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Unit-IV
Crystallography
Space lattice
An infinite array of points in space (3Dimensions) such that every point has an identical environment as
that of any other point in that array is known as a space lattice.
Basis
An atom or an ion or a group of atoms which is associated with the space lattice to form a crystal is known
as Basis. Basis is a repetitive pattern of atoms or molecules.
Lattice + Basis= Crystal

Fig 4.1
Unit Cell
The smallest geometric figure, which up on regular repetition gives the actual crystal structure, is known as
unit cell.

Lattice Parameters
The intercepts made by the unit cell on the
crystallographic axes are called primitives. The angles
between the 3 crystallographic axes are called inter-axial
or inter-facial angles. The 3 primitives (a, b, c) and the 3
interfacial angles (,,) together are called as lattice
parameters.
Fig 4.2
Primitive Cell
A unit cell which is made up of the 3 primitives as its sides and which encloses only one lattice point in it,
called as a primitive cell.

Crystal Systems
Based on the relation between the 3 primitives and relation between the 3 interfacial angles crystal shapes
have been divided into 7 categories as given below.
S. No Name of the Relation Relation Examples
Crystal between between
System a, b, ,c ,,,
1. Cubic a=b=c ===90o NaCl, Diamond

2. Trigonal a=b=c ==90o As, Sb, Bi, Calcite

3. Tetragonal a=b c ===90o TiO2, SnO2, In

4. Hexagonal a=bc ==90o, =120o Zn, Mg, Cd, SiO2

5. Orthorhombic abc ===90o KNO3, BaSO4,

PbCO3
6. Monoclinic abc ==90o FeSO4, Na2SO4,
CaSO4.2H2O
7. Triclinic abc 90o K2Cr2O7,CuSO4
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The Seven Crystal systems

Cubic Trigonal Tetragonal Hexagonal

Orthorhombic Triclinic
Monoclinic
Fig 4.3
Bravais Lattices
Bravais in 1848 has shown that there exist only 14 possible combinations of crystal groups out of which
there are 7 crystal systems and 4 crystal structures, called as Bravais lattices.
S. No Name of the Types of No. of
Crystal Bravais Bravais
System Lattices Lattices
1. Cubic P, I, F 3

2. Trigonal P 1

3. Tetragonal P, I 2

4. Hexagonal P 1

5. Orthorhombic P, I, F, C 4

6. Monoclinic P, C 2

7. Triclinic P 1

Total 14

The following are some important parameters which are used to describe the crystal structure.

Nearest neighbouring distance (2r): the distance between the centres of two nearest neighbouring atoms
is called nearest neighbouring distance. If r is the radius of the atom, nearest neighbouring distance= 2r.
Atomic radius (r): It is defined as half the distance between the nearest neighbouring atoms in a crystal.
Coordination number (N): It is defined as the number of nearest and equidistant neighbours that an atom
has in a given structure.
Atomic packing factor or fraction (p): It is the ratio of the volume occupied by all the atoms in unit cell to
the total volume of the unit cell.
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Cubic Structures
Simple cubic structure (SC)
The cubic structure in which atoms are present only at the corners is known as a simple cubic structure.

Fig 4.4: Simple cube

 Number of atoms in a unit cell=[(8x1/8) CA]=1
Since each corner atom is shared by eight adjacent cubes, the share of each cube is 1/8 th of the
atom. Hence it is a primitive structure.
 The atomic radius r=a/2 (since any two corner atoms touch each other in this structure, a=2r)
 Coordination number is 6 (since each corner atom is surrounded by 6 nearest and equidistant
neighbours at a distance a, two in each direction on either side of it.)
1x 4  r 3 4  r 3 
 Packing fraction= volume of all the atoms in the unit cell = 3 3  3 3   0.52 or 52%
total volume of the unit cell a 8r 6
 This is a loosely packed structure.
 Example: Polonium

Body centred cubic structure (BCC)

The cubic structure in which atoms are present not only at the corners but also at the body centre is known
as a body centred cubic structure.

Fig 4.5: Body centred cube

 Number of atoms in a unit cell=[(8x1/8) CA +(1)BCA]=2
(There is one full atom at the body centre apart from the corner atoms.)
 The atomic radius r=3a/4 (since the distance from the body central atom to any corner atom is
3a/2, 3a=4r)
 Coordination number is 8
(the body central atom is surrounded by 8 nearest and equidistant corner atoms at a
distance3a/2)
Packing fraction= volume of all the atoms in the unit cell = 2 x 3  r 3r 3
4 3 8 3
    0.68 or 68%
total volume of the unit cell a3 64
3 3
r3 8
 This is a closely packed structure.
 Examples: Na, Fe, Cr, W

Face centred cubic structure (FCC)

The cubic structure in which atoms are present not only at the corners but also at the centre of each face is
known as a face centred cubic structure.
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Fig 4.6: Face centred cube

 Number of atoms in a unit cell= (8x1/8) + (6x1/2) = 4

(six faces give 3 atoms as the share of each face centre is one half of an atom apart from the
corner atoms)
 The atomic radius r=a/22 (any face diagonal covers one face centre and two corners)
 Coordination number is 12 (any corner atom of this structure is surrounded by 12 nearest and
equidistant face central atoms of other unit cells at a distance a/2, 4in its own plane, 4 in the
plane above and 4 in the plane below)
Packing fraction= volumeof all the atoms in the unit cell = 4 x 3 3 r   r3 
4 3 16
 3
3
  0.74 or 74%
total volumeof the unit cell a 8 8r 3 2
 This is a very closely packed structure.
 Eg: Al, Cu, Ag, Au

Diamond cubic structure (DC)

The structure of diamond can be considered as the interpenetration of two FCC sub-lattices of carbon in
such a way that if the origin of one sub-lattice lies at (0,0,0), then the origin of the second sub-lattice lies at
(a/4, a/4, a/4). The two sub-lattices are by ¼ of the cube edge along the body diagonal. The basic lattice
and the atomic positions in the cubic unit cell of diamond projected on a cube face are as shown in the fig.
The fractions denote the height from the base in terms of cube edge.

Fig 4.7: Diamond cubic structure Fig 4.8: Top view of diamond
 Number of atoms in a unit cell = 8 {(8x1/8) [CA] + (6x1/2) [FCA] + 4 [BCA]}
(In this structure, the 8 corners of the cube contribute 1 full atom, the 6 face centers contribute
3 atoms as a whole and there are 4 complete atoms, one each on the four body diagonals)
 The atomic radius r = 3a/8.
 The coordination number of this structure is 4, since each body diagonal atom is surrounded by 4
nearest and equidistant neighbours at a distance 3a/4(a = cube edge), one atom being the corner
from which it has originated and the other 3 are the face centered atoms of the faces intersect at
that corner.
  83 a 
3
8 x 43  r 3
32

  0.34 or 34%
3
 Packing fraction of this structure=
a3 a3
 This is a very loosely packed structure.
 Examples: Si, Ge and gray tin
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Hexagonal Close Packing

In this structure, every unit cell consists of 6 atoms at the corners, an atom at the base centre of each base of a
regular hexagon and 3 atoms in the middle layer of the cell as shown in fig 4.9(a).

Fig 4.9 (a) Fig 4.9(b)

 Number of atoms in a unit cell =6 {(6x1/6) [corners] + 1/2 [base centre]} x2[bases]+ 3 (middle layer)} i.e.,
there will be atoms at corners and at the center of each base contributing 3/2 atoms per base and there are
3 complete atoms in the middle layer)
 Atomic radius r=a/2 (Since any two nearest atoms touch each other)
 Coordination number=12 (Since each base central atom is surrounded by 12 nearest and equidistant
neighbours at a distance a, 6 in its own plane, 3 in the plane above and 3 in the plane below).
 Area of the base= 6 x Area of each triangle= 6 x 12 xbase x height  6 x 12 x 3 a x a  3 3 a 2
2 2
Height of the cell c  8
3 a (a is the edge of the base)
Packing fraction = volume of all the atoms in the unit cell = 6x 43  r 3
total volume of the unit cell Area of thebase x height of the cell
24
 r3  r3
24 24
 a3

 3 3
3
2
 3
3 3 2 2 2
 3 8
3
  0.74 or 74%
2 a xc 2a x 3 a 3 2 xa 3 2
 It is a very closely packed structure.
 Examples: Mg, Cd, Be, Zn, Ti etc.

Direction Indices
The crystallographic direction indices are the vector components of direction, resolved along each of the 3
crystallographic axes which are made into smallest integers.

Fig 4.10: Directions in a cube Fig 4.11: Planes in a cube

Miller indices
The Miller indicies for a plane or set of parallel planes are defined as the smallest integers which have the
same ratio as that of the reciprocals of the intercepts made by the palne on the 3 crystallographic axes.
Miller Indices can be obtained by adopting the following procedure.

1. Find the intercepts the plane makes with three crystallographic axes. Say p,qand r.
2. Take the reciprocals of these numbers i.e. 1/p, 1/q and 1/r.
3. Convert them into smallest integers by multiplying each with LCM.(h:k:l)
4. The plane is now designated & idientified by enclosing these integers in brackets i.e. (h k l).
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Salient features of Miller indices

1. When the plane is parallel to an axis, the intercept is infinity and hence miller index is zero.
2. Negative indices are denoted placing a bar on them.
3. All equally spaced parallel planes are represented by the same set of Miller indices.
4. A plane and a direction having same indices are perpendicular to each other.

Inter planar spacing or Distances of separation between successive (h k l) planes

The distance between any two successive parallel planes in a crystal is called as interplanar spacing (d).
Let (h k l) be the Miller indices of the plane ABC. Let ON = d1 be the normal to the plane passing through
the origin O. Let α’, β’ and γ’ be the angles ON makes with x, y and z axes respectively.
d d dh
Then cos a ' = 1 = 1 = 1 , [1]
OA a a
h
d1 d dk
cos b ' = = 1 = 1 [2]
OB a a
k
d1 d dl
and cos g ' = = 1 = 1 [3]
OC a a
l
Fig 4.12: Parallel planes in a cube
Since cos a ', cos b ' and cos g ' are the direction cosines, the relation for sum of their squares is
cos2 a '+ cos2 b '+ cos2 g ' = 1 [4]
Hence {d1h/a}2 + {d1k/a}2 +{d1l/a}2 =1
a
(or) d1 = ON =
h2 + k 2 + l2
2a 2a
Let A’ B’ C’ parallel to A B C be at a distance OM from the origin. Then its intercepts are , and
h k
2a
. Let ON be extended to a point M, on the plane A’B’C’, so that OM= d2. As α’, β’ and γ’ be the angles
l
made by OM with x, y and z axes respectively, we have
d2 d dh d d dk d2 d dl
cos a ' = = 2 = 2 , cos b ' = 2 = 2 = 2 and cos g ' = = 2 = 2
OA ' 2a 2a OB ' 2a 2a OC ' 2a 2a
h k l
Applying equation [4] and solving, we get
2a
 d2 = OM =
h2 + k 2 + l2
a
Now, the interplanar spacing is d2-d1 = d =
h2 + k 2 + l2