of parallel planes.
For example consider a plane with intercepts 4a, 6b and 3c on the crystal axes. In terms of
axial units, the intercepts are 4, 6, 3. The reciprocals of these numbers are
1 1 1
, ,
4 6 3
. By multiplying
each of these numbers with lowest common multiple 12, these are reduced to smallest integers 3, 2,
4. The Miller indices of the plane are (324).
Fig. 1.6.1 Miller indices of a plane cutting intercepts 4a, 6b, 3c on crystallographic axes
If a plane intersects the crystal axes on the negative side of origin, the corresponding index is
negative. By convention a minus sign is placed above the corresponding index. A plane intercepting
the crystal axes at 4a, 2b, c, has Miller indices (12 4).
Miller indices of some important planes of cubic lattices are shown in the Fig. (1.6.2).
Fig. 1.6.2 Miller indices of some important planes of cubic lattices
1.7 INTERPLANAR DISTANCE
To find the interplanar spacing for the set of planes with Miller indices (hkl), take the origin on any
one plane of this set and erect axes in the directions of crystal axes a, b and c. The interplanar spacing
d for the planes of indices (hkl) is equal to the distance from origin to the nearest plane of the set
under question. The distance d is measured along the normal drawn from origin to the plane (hkl).
Let the normal to the plane make angles o
1
, o
2
and o
3
with a-axis, b-axis and c-axis respectively.
The plane (hkl) intersects a-axis at a/h, b-axis at b/k and c-axis at c/l.
Fig. 1.7.1 Interplanar spacing for set of planes (hkl )
From Fig. (1.7.1) we see that
1 2 3
cos , cos , cos
/ / /
d d d
a h b k c l
For orthogonal axes,
cos
2
o
1
+ cos
2
o
2
+ cos
2
o
3
= 1
Hence,

1
+ + 1
1
]
2 2 2
2
2 2 2
1
h k l
d
a b c

+ +
2 2 2
2 2 2
1
d
h k l
a b c
...(1.7.1)
For cubic system a = b = c

+ +
2 2 2
a
d
h k l
...(1.7.2)
Direction in a Crystal
The direction in a crystal is expressed as a set of integers which has the same ratio as the components
(in terms of axial units a, b, c) of the vector in that direction. For example, the direction of vector
ha + kb + lc is expressed as [hkl]. In a cubic system the direction [hkl] is perpendicular to the plane
(hkl) but this is not true for other systems.
Position of a Point in Unit Cell
The position of a point in unit cell is specified in terms of its coordinates, which are expressed in
terms of unit cell edges. For example, [[324]] is reached by moving along a-axis a distance three
times the length of vector a, then parallel to b-axis a distance twice the length of vector b and finally
parallel to c-axis a distance four times the length of vector c. The indices of a point are written
inside a double square bracket. The indices of a point with coordinates x = 3a, y = 4b, z = 2c are
written as [[ 342 ]].
1.8 SOME CHARACTERISTICS OF CUBIC SYSTEM
There are three possible cubic lattice: simple cubic (s.c.), body centered cubic (b.c.c.) and face centered
cubic (f.c.c).
Simple cubic structure: The cubic unit cell for simple cubic lattice is shown in the figure.
There are 8 atoms at the 8 corners of the cell, each corner atom is shared by 8 unit cells that adjoin
at each corner. The share of each corner atom to a unit cell is 1/8 of an atom. Total number of atoms
per unit cell is
1
8 1
8
. Thus, simple cubic cell is a primitive cell. Since 6 equidistant nearest
neighbours surround the atom at one corner, the coordination number is 6.
In a close packing with hard spheres, the hard sphere radius r is given by a = 2r. where a is
length of side of cubic cell. The distance 2r is called the distance of nearest neighbour.
The volume of unit cell V = a
3
Volume of all atoms in a unit cell O =

3
3
4
1
3 6
a
r
Packing fraction f =

0.52
V 6
Simple cubic structure is a loosely packed structure. The only one element polonium forms
simple cubic structure for a particular range of temperature.
Fig. 1.8.1 Simple cubic unit cell
Body centered cubic structure: The conventional unit cell for b.c.c. structure is shown in the
figure. There are 8 atoms at the 8 corners, each shared by 8 unit cells and one atom at the body
center, which wholly belongs to the unit cell. Thus, the total number of atoms per unit cell is
+
1
8 1 2
8
. The b.c.c. is not a primitive cell. The primitive cell is a rhombohedral in shape as
shown in the Fig. (1.4.4). The primitive cell contains only one atom.
In close packing, the hard sphere radius is given by
+
2 2 2
(4 ) ( 2 ) r a a
.
3
4
a
r
Fig. 1.8.2 Calculation of hard sphere radius r in terms of a
Volume of unit cell V = a
3
Volume of all atoms in unit cell O =
3
4
2
3
r
=
_


,
3
4 3
2
3 4
a
Packing fraction f =


3
0.68
V 8
Lithium, sodium, potassium, chromium crystallize in b.c.c. structures.
Face centered cubic structure: The conventional unit cell for face centered structure is shown
in the figure. There are 8 atoms, each shared by 8 unit cells at 8 corners and 6 face-centered atoms,
each shared by 2 cells. The total number of atoms per unit cell is +
1 1
8 6 4
8 2
. Thus, the
conventional unit cell is not a primitive cell.
In close packing, the hard sphere radius is given by
(4r)
2
= a
2
+ a
2
.
2
4
a
r
Fig. 1.8.3 Conventional unit cell for f.c.c. structure
Volume of cubic unit cell V = a
3
Volume of all atoms of unit cell

3
3
4 2
4
3 6
a
r
Packing fraction


2
0.74
V 6
f
F.C.C. is closest packed structure. Ag, Al, Au, Cu, Pb, Pt crystallize in f.c.c. structure.
1.9 HEXAGONAL CLOSE PACKED (H.C.P.) STRUCTURE
The conventional unit cell for hexagonal packed structure is shown in Fig. (1.9.1). This unit cell is
equivalent to three primitive cells. If we consider an atom at the center of basal plane, we see that it
has 6 nearest neighbours in its own plane, 3 in a plane above and 3 in a plane below it. The
coordination number is 12. The number of atoms per unit cell is 6.
OB = a cos 30, OA = (2/3) OB =
3
a
OC
2
= OA
2
+ AC
2
_ _
+

, ,
2 2
2
2
3
a c
a
Fig. 1.9.1 Unit cell for hexagonal packed structure
In an ideal close packing all the 12 neighbours are at the same distance i.e.,
a = a'
.
_ _
+

, ,
2 2
2
2
3
a c
a
Hence
8
1.633
3
c
a
In close packing, hard sphere radius is given by
2r = a
The packing fraction is given by



_


,
3
4
3
2
6 2
0.74
V 6
3 3
2
r
f
a c
Be, Mg, Zn, and Cd are some metals, which crystallize in hexagonal closed packed structure.
1.10 SOME CRYSTAL STRUCTURES
Sodium chloride (rock salt) NaCl structure: The sodium chloride structure results by arranging
Na
+
and Cl

alternately at the lattice points of a cubic lattice. The crystal structure can be thought of
as superposition of two f.c.c. sub-lattices, the lattice points of one sub-lattice are occupied by Na
+
and those of other are occupied by Cl

. The two f.c.c. sub-lattices are displaced from each other by

one-half of the body diagonal of the unit cube. The positions of Cl

and Na
+
are:
Cl

0 0 0 0 0 0
Na
+
0 0 0 0 0 0
Fig. 1.10.1 Conventional unit cell of sodium chloride structure
Six neighbours of opposite kinds surround each ion. The coordination number is 6. The number
of Na
+
per unit cell is +
1 1
8 6 4
8 2
. Similarly the number of Cl

per unit cell is also 4. Thus

there are four sodium chloride molecules in a unit cell.
Cesium chloride structure: In cesium chloride crystal, the Cs
+
lie at the corners of a cubic
cell and Cl

at the body centered position. The CsCl crystal may be thought of as superposition of
two simple cubic lattices, the corner of one sub-lattice lies at the body center of the other. Cesium
ions lie at the lattice points of one sub-lattice and chloride ions at those of the other sub-lattice. Each
ion is at the center of the cube whose corners are occupied by ions of opposite kind. The coordination
number is 8. The number of Cs
+
per unit cell =
1
8 1
8
. The number of Cl

per unit cell is also 1.

So there is one cesium chloride molecule per unit cell.
Fig. 1.10.2 Conventional unit cell of cesium chloride
Summary of properties of some crystal structures
Property SC BCC FCC HCP
Volume of unit cell a
3
a
3
a
3
33a
2
c/2
No. of atoms per unit cell 1 2 4 6
Coordination number 6 8 12 12
Nearest neighbour distance a a3/2 a2/2 a
(2r)
Atomic radius (r) a/2 a3/4 a2/4 a/2
Atomic packing fraction r/6 = 0.52 3r/8 = 0.68 2r/6 = 0.74 2r/6 = 0.74
SOLVED EXAMPLES
Ex. 1. Show that the lattice constant for cubic cell is given by

_

,
1/ 3
A
M
N
n
a
where n = number of molecules per unit cell, M = molar mass, H = density, N
A
= Avogadros
number.
Sol. Let a = length of side of cubic cell.
Volume of unit cell v = a
3
Molar volume of crystal V
M
=

M
This volume contains N
A
molecules.
Volume available to a single molecule

A
M
N
m
v
If there are n molecules in a unit cell, then the volume of unit cell is

A
M
N
n
v
This is equal to a
3
. Hence

_

,
1/ 3
A
M
N
n
a
Ex. 2. Show that the number of lattice points per unit area of a lattice plane with interplanar
spacing d is given by

s
nd
where n = number of lattice point per unit cell and O is volume of unit cell.
For crystal with orthogonal axes, abc , the above formula reduces to

s
nd
abc
Sol. Consider a crystal region of volume V containing N lattice planes, each of area S. Let p
s
represent the number of lattice points per unit area of lattice plane. The number of lattice points in
the volume V is
N' = p
s
S N ...(1)
This number may also be calculated as follows.
Let O = volume of unit cell
n = number of lattice points per unit cell.
The number of unit cells in volume V is

V
.
The number of lattice points in volume V is N' =

V
n
Thus

V
SN
s
n
Whence

V
SN
s
n
...(2)
If d is interplanar spacing of the lattice planes then
V = S d N ...(3)
Making use of (3) in (2), we get

s
nd
...(4)
For crystals with orthogonal axes (cubic, tetragonal, orthorhombic) O = abc. We have

s
nd
abc
...(5)
In cubic crystal O = a
3
we have

3
s
nd
a
...(6)
Ex. 3. The rock salt (NaCl) has fcc structure and contains 4 molecules per unit cell. Calculate the
lattice constant for the crystal.
Molecular weight of NaCl = 58.45 kg/kmol
Density = 2180 kg/m
3
Avogadro Number N
A
= 6.02 10
26
kmol
1
Sol.

_ _

, ,
1/ 2
26
A
M 4 58.45
5.63
N
2180 6.02 10
n
a
Ex. 4. Find the ratio of intercepts on the crystal axes by plane (231) in a simple cubic lattice.
Sol. Let x
1
, x
2
, x
3
be the intercepts by the plane on the axes. In terms of axial units the intercepts
are

1 2 3
, ,
x x x
m n p
a b c
where m, n, p are numbers.
Now

1 1 1
: : 2 : 3 : 1
m n p
.

1 1 1
: : : :
2 3 1
m n p
= 3 : 2 : 6
x
1
: x
2
: x
3
= 3 : 2 : 6
Ex. 5. Find the ratio of interplanar distances of planes (100), (110) and (111) in a simple cubic
lattice.
Sol.
+ +
2 2 2
hkl
a
d
h k l

+ +
100
1 0 0
a
d a

+ +
110
1 1 0 2
a a
d

+ +
111
1 1 1 3
a a
d

100 110 111

1 1
: : 1: :
2 3
d d d
Ex. 6. In a tetragonal lattice a = b = 2.5 , c = 1.8 . Calculate the lattice spacing between the
(111) planes.
Sol.
+ +
2 2 2
2 2 2
1
hkl
d
h k l
a b c


+ +
111
2 2 2
1
1.26
1 1 1
2.5 2.5 1.8
d
Ex. 7. Calculate the density of lattice points in the lattice plane (100) in a simple cubic lattice of
lattice constant a = 2.5 .
Sol. Density of lattice points
3
s
nd nd
abc
a
For simple cubic lattice n = 1, d
100
= a = 2.5 10
10
m
.

19 2
3 2 10 2
1 1
1.6 10 m
(2.5 10 m)
s
a
a a
Ex. 8. Zinc has hcp structure. The height of unit cell is 4.9 , the nearest neighbour distance is
2.7 . Calculate the volume of the unit cell.
Sol. Lattice constant a = 2r = 2.7
Volume of unit cell

2
3 3
V
2
a c
=


10 2 10
3 3(2.7 10 m) (4.9 10 m)
2
= 9.4 10
29
m
3
Ex. 9. Calculate the volume of unit cell for a hexagonal close packed structure in which the atom
occupying the lattice points has radius of 1.6 .
Sol. Volume of the unit cell

2
3 3
V ,
2
a c
where a = 2r = 3.2
and
8
5.2
3
c a
. V = 1.4 10
28
m
3
QUESTIONS AND PROBLEMS
1. Distinguish between amorphous and crystalline solids. Define the following:
(a) Space lattice
(b) Unit cell
(c) Primitive cell
(d) Basis
2. Describe the seven system of crystals with examples. Give diagrams of simple cubic, body
centered and face centered cubic cells. Calculate the number of atoms per unit conventional
unit cell.
3. What are Miller indices? How are they specified?
4. Derive an expression for inter-planar spacing for orthogonal systems.
5. Obtain an expression for the number of lattice points per unit area of a lattice plane in a cubic
crystal.
6. Obtain an expression for the lattice constant of a cubic crystal in terms of molar mass and
density of the crystal.
7. With diagram describe the structure of sodium chloride and cesium chloride structure.
8. Calculate the number of atoms per unit area in the plane (100), (110), (111) in simple cubic
structure of lattice constant 2.5 .
9. Copper has fcc structure. Radius of copper atom is 1.28 . Calculate the inter-planar distance
for plane (111).
[Hint: a = 4r/2]
10. Magnesium has hcp structure. Atomic radius of Mg is 1.6 . Calculate the volume of unit cell.