Crystallography

 Experimental science of
determining the arrangement of
atoms in solids and study physical
properties of solid.
 Scientific study of crystals.

Dr. Swapnil Sureshrao Pote

Physics Department,
VNIT ,NAGPUR
 Crystal Structure (Classification)
– Single Crystals: regular periodic arrangement of atoms, distinctive shape,
smooth faces and straight edges. Follows law of constancy of angles.
Possess both short range and long range order. Anisotropic. Examples:
quartz, rocksalt, alum, diamond etc..
– Polycrystalline Solids: fine grains (103-104 Å single crystals of irregular
shape), separated by well defined boundaries and oriented in different
directions. Examples: metals. Isotropic.
– Amorphous Solids: No ordered crystalline state. Short range order in
atomic arrangement. Examples: glass, rubber, polymers etc.
 Crystal Structure (Crystal Lattice)

+ =
Basis

Lattice Sites Crystal Structure

• A atom or group of atoms identical in
composition, arrangement and orientations is
called basis.
 Crystal Structure (Unit Cell)
• Fundamental block
• The unit cell is the smallest
geometrical unit , which when
repeated in space indefinitely
generates the space lattice.
• Can be chosen in a number of ways
• Is the smallest volume that carries a
full description of the entire lattice

Primitive Cells
Nonprimitive Cells
 UNIT CELL = The smallest component of the crystal, which
when stacked together with pure translational repetition
reproduces the whole crystal

Unit Cell Parameters:-

Lattice Constants
a , b, c
&

Angles between Crystallographic c

Axes b  
, , 
a
Crystal Systems(14 Bravias lattices)
Simple Cubic
Body Centered Cubic
Face Centered Cubic
Structural Relationship
The Unit Cell Characteristics

• Unit Cell Volume, V

V = abc(1-cos2-cos2-cos2+2coscoscos)
• Effective Number of Atoms per Unit Cell, Z
• Atomic Radius r
• Nearest Neighbour Distance 2r
• Coordination Number, CN
• Atomic Packing Fraction, APF
– APF = Zv / V
• Void Space
– Void Space = (1- APF) x 100
• Density
 = ZM / NAV
CHARACTERISTICS OF UNIT CELLS
1. Unit Cell Volume, V

V = a b c (1-cos2-cos2-cos2+2coscoscos)1/2

For Cubic unit cell a=b= c= &

===90 hence

V = a3 for SC, BCC & FCC unit cell

Effective Number of Atoms per Unit Cell, Z

Simple Cubic Cell (SC) Body centered Cubic (BCC) Face Centered Cubic (FCC)

a a

r r a
a
a a
Z = 1/8 x 8 ( corners/cell) Z = 1(body centre atom/unit cell) Z = ½ (atom/face) x 6(faces/unit cell)
Z = 1 atom/unit cell +1/8x 8( corners/cell) +1/8x 8( corners/cell)
Z = 2 atoms/unit cell Z = 4atoms/unit cell
 3. Atomic radius , r
Simple Cubic Cell (SC) Body centered Cubic (BCC) Face Centered Cubic (FCC)
H G D C
r r
E F
a 2r
a a
2r
r

rr C
a
r A B
r a a
a A a B
2r = a Body diagonal AG = 4r Face diagonal AG = 4r
r = a/2 AG2 = AC2 + CG2 AC2 = AB2 + BC2
= (AB2 + BC2) + CG2 (4r)2 = a2 + a2
(4r)2 = a2 + a2 + a2
(4r)2 = 3a2 (4r)2 = 2a2
r =(3/4) a r =(2/4) a = a / (22)
 4. Nearest neighbour distance, 2r

Simple Cubic Cell (SC) Body centered Cubic (BCC) Face Centered Cubic (FCC)

r = a/2 r =(3/4) a r = a / (22)

2r = a 2r = (3/2) a 2r = a/2
 5. Coordination Number, CN

Simple Cubic Cell (SC) Body centered Cubic (BCC) Face Centered Cubic (FCC)
ZX-plane
YZ-plane

1
11 10 22

6 XY-plane
8
9
A 7

5 6

2 4

5
3

1 2

4
4 3

CN = 6 CN = 8
YZ-plane

CN = 12
 Co ordination No (N) -No of Nearest
atoms
Face Centered Cubic
 Co ordination No (N) -No of Nearest
atoms
Face Centered Cubic
 6. Atomic Packing Fraction

Simple Cubic Cell (SC) Body centered Cubic (BCC) Face Centered Cubic (FCC)

APF = (Z )/V APF = (Z )/V APF = (Z ) /V

For SC cell, Z = 1 For BCC cell, Z = 2 For FCC cell, Z = 4
u =volume of spherical u =volume of spherical u =volume of spherical
atom atom atom
u = 4/3r3 u = 4/3r3 u = 4/3r3
V = volume of the unit cell V = volume of the unit cell V = volume of the unit cell
= a3 = (2r)3 = 8r3 = a3 = (4r/3)3 = 64r3 /33 = a3 = (22r)3
APF = [1 x (4/3r3)] / (8r3) APF = [2 x (4/3r3)] / [64r3/ 33] APF = [4 x (4/3r3)] / [162r3]

APF = /6 = 0.52 APF =  3 /8 = 0.68 APF =  /32 = 0.74

 6. Voids Space

Void Space = [1- APF] x 100

Simple Cubic Cell (SC) Body centered Cubic (BCC) Face Centered Cubic (FCC)

Void Space = [1-0.52] x 100 Void Space = [1-0.68] x 100 Void Space = [1-0.74] x 100
= 48% = 32% = 26%
 7.Density, 

 = Mass/Volume = ZW/V ;
where W = mass of each atom given by M/NA
where M is molecular weight of the material and NA is Avogrado number
Hence  = ZM/(VNA)

Simple Cubic Cell (SC) Body centered Cubic (BCC) Face Centered Cubic (FCC)

 = ZM/VNA  = ZM/VNA  = ZM/VNA

for SC, Z = 1 for BCC, Z = 2 For FCC, Z = 4
Hence,  = 1M/(NAa3) Hence,  = 2M/(NAa3) Hence,  = 4M/(NAa3)
 Cubic Crystal
Parameters
SC BCC FCC

Lattice Constant a a a

Effective no. of atoms per unit cell (n), 1 2 4

Atomic Radius (r)

Volume of Unit Cell (Related to Atomic Radius)

Coordination Number (CN) 6 8 12

Atomic Packing Fraction (APF), 0.52 0.68 0.74

Percentage of Void Space 48 % 32 % 26 %

Density,
ZnS Unit Cell
CaF2 Unit Cell
Voids

•The vacant space between the atoms in the crystal are

called voids or interstices
•Three dimensional arrangement of spheres gives rise
to voids between their curved surfaces
•Mainly two kinds of voids in a close packed structure
–Tetrahedral
–Octahedral
Tetrahedral Void
• Produced by a sphere fitting
into the valley formed between
three adjacent spheres of a
closed pack structure.
• If centers of four atoms are
joined, a regular tetrahedron is
produced
• The vacant site enclosed by
the tetrahedron is called
tetrahedral void
• If fourth sphere belongs to
upper layer- upright tetrahedral
void, else, inverted..
 Octahedral Void
• Produced when a void formed by
three adjacent spheres in one
layer comes on the top of the
void formed by three spheres in
contact in the adjacent layer
• Surrounded by six spheres
• The centers of the three spheres
in a layer comes exactly on the
top of the triangular peripheral
valleys formed by the spheres in
the bottom layer
• Octahedron is obtained on
joining centers of six spheres,
hence space enclosed is called
octahedral void
 Octahedral Voids
Tetrahedral
Two voids per sphere
Surrounded by four atoms
Smaller in size and greater
number
Tetrahedral Voids
Octahedral
One void per sphere
Surrounded by six atoms
Bigger in size and smaller in
number
 Miller Indices
• The crystal is made up of a large no. of parallel
equidistant planes passing through the lattice points
which are known as lattice planes. For a given lattice, the
lattice planes can be chosen in a different ways as shown
in fig. i.e. (a), (b), (c) & (d)

• The perpendicular distance between adjacent planes is

called interplanar spacing. The position and orientation of
a lattice plane is determined by three smallest whole
numbers which have the same ratios with one another as
the reciprocals of the intercepts of the plane on three
crystal axes. These numbers denoted by h, k, l are known
as “Miller indices” of that plane and the plane is specified
by (hkl).

• Definition- Miller indices are the three smallest

possible integers which have the same ratios as the
reciprocals of the intercepts of the plane concerned
on the three axes.
 How To Find The Miller Indices Of A Plane:

o Find the intercepts of the plane on the three crystallographic axes.

o Take the reciprocal of these intercepts.
o The reciprocals are reduced to the smallest set of integers by taking LCM.
o Enclose these integers in round bracket (h,k,l)
 
Example:
• Consider a plane ABC has intercepts of 4a on x-axis, 2b on y-axis & 3c on z-axis.
• Hence a = 4, b = 2, c =3
• The intercepts are :- 4,2,3
• Reciprocals of intercepts = 1/4, 1/2, 1/3
• Taking LCM , &multiply each reciprocal by LCM : 3,6,4
• Miller indices of plane ABC are (3,6,4)
 How To Draw Lattice Plane ()

• Draw the cube with three coordinate axes.

• From (hkl) find intercepts on three coordinate axes as 1/h, 1/k, and
1/l.
• Make the intercepts on three coordinate axes.
• Draw a plane passing through these intercepts and shade it.

Example:
•  Draw a plane (2 3 1)
• A cube is drawn with three coordinate axes as shown in fig.
• Intercepts are found as reciprocals of Miller indices
• a=1/2,b=1/3,c=1
• Mark the intercepts within the cube. Cube length is considered as one.
• Draw a plane through these intercepts and shade it as shown in fig. 
 Some Features Of Miller Indices:

• Miller indices (hkl) represent set of parallel,

equally spaced planes.
• A plane parallel to one coordinate axis has
Miller index 0 for that direction e.g. a plane
(011) is parallel to X-axis.
• When the intercept of a plane on any axis is
negative bar should be kept on the
corresponding Miller index. e.g. (210) has Y-
intercept -1.
Interplanar distance in a cubic crystal
The intercepts of the plane on the coordinate axes are

The sum of squares of direction cosines of a line equals unity. Thus,

 The interplanar spacing is given by,

Where, a -length of the cube edge

h,k,l- miller indices

This is the relation between interplanar spacing (d) and cube edge (a) of
the unit cell.
Directions in Cubic Unit Cells
(0,0,1) (0,1,1)

(1,0,1)
(1,1,1)

(0,0,0) (0,1,0)

(1,0,0) (1,1,0)
Family of Symmetry Related Planes

( 1 1 0 ) {110}
= Plane ( 1 1 0 )
( 1 0 1 ) and all other
planes related
by symmetry
( 0 1 1 ) to ( 1 1 0 )

{111}
( 1 1 1 )
= Plane ( 1 1 1 )
and all other
( 2 2 1 ) planes related
by symmetry
to ( 1 1 1 )
Miller indices of common planes
 Bragg’s Law

• When an X-ray beam is incident on the crystal, each atom in the

crystal acts as a source of scattered radiation of same wavelength.
The scattered waves travel in all directions. The combined scattering
of X-rays from the planes can be looked upon as diffraction.
• Bragg made some simplifications to diffraction of X-rays from
crystal:
– Any crystal can be considered as a stack of atomic planes.
– The atomic planes act like semi-transparent mirrors or X-rays.
– X-rays reflected from successive atomic planes would interfere constructively
or destructively depending upon the path difference between the rays.
– When the path difference is an integral multiple of wavelength, the rays
interfere constructively.
 Bragg’s Law

Path Difference = n  for Constructive Interference


A

90-  
B D

C
From figure
The path difference between the rays reflected along BC & EF is,

When the path difference is an integral multiple of wavelength i.e. nλ, then two rays will
reinforce each other and produce an intense spot.
Thus, the condition for reinforcement is,

BE is normal to the plane MN. Therefore,

From equations (3) and (4), we get,

Therefore, path difference

The rays BC and EF will constructively interfere only when ∆=nλ, where
n=1,2,3----.Therefore the condition for reinforcement of scattered waves is,

The Equation (5) is known as Bragg’s equation or Bragg’s law.

The angle θ between Bragg plane & the direction of the incident beam is known as glancing angle
or Bragg angle.
 A Modern Automated X-ray Diffractometer

X-ray Tube
Detector

Sample stage

Cost: $560K to 1.6M

Detection of Diffracted X-rays by a Diffractometer
X- Ray Diffraction
XRD Pattern of NaCl Powder

Miller indices: The peak is due to Xray

diffraction from the {220} planes.

Diffraction angle 2Ѳ(degrees)