RSET, 2011-12

Crystallography

Engineering Physics

Crystallography

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RSET, 2011-12

Crystallography

Engineering Physics

0. Introduction
Crystallography
Branch of solid state physics dealing with the structure of
crystalline solids
Tools of crystal analysis: X-ray, electron beam
Properties of solids depend on their crystal structure
E.g. Elasticity, electrical conductivity, magnetism

Classification of solids
Crystalline solids
Solids with atoms/molecules/groups arranged in a regular fashion such
that their positions are exactly periodic
E.g. NaCl

Polycrystalline solids
Composed of many microscopic crystals, called crystallites or grains
Solids with the periodicity of spiecies interupted at grain boundaries
Grain: Region within which particular periodicity exists
E.g.: Metals, Ceramics

Amorphous solids
Solids with atoms distributed irregularly or randomly
E.g. Glass
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Crystallography

Engineering Physics

1. Crystal Structure: Space lattice

Crystal structure = Space lattice + basis
Space Lattice
It is the geometry of a set of points in space
Space lattice represents an array of points in space such that the
environment about each point is the same

Mathematical representation

p
T

Using basic vectors and their translation or parallel displacement

Position vector of any point P in a space lattice can be represented as
sum of integral
multiples
of basic vectors

2D: T
n1a n2b

3D: T n1a n2 b n3c

a , b and c are non-collinear vectors or basic vectors of the

lattice
Lattice has translational symmetry (non-variability under
displacement) specified by the lattice vectors
Crystal looks the same when viewed from any of lattice points

2D Lattice

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Crystallography

Engineering Physics

2. Crystal Structure: Basis

Basis
The atom, ions, or group which constitute the geometrical
pattern of a crystal lattice
It may be monoatomic (e.g. Al, Ba), diatomic (e.g. NaCl, KCl)
or triatomic (e.g. CaF2), etc.
Basis is identical in composition, arrangement and orientation

Crystal structure = Space lattice + Basis

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Basis with 3 atoms

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Crystallography

Engineering Physics

3. Crystal Structure: Unit Cell

Primitive cell
Volume of the space that when translated through all the vectors in a
space lattice, fill the space without overlapping or leaving void
It is the minimum volume cell which contains precisely one lattice point
If a, b and c are primitive vectors, then the volume of the primitive cell is
given by Vcell = a x b.c (Box product); a, b and c are lattice vectors

Unit cell
The smallest geometric unit, repetition of which in 3-D gives the actual
crystal structure
Fundamental pattern of minimum atoms, ions or groups of atoms which
represent all the characteristics of the crystal

Unit cell may contain more than one lattice point

Unit cells may be identical to a primitive cell, but all primitive cells are not
unit cells

Volume of a unit cell is an integral multiple of the volume of the primitive

cell
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Crystallography

Engineering Physics

4. Unit Cell Parameters

Lattice/Unit Cell parameters
Full set of lattice parameters
Three lattice constants (a, b, c)
Three angles between them (, , )

E.g. Unit cell definition using parallelepiped with

lengths a, b, c and angles between the sides given by
, ,
Cubic crystal structures
All three lattice constants are equal and we only refer to a

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Crystallography

Engineering Physics

5. Crystal Systems (Bravais Lattices)

Bravais space lattices (Auguste Bravais, France, 1848)
There are 14 unique lattices (ways of arranging points) in 3-D
crystal systems (x Frankheim, 1845: 15 unique lattices)
7 crystal systems and 6 lattice centerings

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Crystal systems
Triclinic, Monoclinic, Ortorhombic, Tetragonal, Rhombohedral
(trigonal), Hexagonal, Cubic
Defined by different relations between unit cell parameters (a, b, c,
and , , )
Lattice centerings
Primitive centering (P): Lattice points on cell corners only
Body centered (I): One additional lattice point at the center of the
cell
Face-centered (F): One additional lattice point at the center of each
of the faces of the cell
End-centered (A, B or C centering): One additional lattice point at
the center of one pair of the cell faces
Number of unique lattices
Total number of combinations: 7 x 6 = 42
Several are but equivalent to each other. E.g. All A and B centered
lattice can be described by either C or P centering
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There are only 14 unique lattices: Bravais lattices

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Crystallography

Engineering Physics

5. Crystal Systems (Bravais Lattices)

Crystal System

Possible Variations

Axial Distances (edge

Axial Angles
lengths)

Cubic

Primitive, Body centred,

Face centred

a=b=c

= = = 90

NaCl, Zinc Blende, Cu

Tetragonal

Primitive, Body centred

a=bc

= = = 90

White tin, SnO2, TiO2,

CaSO4

Orthorhombic

Primitive, Body centred,

Face centred, End centred

abc

= = = 90

Rhombic Sulphur, KNO3,

BaSO4

Hexagonal

Primitive

a=bc

= = 90, = 120

Graphite, ZnO, CdS

Rhombohedral (trigonal)

Primitive

a=b=c

= = 90

Calcite (CaCO3, Cinnabar

(HgS)

Monoclinic

Primitive, End centred

abc

= = 90, 90

Monoclinic Sulphur,
Na2SO4.10H2O

Triclinic

Primitive

abc

90

K2Cr2O7, CuSO4.5H2O,
H3BO3

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Examples

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Crystallography

Engineering Physics

6. Three Cubic Lattices

Primitive or Simple Cubic(P)
Consists of one lattice point on each corner of the cube.
Each atom at a lattice point is then shared equally between eight
adjacent cubes, and the unit cell therefore contains in total one atom
(18 8).

Body-centered Cubic(I)
One lattice point in the center of the unit cell in addition to the eight
corner points.
It has a net total of 2 lattice points per unit cell (18 8 + 1).

Face-centered Cubic(F)
Lattice points on the faces of the cube, that each gives exactly one half
contribution, in addition to the corner lattice points
A total of 4 lattice points per unit cell (18 8 from the corners plus 12
6 from the faces).
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Engineering Physics

7. Number of atoms per unit cell

Number of atoms per unit cell
Simple cubic (sc)
E.g. Alpha-polonium
Lattice point at the corner is shared by 8 unit cells
Share of one cell = 1/8
Lattice points at the 8 corners = 8

Lattice point/unit cell = 1/8 x 8 = 1

Body-centered cubic (bcc)

E.g. Li, Na, Ba, Cr, Mo

Contribution from 8 corner points = 1/8 x 8 = 1
Lattice point at the center of the cell = 1
Lattice point/unit cell = 1+1 = 2

Face-centered cubic (fcc)

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E.g. Ca, Ni, Ag, NaCl, Pb, Pt, Au

Contribution from corner points = 1/8 x 8 =1
Contribution from the face-centered lattice points = 6 x = 3
Lattice point/unit cell = 1+3 = 4
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Engineering Physics

8. Co-ordination number
Co-ordination number
Number of nearest neighbours in a given structure
Characteristic feature of a given Bravais lattice
Co-ordination number Packing density

Simple cubic

4 nearest neighbours in the same plane

2 nearest neighbours exactly above and below in a vertical plane
Co-ordination number = 4+2 = 6

Body-centered cubic
Every centered atom has 8 nearest neighbours
Co-ordination number = 8

Face-centered cubic
Nearest neighbours in the same plane = 4
No of perpendicular planes = 2
Number of atoms in one perpendicular plane = 4
Total neighbours in two perpendicular planes = 2 x 4 = 8

Co-ordination number = 4 + 8 = 12
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Engineering Physics

9. Atomic Radius
Atomic radius (R)
Assumption: Atoms as spheres in contact in a crystal
Definition: R is half the distance between the nearest neighbours in a crystal
R = R(a)
a = side of simple cubic unit cell
R
R
Simple cubic
H
G
R = a/2 or a = 2R
Body-centered cubic (bcc)
a
D
C
4R
2
2
2
(DF) = (DA) + (AF)
Simple cubic
E
F
2
2
2
(4R) = (a) + (a2)
a2
B
2
2
(4R) = 3a ; R = 3 a/4 or a = 4R/(3)
R
A
B
bcc
Face-centered cubic (fcc)
(DB)2 = (DC)2 + (CB)2
2R
2
2
2
2
a
(4R) = (a) + (a) = 2a
R = (2 a)/4 or a = 4R/ 2
R
D

C
a

fcc

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Engineering Physics

10. Packing Factor (Density/Fraction)

Packing density (fraction)
Ratio of the volume of the atoms per unit cell to the
total volume of the cell
Simple cubic

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No. of atoms/unit cell = 1

Volume of one atom = 4/3R3
Side of the unit cell, a = 2R
Volume of the cell = a3
Packing density = (4/3R3)/a3 = (4/3R3)/(2R)3 = /6 = 0.52

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Engineering Physics

10. Packing Factor (Density/Fraction)

Body centered cubic (bcc)

No. of atoms/unit cell = 2

Volume of two atoms = 2 x 4/3R3
Side of the unit cell, a = 4R/3
Volume of the cell = a3
Packing density =(2 x 4/3R3)/a3 = 2 x 4/3R3/(4R/3)3 = 3 x /8 =
0.68

Face centered cubic (fcc)

No. of atoms/unit cell = 4

Volume of four atoms = 4 x 4/3R3
Side of the unit cell, a = 4R/2
Volume of the cell = a3
Packing density =(4 x 4/3R3)/a3 = 4 x 4/3R3/(4R/2)3 = 22 x /6
= 0.74

Utilization of space is maximum for fcc and simple cubic

structure is least dense.

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Engineering Physics

11. Density and crystal lattice constants

Relation between density and crystal lattice
constants
Cubic crystal of lattice constant, a
Number of atoms per unit cell, n
Volume occupied by n atoms

Density,
Atomic weight of material, MA
Avogadro Number, NA
Volume occupied by NA atoms = [MA / ] m3
Volume occupied by 1 atom = [MA/ . NA]
Volume occupied by n atoms = [MA.n / . NA] = a3

= [MA.n / NA.a3]
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Engineering Physics

12. Lattice Planes and Miller Indices

Miller indices (William Hallowes Miller, UK)

A treatise on Crystallography, 1839

A designation scheme to describe the orientation of crystallographic
planes and crystal faces relative to crystallographic axes

They are symbolic vector representation for the orientation of an atomic

plane in a crystal lattice

Method of finding Miller indices:

Step 1: Ascertain the fractional intercepts that the plane/face makes with
each crystallographic axis.

Step 2: Take the reciprocal of the fractional intercept of each unit length for
each axis.
Step 3: Clear the fractions by multiplying with least common multiple
(LCM). The cleared fractions result in 3 integer values, designated h, k,
and l.
Step 4: These integers are paranthetically enclosed (hkl) to indicate the
specific crystallographic plane within the lattice.

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Find how far along the unit cell lengths does the plane intersect the axis

Since the unit cell repeats in space, the (hkl) notation actually represents a
family of planes, all with the same orientation.

Miller Indices are defined as the reciprocals of the fractional intercepts

which a crystal plane makes with the crystallographic axes reduced to
smallest integer numbers
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Engineering Physics

12. Lattice Planes and Miller Indices

Problem 1: Find Miller indices of the plane whose
intercepts are 1a, 2b, and 3c.

Step 1: Find fractional intercepts: 1a/a, 2b/b, 3c/c or 1,2,3

Step 2: Take reciprocals: 1/1, , 1/3
Step 3: Clear fractions or Multiply with LCM: 6/1, 6/2, 6/3
Step 4: Miller indices are (632)

Problem 2: The crystal cuts the intercepts 2, 3, and 4

along the three axes. Find the Miller indices of the plane

Step 1: Find fractional intercepts: 2, 3, 4

Step 2: Take reciprocals: 1/2, 1/3, 1/4
Step 3: Clear fractions or Multiply with LCM: 12/2, 12/3, 12/4
Step 4: Miller indices are (643)

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Engineering Physics

12. Lattice Planes and Miller Indices

Problem 3: Find Miller indices of three principal planes
x = a; y = 0; z = 0
Step 1: Fractional intercepts: 1, , (When a face is parallel to the axis, its
intercepts on the axis is taken as infinity)
Step 2: Take reciprocals: 1/1, 1/, 1/
z
z
Step 3: Clear fractions or Multiply with LCM: 1/1, 0, 0
Step 4: Miller indices are (100)

x = a; y = b; z = 0

Step 1: Fractional intercepts: 1, 1,

(100)
y
Step 2: Take reciprocals: 1/1, 1/1, 1/
Step 3: Clear fractions or Multiply with LCM: 1/1, 1/1, 0
Step 4: Miller indices are (110)

(110)

x = a; y = b; z = c

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Step 1: Fractional intercepts: 1, 1, 1

Step 2: Take reciprocals: 1/1, 1/1, 1/1
Step 3: Clear fractions or Multiply with LCM: 1/1, 1/!, 1/1
Step 4: Miller indices are (111)

x
y

(111)

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Engineering Physics

13. Separation between lattice planes

C

C
P
A

[For orthogonal crystal systems, i.e. cubic, orthorhombic and tetragonal crystal
systems for which = = = 90 )
Suppose the plane ABC, belonging to a family of planes whose Miller indices are (hkl)
Sides of lattice a, b and c respectively
Intercepts OA = a/h (since, h = a/OA); OB = b/k, OC = c/l
Let OP be perpendicular drawn from the origin to the plane ABC.
Distance OP represents interplanar spacing d of the family of planes
Let , and be the angles between coordinate axes x, y, z and OP respectively
For an orthogonal cartesian coordinate system, there is an identity: cos2 + cos2 +
cos2 = 1
Direction cosines of OP are: cos = d/OA, cos = d/OB, cos = d/OC
Substitute for cos , cos and cos
(d/OA)2 + (d/OB)2 + (d/OC)2 or (dh/a)2 + (dk/b)2 + (dl/c)2 = 1 or d = 1/[h2/a2 + k2/b2 +
l2/c2]1/2
For cubic system a = b = c: d = a/[h2 + k2 + l2]1/2

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Engineering Physics

13. Separation between lattice planes

Find interplanar distance for simple cubic lattice

1) d100 = a /(h2 +k2 +l2) = a/1 = a

2) d110 = a /(h2 +k2 +l2) = a/(12 +12) = a/2
2) d111 = a /(h2 +k2 +l2) = a/(12 +12 +12) = a/3
Ratio of the reciprocals of interplanar distances:
1/d100: 1/d110: 1/d111 = 1: 2: 3

Find interplanar distance of fcc

1) (d100)fcc = (d100)sc = a/2

Find interplanar distance of bcc

1) 1) (d100)bcc = (d100)sc = a/2
z

bcc

fcc
y

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d100

d100

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Engineering Physics

14. Braggs Law

Braggs law of x-ray diffraction
[William Henry Bragg (Spectrometer) and son W.Lowerence Bragg (Braggs law) UK, Nobel
prize: 1915: Analysis of crystal structure using x-rays]

Crystal as diffraction grating for x-rays

Laue (1912)

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X-ray is of very short

Grating with 40 million lines per cm required for producing
diffraction pattern
Crystals can act as a space grating (not a plane grating)
Interatomic separation is of the same order of magnitude as
wavelength of x-rays
Laue spots : Diffraction pattern from NaCl crystal
W.L. Braggs Explanation
Assumption: x-rays are not refracted (mirror-like or specular
reflection)
Diffraction pattern are due to reflections of x-rays from various
sets of parallel crystal planes which contain large number of atoms
Each atom acts as a source of secondary wavelets
As different from ordinary mirror, x-rays penetrate through crystal
to encounter thousands of planes parallel to one another
Radiations reflecting from two successive parallel planes produces
diffraction pattern

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14. Braggs Law

Plane 1

Plane 2

d
D
d

Plane 3

Braggs law
Consider a ray PA gets reflected from atom A in the direction AR from plane 1
Another ray QB gets reflected at another atom B in the direction BS
Draw perpendiculars AC and AD on the incident ray QB and reflected ray BS
respectively
P.d between two reflected rays = CB + BD
Condition for constructive interference (reinforcement): p.d = n
CB + BD = n
CB = BD = dsin
Or 2dhklsin = n, n = 1,2,3,... for first order, second order or third order ..maxima
respectively
The intensity goes on decreasing as the order of the spectrum increases
Only first few orders are of importance

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Engineering Physics

15. Braggs X-ray spectrometer & Crystal Analysis

Braggs X-ray spectrometer [W.H. Bragg]

[A single crystal method or rotating crystal method]
X-ray tube

Matched filters
S1 and S2

To produce x-ray

To collimate incident x-ray into a pencil of beam onto the cleavage plane of the crystal C
X-ray absorbers, e.g. Lead

Rotatable table

It is provided with a vernier, V1 and graduated circlar platform, S

To mount crystal to be analyzed
Rotating crystal method: Sample crystal is rotated to get diffraction maxima

Spectrometer couples the rotation of the crystal and the detector

Angle of rotation of detector is twice the angle of rotation of crystal

Slit S3

To collimate the diffracted beam of x-ray

S1 S2

= Glancing angle

v1

Sin1: Sin2: Sin3 =1/d1:1/d2:1/d3

S
v2

S3
w

G
1

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15. Braggs X-ray spectrometer & Crystal Analysis

Braggs X-ray spectrometer ctd...
Ionisation chamber (detector)
Filled with ethyl bromide which is highly sensitive to x-ray ionisation
Anode A
Long wire insulated from the chamber kept away from axis:To avoid direct hit with
x-ray and hence photoelectric emission

Cathod: The chamber

Window, W: Aluminium foil

Ionization current measurement

Ionisation current: Measured by Electrometer G
The current is a measure of the intensity of x-ray
X-ray produces high energy electrons by photoelectric effect and Compton effect
(reduction of energy of x-rays due to scattering at matter).

High energy electrons ionize the gas

Peaks in Ionisation current refers to incidence angles corresponding to
different interference maxima
2dsin = n: from knowledge of of x-ray and , lattice parameter, d can be
determined
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Engineering Physics

15. Braggs X-ray spectrometer & Crystal Analysis

Sample analysis (KCl crystal with (100) plane
Peak intensities at 1 = 5.22 ; 2 = 7.30 ; 3 = 9.05
Braggs angles for first order of diffraction

2d1sin 1 = ; 2d2sin 2 = ; 2d3sin 3 =

1/d1 : 1/d2: 1/d3 = sin 5.22 : sin 7.30 : sin 9.05
=0.091:0.0127:0.157 = 1:1.4: 1.73 = 1:2:3
The crystal is simple cubic

Comments
Single crystal method: Useful when perfectly ordered
geometrical array of atoms is investigated (Single crystal free
of distortions)
Determination of crystal orientation
Determination of crystal quality
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9. Powder Crystal Diffraction

Powder Crystal method (Debye and Scherrer)
Suitable for analysis of materials that are available in micro-crystalline
or powder nature
Though atoms in individual crystals are ordered, the orientations of crystals
themselves are disordered
No sigle crystal requirement
Suitable for metals and alloys

Crystal structure (lattice parameters), presence of impurities, distortions,

preferred crystal orientation, grain size, stresses present in the material etc.
are studied

Debye-Scherrer camera

X-ray
source

Filter

Transmitted beam

Specimen

Collimator
Photographic film

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Engineering Physics

9. Powder Crystal Diffraction

Working
X-ray Filtering
To obtain monochromatic radiation

X-ray is incident on powder sample mounted at the centre of the camera

Photographic film is placed cylindrically about the sample
Powdered crystal statistically contains crystallites which are so oriented that
reflection from a particular plane (hkl) is possible
Debye-Scherrer pattern

entrance

Large number of curved surfaces corresponding to the Bragg planes truncated by

the edges of the film due to its limited width
Diffracted beams lie on a circular cone of half angle 2
Beams are bent through all angles upto nearly 180 are recorded
Rays diffracted through small angles make arcs around the central spot on
45
exit
the film
When incident beam is diffracted through 90 the cone becomes a flat sheet
l1 l2
and the trace is a straight line
Then onwards curvature will be reversed
Spacing between pairs of arcs Bragg angle corresponding to diffraction
2 1 0 1 2
from a particular plane
r

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Engineering Physics

9. Powder Crystal Diffraction

Theory
Angle 2 is formed between the diffracted rays and the direction
of incident beam
There exists one cone corresponding to each solution of the Bragg
equation
Let l1, l2, l3, etc. be the central distances between symmetrical lines on
the streched photograph and r, the radius of the cylindrical film

l1/( 2r) = 4/360

= l1/2r x 90 / ....(1)
sin = n/2dhkl .....(2)

Interplanar distance dhkl can be calculated from (1) and (2)

Reflecting
plane

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