Module-IV

Crystallography

Crystallography: Lattice, unit cell, lattice parameters, crystal systems, Bravais lattices,
Packing fraction for SCC, BCC and FCC crystal systems. Introduction to Miller Indices.
Determination of Crystal structure by Miller Indices. Expression for Inter-planar distance.
X-ray diffraction, Bragg’s law and Determination of Crystal structure by Powder method.
Numericals

(Text book 1: Chapter 7 all units)

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 CRYSTALLOGRAPHY

What is crystallography?

The branch of science that deals with the geometric description of crystals and their
internal arrangement.

SOLID MATERIALS

AMORPHOUS
CRYSTALLINE POLYCRYSTALLINE
(Non-crystalline)

Single Crystal

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 Types of Solids

• Single crsytal, polycrystalline, and amorphous, are the

three general types of solids.

• Each type is characterized by the size of ordered

region within the material.

• An ordered region is a spatial volume in which atoms

or molecules have a regular geometric arrangement
or periodicity.

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 Crystalline Solid
• Crystalline Solid is the solid form of a substance in which the
atoms or molecules are arranged in regular and periodically,
repeating pattern in three dimension.

• Single crystals, ideally have a high degree of order, or regular

geometric periodicity, throughout the entire volume of the
material.
• Sharp melting point
• Anisotropic character

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 Single-crystalline Solid

 Single crystal has an atomic structure that repeats periodically

across its whole volume. Even at infinite length scales, each
atom is related to every other equivalent atom in the structure by
translational symmetry.

Single Pyrite
Crystal

Amorphous
Solid
Single Crystal

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 Poly-crystalline Solid
 Polycrystal is a material made up of an aggregate of many small single
crystals (also called crystallites or grains).
 Polycrystalline material have a high degree of order over many atomic or
molecular dimensions.
 These ordered regions, or single crytal regions, vary in size and orientation
wrt one another.
 These regions are called as grains ( domain) and are separated from one
another by grain boundaries. The atomic order can vary from one domain to
the next.
 The grains are usually 100 nm - 100 microns in diameter. Polycrystals with
grains that are <10 nm in diameter are called nanocrystalline

Polycrystalline
Pyrite form
(Grain)
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 Non-crystalline/Amorphous Solid
• Amorphous Solid is composed of randomly orientated atoms, ions,
or molecules that do not form defined patterns or lattice structures.
• Amorphous materials have order only within a few atomic or molecular
dimensions.
• Amorphous materials do not have any long-range order, but they have
varying degrees of short-range order.
• Low melting point
• Isotropic character
• Examples to amorphous materials include amorphous silicon, plastics, and
glasses.
• Amorphous silicon can be used in solar cells and thin film transistors.

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 Lattice
 It is a mathematical concept. It represents arrangements of atoms or
molecules in a plane or space.
 An infinite array of points in space,
 Each point has identical surroundings to all others.
 Arrays are arranged exactly in a periodic manner.
 The set of mathematical points to which the basis is attached is called the
lattice.

Plane lattice: 2-D

Space lattice: 3-D

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 Basis
A crystal structure is formed only when a group of atoms or molecules is attached
identically to each lattice point. This group of atoms or molecules is called the basis.

Crystal Structure
Crystal structure can be obtained by attaching atoms, groups of atoms or
molecules which are called basis (motif) to the lattice sides of the lattice
point.

Crystal Structure = Crystal Lattice + Basis

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A two-dimensional Bravais lattice with
different choices for the basis

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 Unit Cell
The smallest volume which when repeated in all directions builds
the entire crystal, is called the Unit cell.

S S

S S S
b S S S S S
a
S S S S S

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Unit Cell in 2D
• The smallest component of the crystal (group of atoms, ions or
molecules), which when stacked together with pure translational
repetition reproduces the whole crystal.

S
The choice of
S
unit cell
is not unique.

b S S

a
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2D Unit Cell example -(NaCl)

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Choice of origin is arbitrary - lattice points need not be
atoms - but unit cell size should always be the same.

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This is also a unit cell - it doesn’t matter if we start from Na or Cl

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 UNIT CELL

Primitive Non-primitive

Atoms are in corner as well as face or

Total contribution of lattice point should be 1. center i.e more than one lattice point
Minimum volume cell. per cell
Repetition of primitive cell should cover entire
lattice without any vacant space or over
lapping.

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Primitive Unit Cell

 The primitive unit cell must have only one lattice point.
 There can be different choices for lattice vectors, but the
volumes of these primitive cells are all the same.

a1

P = Primitive Unit Cell

NP = Non-Primitive Unit Cell

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 Three common Unit Cell in 3D

The unit cell and, consequently,

the entire lattice, is uniquely
determined by the six lattice
constants: a, b, c, α, β and γ.

Only 1/8 of each lattice point in a

unit cell can actually be assigned
to that cell.

Simple cubic (SC) Primitive (P) Body centered (BCC) (I)

No. of atoms = 8 ×1/8= 1 No. of atoms = 8 ×1/8 + 2 ×1/2 = 2

Face centered (FCC) (F)

No. of atoms = 8 ×1/8 + 6 ×1/2= 4
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Primitive Unit Cell and vectors

• A primitive unit cell is made of primitive

translation vectors a1 ,a2, and a3 such that
there is no cell of smaller volume that
can be used as a building block for
crystal structures.

• A primitive unit cell will fill space by

repetition of suitable crystal translation
vectors. This defined by the parallelpiped
a1, a2 and a3. The volume of a primitive
unit cell can be found by
• V = a1.(a2 × a3) (vector products)
Cubic cell volume = a3

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 Crystal
Lattice

Bravais Non-Bravais
Lattice (BL) Lattice (non-BL)

All atoms are of the same kind Some of lattice points is non-equivalent when you
All lattice points are equivalent. look at them from different orientation.
The BL looks same when viewed Atoms placed at the lattice points are not the same
from any lattice point. Some lattice points are not equivalent
Atoms can be of different kind
A combination of two or more BL

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Types Of Crystal Lattices

1) Bravais lattice is an infinite array of discrete points with an

arrangement and orientation that appears exactly the same, from
whichever of the points the array is viewed. Lattice is invariant
under a translation.

Nb film
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 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. : 2-dimensional honeycomb structure

2D honeycomb structure
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7-Crystal Systems with 14 Bravais Lattices

Seven crystal systems

are results from the
arrangement of 14
different ways of
arranging equivalent
points in space – Bravais
lattices (3-D)
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24
 1. Cubic Crystals • Simple Cubic (P) - SC
a = b= c • Body Centred Cubic (I) – BCC
α = β = γ = 90º • Face Centred Cubic (F) - FCC

 Elements with Cubic structure → SC: F, O, Po Note Ge has two atoms per lattice
BCC: Cr, Fe, Nb, K, W, V point (has DC crystal structure
FCC: Al, Ar, Pb, Ni, Pd, Pt, Ge
Note: here SC, BCC & FCC are lattices
Examples of elements with Cubic Crystal Structure

 Depending on the type of lattice and the motif the number of atoms per unit cell can vary.

Fe Cu
Po

n=1 SC n=2 BCC n = 4 FCC/CCP n=8 DC

C (diamond)

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2. Tetragonal Crystals
a=b≠c
α = β = γ = 90º

• Simple Tetragonal
• Body Centred Tetragonal -BCT

 Elements with Tetragonal structure → In, Sn 27

In Example of an element with Body Centred Tetragonal Crystal Structure

[100] views

BCT

All atoms are In → coloured

for better visibility

[001] view

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 3. Orthorhombic Crystals
a≠b≠c
α = β = γ = 90º

• Simple Orthorhombic
• Body Centred Orthorhombic
• Face Centred Orthorhombic
• Base Centred or End centred Orthorhombic (C)
(note: the only lattice with all possibilities present)

c<a<b

Base Centered (C)

No. of atoms = (8 ×1/8) + (2 ×1/2)= 2

 Elements with Orthorhombic structure → Br, Cl, Ga, I, S, U

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Ga Example of an element with Orthorhombic Crystal Structure

[010] view

[001] view

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4. Hexagonal Crystals
a=b≠c
α = β = 90º γ = 120º

• Simple Hexagonal
(note: there is only one type of
hexagonal lattice)

 Note that the unit cell is not the hexagonal prism, but the blue shaded rhombic prism. This
unit cell does not have the hexagonal symmetry and hence we often show a compound of 3
unit cells (as above), which has 6-fold symmetry.

 Elements with Hexagonal structure → Be, Cd, Co, Ti, Zn

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Mg Example of an element with Hexagonal Crystal Structure

This is a HCP structure

(it has only a 3-fold pure rotation
axis along z-direction, along ‘z’ it
has a 63 screw axis)

More about this in the chapter on Structure_of_Solids_Metallic

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 Some times an alternate hexagonal cell
5. Trigonal/Rhombohedral Crystals is used instead of the Trigonal Cell
a=b=c
α = β = γ ≠ 90º

• Rhombohedral (simple/primitive)

 Elements with Trigonal structure → As, B, Bi, Hg, Sb, Sm

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 Example of an element with Simple Trigonal Crystal Structure
α-Hg

[111] view

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6. Monoclinic Crystals
a≠b≠c
α = γ = 90º ≠ β

• Simple Monoclinic (P)

• Base-Centred (end centered)
Monoclinic (C)

 Elements with Monoclinic structure → P, Pu

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7. Triclinic Crystals
a≠b≠c
α ≠γ ≠β

• Simple Triclinic (P)

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 Coordination Number
• Coordination Number (CN): The Bravais lattice
points closest to a given point are the nearest
neighbours.

• Because the Bravais lattice is periodic, all points have

the same number of nearest neighbours or coordination
number. It is a property of the lattice.

• Simple cubic lattice has coordination number = 6

• Body-centered cubic lattice = 8
• Face-centered cubic lattice = 12
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 Atomic Packing Factor

Atomic Packing Factor (APF) is the ratio of the total volume

of the atoms present within the unit cell to that of total volume
of the unit cell.

total volume of the atoms present in unit cell

APF =
total volume of unit cell

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Atomic Packing Factor of SC
Assume atoms are spherical in
shape and touching each other.
Since, unit cell a=b=c
So, Volume= 𝒂𝒂𝟑𝟑

a 2R= a
R= 0.5a

No. of atoms × Volume of Atoms in Unit Cells

APF for SC =
Volume of Unit Cell

1× 43π𝑅𝑅3
= 𝑎𝑎3

4
π(0.5𝑎𝑎)3
4
× 3.14 × 0.125𝑎𝑎3
= 3
𝑎𝑎3
= 3
𝑎𝑎3

= 0.5233

= 52.33%
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 Atomic Packing Factor of BCC

AB2 = a2+a2
AC2 = AB2+ BC2
C (4R)2 = a2+a2 +a2
√3𝑎𝑎 1.732𝑎𝑎
R = = = 0.433a
4 4

No. of atoms × Volume of Atoms in Unit Cells

APF for BCC =
Volume of Unit Cell

A B 2× 43π𝑅𝑅3
= 𝑎𝑎3

2× 43×3.14×(0.433𝑎𝑎)3
= 𝑎𝑎3

= 0.6797

= 67.97%

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 Atomic Packing Factor of FCC

C AC2 = AB2+ BC2

(4R)2 = a2 +a2
√2𝑎𝑎 1.414𝑎𝑎
R = = = 0.353a
4 4

No. of atoms × Volume of Atoms in Unit Cells

A APF for FCC =
Volume of Unit Cell
B
4× 43π𝑅𝑅3
= 𝑎𝑎3

4× 43×3.14×(0.353𝑎𝑎)3
= 𝑎𝑎3

= 0.7366

= 73.66%

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APF of SC= 52.33%
APF of BCC= 67.97%
APF of FCC= 73.66%

FCC is densely packed

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