..

Syllabus: Unit III Crystal Structure

Crystal Structure
• Types of solids • Different materials have different Electrical, Magnetic,
• Unit Cell Mechanical, Optical, Thermal properties
• Types of crystals • Properties of Materials are dictated by its constituents (atom,
• Translation vectors
molecules, ions) and their arrangement
• Lattice planes and Miller indices
• Simple crystal structure • The main reason for these different properties of solids is their
• Interplanar spacing crystal structure i.e. the arrangement.
• Crystal structure analysis:
• Thus, study of the crystal structure plays a vital role in
• Bragg's law and Laue method
understanding the behaviour of solids and their properties. .
• Point defects : Schottcky and Frenkel defects
• 'Crystal Physics' or 'Crystallography' is a branch of Physics that
1 deals with the study of all possible types of crystals 2

Matter
• The universe is made up of radiation and matter
• Matter consists of one or more elements or their chemical compounds
• Exists in three states:
• Solid, liquid and gaseous states.
• The inter-molecular forces bind a large number of atoms into a form
which has a volume and definite shape of its own.
Materials Research Society of India • Such aggregates of atoms which preserve their volumes and shapes
unless subjected to a large external force are called solids.
• In case of solids, the atoms, ions and molecules are relatively fixed in
position

MRSI 3
• whereas in case of liquids and gases the particles are in the constant
translational motion. 4

Types of Solids All forms of matter condense in the solid state at a certain
specific temperature.
• When we focus on the solids, they are classified into many types
based on several properties like

• Electrical, Mechanical, Magnetic, Optical, Thermal etc.

• The accurate structure is determined by using X-rays, neutron

beams and electron beams.

5 6

1
 ..

Types of Solids
The solids can be classified into two categories : Amorphous Solids
• Amorphous solids
• Crystalline solids In such solids, the atoms or molecules
are strongly bonded yet hardly there
Both these names have their is any geometrical regularity or
origin in Greek words, periodicity in the way in which atoms
'amorphous' from 'shapeless' and are arranged in space.
crystalline from 'clear ice’
A two dimensional representation of
The distinction between an such a solid is depicted in Fig
amorphous and a crystalline
solid can be shown from their
cooling curve 7 8

Crystalline Solids
The solids are characterised by a perfect or
nearly perfect periodicity of atomic
structure.
The geometrical regularity of structure
provides a simple conceptual picture of a
crystal and help a lot in gaining the
knowledge of the physical properties of the
solids.
Solid in which the atoms are arranged in a
definite repeating pattern
9 10

Distinction between Crystalline and Amorphous Solids Crystallographic Terms

S.N Crystalline Amorphous Crystal
o.
1. Crystalline solids have regular The amorphous solids have a
A Crystal is the regular polyhedral form bound by smooth surfaces,
arrangement of atoms, ions or completely random arrangement. which is assumed by a chemical compound under the action of its
molecules interatomic forces when passing from the state of a liquid or gas to
2. Crystalline solids have different while amorphous substances are that of a solid under suitable conditions or
physical properties in different isotropic i.e., they have their physical a crystal is a homogeneous, anisotropic having natural shape of a
directions i.e., they are anisotropic properties same in all directions.
polyhedron .
3. Cooling curve of the crystalline The cooling curve for amorphous
substance has breaks, substance is smooth, In simple words, we can say that a crystal is a substance
4. In case of a crystalline substance, while the amorphous substance do not (material), in which the constituent particles are arranged in a
the melting point is very sharp have sharp melting points systematic geometrical pattern.
11 12

2
 ..

Space lattice • The points of intersection of these lines are called lattice points.
• Let us consider an ideal crystal. • The network of points in three dimensions, in which the surrounding of
each point is identical with the surrounding of other points, is called space
• A crystal is composed of atoms or groups of atom which are lattice.
arranged in a regular three dimensional periodic manner. • By associating each lattice point with a single atom or group of atoms,
• To describe the periodicity in crystals, Bravais, a French called basis, crystal structure results.
Scientist, in 1848, introduced the concept of space lattice. • Thus, for every crystal, there is a network of lattice points, which are
• Space lattice is a geometrical concept. occupied by either a single atom or group of atoms.

• To have its meaning, imaging a network of straight lines

constructed in such a way that it divides the entire space into
identical volumes.
13 14

Basis

Lattice

15 16

In 1848, a French mathematician Bravais showed that there are just 14 ways
For any .type of lattice, there exist three fundamental translational
of arranging points in space lattice such that all the lattice points have exactly vectors a, b and c, not lying in a plane, in terms of which any lattice
the same surroundings. point can be specified.
Such lattices are called Bravais lattices A translation operation T is defined as
From these 14 space lattices, unlimited number ·of different crystal structures
can be made. T = n1a + n2b + n3c
Two dimensional space lattice spanned by basis vectors a and b is where n1, n2, n3 are integers. –
shown below:
Thus it is meant that by applying the operation T to a point r, we
reach another point r', which has the same environment as r.
r = r' + T = r' + n1a + n2b+ n3c
The set of points r', given above for all possible values of the
integers n1, n2 and n3 defines the space lattice. 18
17

3
 ..

Basis Unit Cell

A crystal structure is formed by associating every lattice point with
A unit cell is defined as a fundamental building block of a crystal
unit assembly of atoms or molecules or ions identical in
structure, which can generate the complete crystal by repeating its
composition, arrangement and orientation. This unit assembly is
own dimensions in various directions.
called the basis.
When the basis is repeated with correct periodicity in all directions,
it gives the actual crystal structure.

Crystal Structure = Lattice + Basis

This equation is not a mathematical expression, but it is used to

explain the formation of crystal structure 19 20

Crystallographic Axes Primitives

• Consider the unit cell.
Let us consider a unit cell • Let OA, OB and OC be the
consisting of three mutually intercepts made by the unit
perpendicular edges OA, OB cell along the crystallographic
and OC axes.
Draw parallel lines ·along the • These intercepts are known as
three edges. primitives.
• In crystallography, the
These lines are taken as intercepts OA, OB and OC are
crystallographic axes and represented as a, b and c
they are denoted as x, y and z respectively.
axes.
21 22

Interaxial Angles (or Interfacial

Angles) Lattice Parameters
• In a crystal, the angle between x, y
and z axes are called interaxial • To represent a lattice, the three interfacial angles and their
angles. corresponding intercepts are essential.
• The angle between x and y axes is • These six parameters are said to be lattice parameter.
.
• Similarly, angles between y & z
and z & x axes are denoted by a.
and b, respectively,
• The angles a, b and  are also
known as interfacial angles. 23 24

4
 ..

Crystal Systems and Bravais Lattices • Depending upon the axial ratios (𝑎∶ 𝑏∶ 𝑐) and angles between
them a, b and , there can be seven types of crystals.
• In order to specify the given arrangement of points in a space
lattice or of atoms in a crystal it is certainly important to define • In the nineteenth century, French crystallographer Auguste
its coordinates with reference to a set of axes chosen with its Bravais explained 14 different types of space lattices.
origin at a lattice point. • According to him, in a three
• The three axes or the axial lengths a, b, c and the interaxial dimensional space, the arrangement of
angles a, b and  are defined as the basic lattice parameters. identical points can be made on the
basis of periodicity such that those
points are identical in every way in their
surroundings.
• These 14 different types of space lattices
are called as Bravais lattices or space
25
lattices. 26

1. Cubic Crystals:
• In cubic crystal, axes are orthogonal to one another (a = b =  =
• Further each space lattice has a convenient set of axes however 900) and
only seven different system of axes have been found to be • the length of the primitives (edges of the unit cell) is the same
sufficient for representing all Bravais lattices. along the three axes (𝑎 = 𝑏 = 𝑐).
• Cubic lattices may be simple, body-centre or face-centred
• Accordingly fourteen space lattices are divided into seven • Simple cubic lattice have the lattice points situated only at the
crystal systems with their characteristic features. corners of the unit cell e.g. CsCl

27 28

Cubic Crystals (bcc): Cubic Crystals (fcc):

• Body-centred lattice have the lattice points situated at the corners
and also at the intersection on the body diagonals of the unit cell i.e • Face-centred lattice have the lattice point at the corners as well as
at the centre of the body e.g. α-iron at the centers of all the six faces of the unit cell e.g. NaCl

29 30

5
 ..

2. Tetragonal Crystals. 3. Orthorhombic Crystals

• The crystal axes are orthogonal to each another (a = b =  = 900). • The crystal axes are orthogonal to one another (a = b =  = 900).
• The length of the edges of unit cell is same along the two axes but
not same for the third such that 𝑎 = 𝑏 ≠ 𝑐. • but the lengths of the edges of unit cell along the three axes is
• Tetragonal lattices may be simple or body-centred different (𝑎 ≠ 𝑏 ≠ 𝑐).
• Orthorhombic crystals may be simple, base-centred, body-
centred, or face-centred

31 32

4. Trigonal (or Rhombohedral) Crystals. 5. Hexagonal Crystals

• The angles between each pair of crystal axes are the same but is
• The crystal axes are such that (a = b = 900 and  = 1200).
not equal to 900 (a = b =  < 120 & ≠ 900).
• The length of the edges of the unit cell along the three crystal axes • The length of the edges of the unit cell is same along all the axes that are
1200 apart, but along the third axis it is different (𝑎 = 𝑏 ≠ 𝑐).
(𝑎 = 𝑏 = 𝑐).
• The trigonal lattice is only simple • The hexagonal lattice is only simple

33 34

6. Monoclinic Crystals. 7. Triclinic Crystals

• Two of the crystal axes are not perpendicular to each other, but
the third is perpendicular to both of them (a =  = 900 and ≠ b) • None of the crystals axes is perpendicular to any of the other
(a ≠ b ≠ )
• The length of the edges of unit cell are different along all three
axes (𝑎 ≠ 𝑏 ≠ 𝑐). • length of the edges of the unit cell is different along all three
axes (𝑎 ≠ 𝑏 ≠𝑐).
• Monoclinic lattice may be simple or base-centred
• The triclinic lattice is only simple

35 36

6
 ..

37 38

v) Atomic Packing Factor (APF) or density of packing

Parameters related to crystals: Definitions
• The ratio of volume occupied by the atoms or molecules in unit
i) Unit cell volume: It is the volume of a unit cell. cell (v) to that of total volume of unit cell (V).
ii) Number of atoms per unit cell (N)
The total number of atoms present in a unit cell defines the number of 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑏𝑦 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
• APF =
atoms per unit cell. 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡h𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
iii) Co-ordination number No of atoms in a unit cell × Volume of an atom
The number of nearest neighbours that an atom has in a given crystal =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡h𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
lattice defines co-ordination number.
iv) Atomic radius 𝟒
𝑵 × 𝝅𝒓𝟑
𝟑
The radius of the atom is called atomic radius. It is also half of the centre =
𝑽
to centre distance of neighbouring atoms in a crystal.
V is the total volume of the cell, r is radius of atom and N is no of
39 40
atoms in a unit cell.

vi) Void space percentage: vii) Density of crystal

• The unutilized space present in a unit cell. It is defined as density, 𝜌 = =

Where Z is the number of atoms per unit cell and W is the mass
of each atom given as :
𝑀
𝑊=
𝑁

Where M is the molecular weight of the material and 𝑁𝐴 is the

Avagadro number (= 6.02214076 × 1023).

The density :
41 42

7
 ..

Calculation of Parameters: sc, bcc and fcc unit cells Simple cubic (sc) unit cell
• Various parameters like density, volume, lattice points per unit
cell, coordination number, atomic packing fraction etc. can be i) Unit cell volume
easily calculated in case of cubic unit cells.
• For a cubic system, we have the following three types of lattices: In a cubic cell, all the length of the edges of the cube are equal, thus
volume is given as: 𝑉 = 𝑎3
i. Simple cubic (sc, P): There is one lattice point at each of the corners
of the unit cell and is called as primitive cell.
Where “a” is the side of the cube.
ii. Body centred cubic (bcc, I): There is one lattice point at each of the
eight corners and one lattice point at the centre of the cubic cell.
iii. Face centred cubic (fcc, 𝐹): There is one lattice point at each of the
eight corners and one lattice point at the centre of each of the six
faces of the cubic cell. 43 44

ii) Number of atoms per unit cell iii) Co-ordination Number

• The number of nearest neighbours that an
• For a simple cubic or a primitive cell, there are 8 atoms: one at each corner atom has in a given crystal lattice defines
and each corner atom is shared by eight unit cells. co-ordination number.
• The share of each unit cell is equal to one eighth of an atom. • Let us consider any corner atom.
• The total number of atoms in one unit cell = 8 × = 1 (one atom) • For this atom, there are four nearest
neighbours in its own plane.
• There is another nearest neighbour in
another plane, which lies just below this
atom:
• Therefore the total number of nearest
neighbours is six. Hence the coordination
45
number is 6. 46

iv) Atomic radius, r v) Atomic Packing Factor (APF) or density of packing

• The ratio of volume occupied by the atoms or molecules in unit
• The distance between nearest neighbouring atoms in a unit cell is cell (v) to that of total volume of unit cell (V).
called atomic radius.
• For simple cubic, since the atoms are at the corners, thus the No of atoms in a unit cell × Volume of an atom
APF =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡h𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
atoms touch at cube edges.
• If r is the atomic radius and a is the cube edge, the nearest 𝑵 × 𝝅𝒓𝟑
𝟒
neighbouring distance can be calculated as: = 𝟑
𝑽
𝒂 𝟒 𝒂
• 2𝑟 = 𝑎 or 𝒓 = 𝟏× 𝝅
𝟑 𝟐
𝟑
𝝅
𝟐 = =
𝒂𝟑 𝟔

47 = 0.52 = 52% 48

8
 ..

vi) Percentage void effect Body centred cubic lattice (bcc lattice) or cubic I lattice
It can be defined as:
% void effect = ( 1- APF) × 100 i) Unit cell volume
= (1 - 0.52) × 100
= 48% In a cubic cell, all the length of the edges of the cube are equal, thus
vii) Density volume is given as:

𝜌= 𝑉 = 𝑎3
For simple cubic since Z = 1 Where “a” is the side of the cube.
𝑴
𝝆=
𝑵𝑨 𝒂𝟑
49 50

ii) Number of atoms per Unit Cell Coordinatioa Number (CN)

There are eight atoms at the eight corners of the unit cell and one
atom at the body centre. • Let us consider a body centered atom.
The contribution of corner atoms to each cell is 8 x 1/8 i.e. one. • The nearest neighbour for a body centered atom is a corner atom.
• A body centered atom is surrounded by eight corner atoms.
Also there is one atom per unit cell contribution from central atom
• Therefore, the coordination number of a bcc unit cell = 8.
Thus, the total number of atoms per unit cell is 1+1 i.e. 2 .

51 52

iv) Atomic radius, r v) Atomic packing fraction (APF)

In body centred cubic lattice, the atom at the body
centre touches the spheres at the corners The number of atoms per unit cell is 2 for bcc, atomic radius is r = a/2 and the
volume of the unit cell is a3, then

No of atoms in a unit cell × Volume of an atom

APF =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡h𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

53 54

9
 ..

vi) Percentage void effect Face centred cubic lattice (𝐟𝐜𝐜 lattice) or cubic F lattice
It can be defined as:
% void effect = ( 1- APF) × 100 Face-centred lattice have the lattice point at the corners as well as
= (1 - 0.68) × 100 at the centers of all the six faces of the unit cell e.g. NaCl
= 32%
vii) Density i) Unit cell volume

𝜌= In a cubic cell, all the length of the edges

of the cube are equal , thus volume is
For bcc, Z = 2 given as: 𝑉= 𝑎3

𝟐𝑴 Where “a” is the length of cube.

𝝆=
𝑵𝑨 𝒂𝟑 55 56

iii) Co-ordination Number (CN)

ii) Number of atoms per Unit Cell
• Let us consider a corner atom. In its own
• Contribution of 8 corner atoms to plane it touches four ·face centered atoms.
• These face centered atoms are its nearest
each unit cell = 8 × 1/8 i.e. one. neighbours.
• In a plane, which lies just above this corner
• Contribution of 6 atoms, one each atom, it has four more face centered atoms
on 6 faces, to each unit cell = 6× as nearest neighbours.
• Similarly, in a plane, which lies just below
½=3 this crner atom, it has yet four more face
centered atoms as its nearest neighbours.
• Thus, the total number of atoms • Therefore, the number of nearest neighbours
i.e., coordination number for fcc unit cell =
per unit cell is 1+ 3 = 4 .
4+4+4 = 12.
57 58

iv) Atomic radius, r v) Atomic packing fraction (APF)

In a FCC cell, atoms are in contact along the face diagonal of the cube.
The number of atoms per unit cell is 4 for fcc,
𝒂
The atomic radius can be calculated as: Atomic radius is 𝒓 = 𝟐 𝟐 and the volume of the unit cell is a3, then
Consider  ABC,
No of atoms in a unit cell × Volume of an atom
AC2 = AB2 + BC2 APF =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡h𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
(4r)2 = a2 + a2
16 r2 = 2 a2 ×
The atomic radius = = =
𝒂
𝒓=𝟐 𝟐 = 0.74 = 74%
59 60

10
 ..

vi) Percentage void effect

It can be defined as:
% void effect = ( 1- APF) × 100
= (1 - 0.74) × 100
= 26 %
vii) Density

𝜌=

For fcc, Z = 4
𝟒𝑴
𝝆=
𝑵𝑨 𝒂𝟑 61

11