Lecture notes on Crystallography

1 Introduction
A solid in which the atoms are placed in a random manner is called amorphous,
while that in which there is an orderly arrangement of atoms is a crystal. The
atomic arrangement in a material/crystal is called as phase. If there is a change
in the atomic arrangement, then a new crystal will be formed resulting in a phase
change.

2 Lattice
A space lattice can be defined an array of points with each of the points having
its nearby space identical, in a 3-dimensional space. The points correspond to the
mean position of an atom or cluster of atoms in a crystal. These points are known
as lattice points. We may create a space lattice by successive translations of an
initial lattice point. The positioning of points around a lattice point is termed as
the environment of the lattice point. At the next lattice point, the environment will
become identical to the initial point. A crystal structure is obtained when a group of
atoms is identically attached to each lattice point. Such group of atoms associated
to one lattice point is called basis. Hence the combination of a lattice and basis forms
a crystal structure.

Figure 1: Left : Space lattice; Right : A unit cell

A unit cell is defined as the smallest repeating unit in a space lattice when re-
peated over again, results in a crystal of the given substance. The translational
vectors a,b and c are existing across a crystallographic axes, which corresponds to

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the lines drawn parallel to the lines of intersection of any 3 faces of the unit cell but
do not exist in the same plane.
It is usually convenient to choose a parallelopipe whose edges are parallel with
the crystallographic axes and with the shortest possible sides. The volume of a
unit cell is (a × b) · c, and if this volume consists of only one lattice point then it
belongs to a primitive unit cell. a,b,c and the angles α, β and γ are called the lattice
parameters. Suppose there are two or more lattice points in a unit cell, then it is a
non-primitive unit cell.

3 Bravais lattice and crystal systems

The Bravais lattice are the fourteen distinct lattice types which when repeated can
fill the whole 3-dimensional space. They are divided into 7 cubic systems as follows
:

• Cubic : a = b = c and α = β = γ

1. Simple cubic : lattice points at all corners

2. Body-centered cubic : at all corners and one at the centre
3. Face-centered cubic : at all corners and one each at the centre of the six
faces

Figure 2: Simple cubic, Body-centered cubic and Face-centered cubic

• Tetragonal : a = b 6= c and α = β = γ

1. Simple
2. Body-centered

• Orthorhombic : a 6= b 6= c and α = β = γ = 90◦

1. Simple
2. Base-centered : lattice points at all corners, one at the base and another
at op face

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 Figure 3: Tetragonal

3. Body-centered
4. Face-centered

Figure 4: Orthorhombic

• Monoclinic : a 6= b 6= c, α = γ = 90◦ 6= β

1. Simple
2. Base-centered

Figure 5: Monoclinic

• Triclinic : a 6= b 6= c and α 6= β 6= γ

1. Simple

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 Figure 6: Triclinic

• Trigonal/Rhombhohedral : a = b = c and α = β = γ 6= 90◦ < 120◦

1. Simple

Figure 7: Trigonal/Rhombhohedral

• Hexagonal : a = b 6= c and α = β = 90◦ , γ = 120◦

1. Simple

Figure 8: Hexagonal

A summary of the different crystal systems along-with examples is shown below.

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4 Non-bravais lattice
• Some of lattice points is non-equivalent when you look at them from different
orientation.

• Atoms placed at the lattice points are not the same

• Such a crystal is a non-Bravais lattice

• e.g. : a 2-dimensional honeycomb structure

Figure 9: 2D honeycomb structure

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5 Important characteristics of a unit cell
• Number of atoms per unit cell (n)

• Atomic radius (r): The half of the distance between nearest neighboring atoms
in a crystal is known as atomic radius.

Figure 10: Estimation of relation between lattice parameter ‘a’ and atomic radius ‘r’
for a cubic system.

• The distance between the centers of two nearest neighboring atoms. For a
simple cubic it is given by 2r where r is the radius of an atom

• Co-ordination number (N) : The number of equi-distant neighbouring atoms,

that one atom will have. If N is more, the crystal structure will be more
closely packed. The nearest neighboring atoms maybe within same unit cell
or nearest cell.

– Simple cubic : 1 corner atom shared with

∗ 4 atoms from same plane
∗ 1 atom above
∗ 1 atom below
Hence 6 equally spaced nearest neighbor atoms at distance a.
i.e. coordination number is 6
– BCC : Consider the body-centered atom in the cell.
∗ All the eight corner atoms are in contact with the body-centered
atom.
i.e. coordination number is 8.
– FCC : Consider any one of the four face-centered atoms. 1 atom is in
contact with

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 ∗ 4 corner atoms in its plane
∗ 4 corner atoms above its plane
∗ 4 corner atoms below its plane of another unit cell
i.e. coordination number of FCC unit cell is 12.

• Atomic Packing factor : ratio of the volume of atoms occupying a unit cell, to
that of the entire unit cell.

6 Estimation of atomic packing factor for different

cubic systems
6.1 Simple cubic
As mentioned earlier, there will be one lattice point at each of the eight corners of
the unit cell. Each atom at the corner will be shared by 8 unit cells. So, each atom
at the corner shares 1/8th of an atom.

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• Total no. of lattice points = 8 × 8 = 1.

• Volume of all the atoms, v = 1 × 43 πr3

• Volume of the unit cell, V = a3 = (2r)3

v π
• Therefore, density of packing/packing factor, P F = V = 6 = 0.52

6.2 Body-centred cubic

one lattice point at each corner, one at the body centre.

√
a 3
• 2r = 2

• No. of atoms per unit cell, n = 2

• v = 2 × 34 πr3
64r 3
• V = a3 = √
3 3
√
v 3π
• AP F = V = 8 = 0.68

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6.3 Face centred cubic
one atom at each corner, one each at the center of each faces.

• Total no. of atoms = 18 ∗ 8 + 6 ∗ 1

2 =4
√ √
• a = 4r/ 2 ⇒ 2r = a 2/2

• No. of atoms per unit cell, n = 4

• v = 4 × 34 πr3
64r 3
• V = √
2 2
π
• Hence, AP F = √
3 2
= 0.74

7 Miller Indices
A crystal lattice consists of a set of parallel equidistant planes called as lattice planes
which will pass through the lattice points. The planes can be designated using 3
numbers h, k, l called as Miller indices.

7.1 Estimation of the indices

• Get the co-ordinates of the inter-
cepts along the axes

• Convert the intercepts as multi-

ples of unit cell dimensions

• Get reciprocal of the above num-

bers Figure 11: Miller index planes
• Reduce the reciprocal into the
smallest set of integral numbers;
write them in brackets

The principal planes are (100),

(110) and (111). The (100) plane has
intercepts at x=1, y=∞, z=∞. Similarly for the others.

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7.2 Applications
7.2.1 Sketch of lattice plane
• Draw a unit cell with 3 co-ordinate axes x, y and z.

• Obtain reciprocals from Miller indices

• Get LCM and multiply by it

• The final products are the intercepts

• Mark these values on the axes; join these points to create a plane

7.2.2 Interplanar spacing

The interplanar spacing corresponds to the distance between successive lattice planes.
It is usually denoted by d.
Let us consider a cubic system,
with one of the planes ABC. For
its Miller indices (h,k,l) the inter-
cepts on the axes can be given
as
OA = a/h, OB = b/k, OC =
c/l.

Length of normal from the origin to

the plane, ON = d.
ON will form angles with the crystallo-
graphic axes such that

d Figure 12: Schematic for estimation of inter-

cos α =
a/h planar spacing
(1)
d
cos β =
b/k
(2)
d
cos γ =
c/l
(3)

We know that, cos2 α + cos2 β +

2
cos γ= 1  
 2 2  2
dh dk dl
+ + =1
a b c

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 h2 k 2 l2
 
2
d + 2 + 2 =1
a2 b c
1
d2 =  2
k2 l2

h
+ 2 + 2
a2 b c
1
Hence, d = r
2
h k2 l2
+ +
a2 b2 c2
For a cubic system we have a = b = c. So, we get
a
dhkl = √
h2 + k 2 + l 2
(4)

8 X-ray diffraction
Since X-rays are electromagnetic waves, they will exhibit both interference and
diffraction. Diffraction gratings cannot produce any observable changes for X-rays
their wavelength being of the order of 0.1 nm. W. L. Bragg found that the X-rays
can be reflected from different sets of parallel crystal planes called Bragg’s planes.
Consider a set of planes as shown.
Let an incident ray PA be reflected at
the atom A towards AR, on the 1st
plane. Similarly QC is reflected from
C towards CS. Let us draw perpen-
diculars from A on the rays QC and
CS.

When the path difference (i.e.

CB+CD) is a whole wavelength or mul-
tiple of wavelength, then the two rays
will strengthen each other thereby pro- Figure 13: Reflection of X-rays
ducing an intense spot. i.e. CB + CD =
mλ
But CB = CD = dsinθ, where θ is the glancing angle. Hence,

2d sin θ = mλ
(5)

Here d is the interplanar spacing between the planes, and m represents the order of
reflection. The above equation is called Bragg’s law. If the value of θ is available
from experiments, and the wavelength λ of X-rays is known then making use of the
Bragg’s law, we can determine the interplanar spacing d.

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 λ
Thus, for 1st maximum, sinθ1 = 2d
2λ
for 2nd maximum sinθ2 = 2d and so on.
This implies that the intensity decreases as the order of reflection increases.

9 Powder crystal method/Debye-Scherrer method

Most of the solids are polycrystalline in nature. In order to obtain the parameters
of such systems, the powder crystal method is used.
The Debye-Scherrer camera is a cylindrical shaped drum with its width lesser
than the diameter. The material is finely powdered and compressed into a thin
road or a capillary tube. Inside the cylinder a photographic film is mounted. The
rod/tube is kept vertically.
A beam of monochromatic X-rays will enter into and come out of the cylindrical
drum through the apertures existing on opposite sides of the drum. Crystals which
satisfy the Bragg’s condition will lie with their planes aligned at glancing angle θ
w.r.t the incident beam. Such a crystal will produce a spot on the photographic film.
Since we have a powdered form,
there will be lots of crystallites result-
ing in many values for θ and interpla-
nar spacing d. The diffracted X-rays will
lie on a cone of semi-vertical angle 2θ
and having its apex at the crystal sam-
ple. Each cone will form arc on both
sides of the exit aperture centering over
it. Figure 14: Set-up for powder crystal
In a cylindrical drum of radius R, let method.
x be the distance at which the diffracted
beam will strike the photographic film.
We get,
180◦ x
2θ =
πR
(6)
90◦ x
Hence, θ = .
πR
Thus we can obtain the interplanar spacing d, with the help of Bragg’s law.

Amorphous materials will not produce arcs on the photographic film, since they do
not have reflecting planes.

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