Crystal structure: Lattice (space, Bravais, Non-Bravais), Lattice Parameters, crystal systems,

Defects in Crystals. Numerical.

Crystal structure:

Introduction
The study of macroscopic matter in terms of microscopic particles is originally called ‘solid
state physics’. This subject primarily deals with the understanding of the structural properties
of the materials such as metals, non-metals, ceramics, semiconductors, insulators and so on.
The matter exists in three states, they are solids, liquids and gaseous form, in the gaseous and
liquid state the atoms or molecules move randomly from one place to other without any fixed
position occupied by them. However, in the solid state the position of the atoms or molecules
are at fixed positions. Based on the internal atomic structure, the solids are classified into two
categories namely (i) crystalline solids and (ii) Non- crystalline or Amorphous solids.

Crystalline solids (or) crystals:

The ‘Crystals (Grains)’ are those in which the constituent atoms or molecules are arranged in
an orderly fashion throughout the crystal in a three-dimensional pattern. The crystalline solids
have directional properties and therefore they are called ‘Anisotropic substances’.
Crystalline materials are of two forms: Single and poly crystal.

Single crystal: In this, the solid contains only one crystal. These are produced artificially from
their vapour (or) liquid state.

Poly Crystal: In this, the solid contains an aggregate of many small crystals (or) grains
separated by well-defined grain boundaries. These materials have a sharp melting point.

Examples for crystalline solids: silicon, germanium, copper, tungsten, diamond, iron, nickel,
aluminium, sliver etc.,
The arrangement of atoms for a two-dimensional system is shown below

Non-crystalline (or) Amorphous solids

In Amorphous solids, the constituent atoms or molecules are not arranged in an orderly
fashion.
These solids have No directional properties and therefore they are called ‘Isotropic
 substances’.
Amorphous solids do not have sharp melting point.

Examples for amorphous solids: Rubber, plastics, glass, mica, wood etc.,
The arrangement of atoms for a two-dimensional system is as shown below

Difference between crystalline and amorphous solids

Crystalline solids Amorphous solids
⚫ These solids have regular and periodic ⚫ These solids have irregular arrangement of
arrangement of atoms. atoms
⚫ Crystalline solids are anisotropic in nature i.e., ⚫ Amorphous solids are isotropic in nature
these solids having different properties in i.e., these solids having properties in all
different directions. directions.
⚫ Crystalline solids have sharp melting points. ⚫ The amorphous solids do not have sharp
melting points.
⚫ Crystalline solids have long range order of atomic ⚫ Amorphous solids have short range order
interaction. of atomic interaction.
⚫ The cooling curve of a crystalline solids has ⚫ The cooling curve of an amorphous solids
breaks. is smooth.
Temp
Temp

Time Time

⚫ Crystalline solids have low lattice energy. ⚫ Amorphous solids have high lattice energy.

⚫ Ex:Nacl, Kcl, calcite, quartz etc., ⚫ Glass, pitch, rubber etc.,

Fundamental aspects of crystal structures

❖ Lattice: “Lattice is defined as an array of points which are imaginarily kept to represent
the position of atoms in the crystal such that every lattice point has got the same environment
as that of the other and hence one lattice point cannot be distinguished from the other lattice
point”.
 ❖ Space lattice (or) crystal lattice: “space lattice is defined as an infinite array of points
in three dimensions in which every point has surroundings identical to that of every other
point in the array”.
Let us consider the case of two dimensional square array of points as shown in fig. By repeated
translation of the two vectors a and b on the paper, we can generate the square array. The
magnitude of a and b are equal and can be taken to be unity. the angle between them is 90o.
a and b are called ‘Fundamental Translational vectors’.

Let us choose any arbitrary point ‘o’ as origin. If we choose a lattice point ‘P’ at position
‘r’ it can be represented by translational vectors as
r = la + mb
Where l and m are integers.
For a three dimensional lattice: r = la + mb + nc
Thus, space lattice is only a geometrical arrangement of lattice points in space. But each lattice
point may be collection of atoms, ions or molecules.

❖ Lattice points: “Lattice points denote the position of atoms or molecules in the crystal”
(or) the points in the space lattice are called ‘Lattice points’.

❖ Basis (or) Motif: “Basis can be defined as the assembly of atoms or molecules identical
in composition, arrangement and orientation”.
It is also called ‘pattern’. The basis can be explained by the following diagram, It can be seen
that a basis consists of two different atoms and also it is identical in composition, arrangement
and orientation.
In crystalline solids like Al, Cu, Ag, Na the basis contains single atom. In the case of Nacl, KBr,
Kcl, Cscl the basis contains two atoms and in CaF2 the basis is three atoms.

❖ Crystal structure: The crystal structure is formed by the addition of basis to every
lattice point in lattice.

The logical relation for crystal structure is

Space lattice + Basis = Crystal structure

❖ Unit cell: “The unit cell may be defined as the fundamental elementary pattern with
minimum number of atoms, molecules (or) group of molecules which represents the total
characteristics of the crystal”.
Let us consider a two dimensional crystal in which the atoms are arranged as shown below.

If we consider a parallelogram with side ‘a’ and ‘b’ then by rotating this parallelogram by any
integral multiple of vectors a & b , the whole crystal lattice may be obtained.
In this way this fundamental unit is called a ‘unit cell’.
The choice f the unit cell is ‘not unique’. It can be constructed in many number of ways like A,
B, C, D, E and F as shown in diagram.

A three-dimensional unit cell is as shown below.

The unit cell is a parallelopiped formed by the basis vectors a , b and c as concurrent edges
and including angles α, β, γ between b and c , c and a , a and b respectively. Thus in general
unit cell may be defined as the volume of a solid from which the entire crystal may be
constructed by translational repetition in three dimensions.

❖ Primitive cell: “A primitive cell is the simplest type of unit cell which contains only one
lattice point per unit cell (contains lattice points at its corners only).
Ex: simple cubic (SC)

❖ Non-primitive cell: “If there are more than one lattice point in a unit cell, it is called a
non-primitive cell.
Ex: body centered cubic structure (BCC), Face centered cubic structure (FCC).
❖ Lattice parameters (or) unit cell parameters:
“The parameters which describe unit cell of a crystal completely are called Lattice
parameters”.
The lines drawn parallel to the lines of intersection of any three faces of the unit cell which do
not lie in the same plane are called ‘crystallographic axes’.
The intercepts a, b, c define the dimensions of an unit cell and are known as its ‘primitives (or)
characteristic intercepts’ on the axes. The angles between the three crystallographic axes (α,
β, γ) are known as ‘interfacial (or) inter axial angle’. Both, the intercepts (a, b, c) and interfacial
angles (α, β, γ) constitutes the lattice parameters (or) cell parameters of the unit cell. The
actual size of the unit cell can be determined by knowing the values of intercepts and
interfacial angles.

❖ Bravais lattice
“A space lattice is an array of points in space such that the environment about each point
is the same. If all the atoms at the lattice points are identical, the lattice is called Bravais
lattice.”
In 1848, Bravais showed that 14 lattices are sufficient to describe all crystals. These 14
lattices are known as ‘Bravais lattices’ and are classified into 7 crystal systems based on the
cell parameters.

The Bravais lattices are categorized as:

Primitive lattice - P Body-centered lattice - I
Face centered lattice – F Base (or) side centered lattice - C

The seven crystal systems and Bravais lattices are as follows: Based on values of lattice
parameters, crystal systems are classified into seven categories. The primitives and interfacial
angles for seven crystal systems are given in the following table.
Crystal Type of Number
Characteristic
lattice Bravais of Bravais Unit cell parameters
symmetry elements
systems lattice lattice
Cubic P, I, F 3 a=b=c  =  =  = 900 Four 3-fold rotation
axes
Tetragonal P, I 2 a=bc  =  =  = 900 One 4-fold rotation
axes
Orthorhombic P, I , 4 abc  =  =  = 900 Three mutually
F ,C perpendicular 2-fold
rotation axes
Monoclinic P, C 2 abc  =  = 900   one 2-fold rotation
axes
Triclinic P 1 abc       900 None
Rhombohedral P 1 a=b=c  =  =   900  1200 One 3-fold rotation
axes
Hexagonal P 1 a=bc  =  = 90 0
and One 6-fold rotation
axes
 = 1200
 ❖ Examples
S.No Name of the crystal primitives Interfacial angles Examples
system
1 Cubic a=b=c  =  =  = 900 NaCl, Ag, CaF2

2 Tetragonal a=bc  =  =  = 900 SnO4, NiSO4, TiO2

3 Orthorhombic abc  =  =  = 90 0
SnSO4, BaSO4,
K2SO4
4 Monoclinic abc  =  = 900   Na2SO4, FeSO4, CaSO4
5 Triclinic abc       900 CuSO4, K2Cr2O7,
(CuSO4.5H2O )
6 Rhombohedral a=b=c  =  =   900  1200 CaCO3, As, Sb
(Trigonal)
7 Hexagonal a=bc  =  = 900 and  = 1200 SiO2, Zn, Cd

The unit cells of all the crystal systems are as shown below.

❖ The Three main types of cubic crystals

1. Simple cubic crystal system (SC) (Primitive cubic): In this structure, the atoms are
present only at the corners of the unit cell, hence, the unit cell of the simple cubic structure
is primitive. The atoms touch each other along the edge of the cube. Ex: Polonium.
 2. Body-centered cubic crystal system (BCC): This structure has one atom in each corner
of
the cube and one atom in the center. This structure is more tightly packed than the simple
cubic structure, because of an additional atom existing at the centre of the cube, hence this
crystal system is not primitive. Ex: lithium, sodium, potassium, rubidium, and cesium.

3. Face-centered cubic crystal system (FCC): This structure has atoms at each corner of
the
crystal lattice and in the centre of each face of the cube. Each atom in the face-centred region
is shared between two adjacent unit cells, so only half of each atom belongs to a single cell.
The unit cell of FCC is a non-primitive cell Ex: aluminum, gold, nickel, copper, platinum.

Crystal defect (Imperfection)

A crystal defect is an imperfection in the regular geometrical arrangement of the atoms
in a crystalline solid. These imperfections result from the deformation of the solid by rapid
cooling from high temperature, or high-energy radiation (X-rays or neutrons) striking the
solid, foreign atoms, external stresses, and thermal effect. These defects influence the
mechanical, electrical, and optical properties of the crystal.
Defects included: Point defects, linear defects, surface defects
1. Point defects:
A point defect is a very localized defect in a lattice's regularity. The defect may be as
small as one or two atomic diameters or roughly the size of a point (zero dimensions).
Types of point defects: Vacancy, Interstitial, Frenkel and Schottky defect.

I. Vacancy: An atom missing from its lattice site in a crystal structure is called a
vacancy (or vacant lattice site). The atoms surrounding a vacancy experience a slight
displacement into the empty lattice site, and thus, a vacancy is a centre of approximately
spherical distortion in the lattice. There could be di-vacancies (an association of two vacancies)
or even tri-vacancies.

II. Interstitial (Self-Interstitial): An atom occupies an interstitial site, which is

different from its typical position. An impurity (foreign) atom is present on the lattice by
substituting the lattice site atom. Substitutional atoms may either be larger than the normal
atom in the lattice (in which case, the surrounding atoms are compressed, or smaller (causing
the surrounding atoms to be in tension).
Typically, creating an interstitial needs a significant amount of energy. Exposure to
high-energy neutrons in a nuclear reactor, or by drastic cold working makes vacancies.
 III. Frenkel Defect: When an atom is shifted from a normal lattice site (thus creating
vacancy) and is forced into an interstitial position, the resulting pair of point defects (a vacancy
as well as the interstitialcy) together is called a Frenkel defect.

IV. Schottky defects: a missing positive ion and negative ion from the crystal.

All in one diagram

2. Linear Defects – Dislocations

Line defects, or dislocations, are lines along which whole rows of atoms in a solid are
arranged anomalously. The resulting irregularity in spacing is most severe along a line called
the line of dislocation. Line defects can weaken or strengthen solids. Dislocations are
generated and move when stress is applied. The motion of dislocations allows slip–plastic
deformation to occur.
There are two basic types of dislocations: the edge dislocation and the screw dislocation.
 I. Edge Dislocations: Edge dislocations occur when an extra half-plane is inserted.
The slip plane is at the end of the plane. This line runs along the top of the extra half-plane.
The inter-atomic bonds are significantly distorted only in the immediate around of the
dislocation line. The dislocation in the top half of the crystal is slipping one plane at a time as
it moves to the right from its position in the image (a) to its position in image (b) and finally
image (c). In the process of slipping one plane at a time, the dislocation propagates across
the crystal. The movement of the dislocation across the plane eventually causes the top half
of the crystal to move concerning the bottom half. However, only a small fraction of the bonds
are broken at any given time. Movement in this manner requires a much smaller force than
breaking all the bonds across the middle plane simultaneously. the edge dislocation moves
parallel to the direction of stress.

II. Screw Dislocations: Screw dislocations result when displacing planes relative to
each other through shear stress. The burgers vector is parallel to the dislocation line.
• The motion of a screw dislocation is also a result of shear stress, but the defect line
movement is perpendicular to direction of the stress and the atom displacement, rather
than parallel.
• To explain a screw dislocation, imagine a block of metal with a shear stress applied across one
end so that the metal begins to rip. It can be seen that only a portion of the bonds are broke
at any given time (EXPLAIN). The movement in this manner requires a much smaller force than
breaking all the bonds across the middle plane simultaneously. If the shear force is increased,
the atoms will continue to slip to the right. A row of the green atoms will find there way back
into a proper spot in the lattice (and become red) and a row of the blue atoms will slip out of
 position (and become green). In this way, the screw dislocation will move upward in the image,
which is perpendicular to direction of the stress. The net plastic deformation of both edge and
screw dislocations are the same. The dislocations move along the densest planes of atoms in
a material, because the stress needed to move the dislocation increases with the spacing
between the planes. FCC and BCC metals have many dense planes, so dislocations move
relatively easy and these materials have high ductility. Metals are strengthened by making it
more difficult for dislocations to move. This may involve the introduction of obstacles:
interstitial atoms or grain boundaries. In ionically bonded materials, the ion must move past
an area with a repulsive charge in order to get to the next location of the same charge.
Therefore, slip is difficult and the materials are brittle. Likewise, the low density packing of
covalent materials makes them generally more brittle than metals.

• The atoms represented by the blue

circles have not yet moved from their
original position.
• The atoms represented by the red
circles have moved to their new
position in the lattice and have
reestablished metallic bonds.
• The atoms represented by the green
circles are in the process of moving.

3. Interfacial Defects (Surface defects):

It may arise at the boundary between two grains, or small crystals, within a larger crystal. The
rows of atoms in two different grains may run in slightly different directions, leading to a
mismatch across the grain boundary. The actual external surface of a crystal is also a surface
defect because the atoms on the surface adjust their positions to accommodate for the
absence of neighboring atoms outside the surface. Come from: between different phases, or
between different crystals.

I. External Surfaces: The environment of an atom at a surface differs from that of

an atom in the bulk, in that the number of neighbors (coordination) decreases. This introduces
unbalanced forces which result in relaxation (the lattice spacing is decreased) or
reconstruction (the crystal structure changes). Surface atoms have unsatisfied atomic bonds,
and higher energies than the bulk atoms ⇒ Surface energy, γ (J/m2).
• Surface areas tend to minimize (e.g. liquid drop)
• Solid surfaces can “reconstruct” to satisfy atomic bonds at surfaces.
 II. Grain Boundaries: Polycrystalline material comprised of many small crystals or
grains. The grains have different crystallographic orientation. There exist atomic mismatch
within the regions where grains meet. These regions are called grain boundaries. Surfaces and
interfaces are reactive and impurities tend to segregate there. Since energy is associated with
interfaces, grains tend to grow in size at the expense of smaller grains to minimize energy. This
is accelerated at high temperatures. The density of atoms in the region including the grain
boundary is smaller than the bulk value, since void space occurs in the interface.
It is convenient to separate grain boundaries by the extent of the mis-orientation between
the two grains.
• low angle grain boundaries: are those with a misorientation less than about 11 degrees.
• high angle grain boundaries : whose misorientation is greater than about 11 degrees.

II. Twin boundaries: A twin boundary has different crystal orientations on its two
sides. But unlike a grain boundary, the orientations are not random, but related in a specific,
mirror-image way. A twin boundary happens when the crystals on either side of a plane are
mirror images of each other. The boundary between the twinned crystals will be a single plane
of atoms. There is no region of disorder and the boundary atoms belonging to the crystal
structures of both twins.
 The twinned crystals come from:
• crystallisation, or the result of mechanical or thermal work.
• Grown twins because of change in the lattice during growth due to a larger substituting ion.
• Annealing results a change in crystal system during cooling.
• gliding twins are the result of stress on the crystal.

II. Stacking Fault: Is any defect that alters the periodic sequence of layers. These defects
may be a wrong layer inserted into the sequence, a change of the layer sequence or a different
translation between two subsequent layers. The common example of stacking faults is in
close-packed crystal structures. Face-centered cubic (fcc) structures differ from hexagonal
close packed (hcp) structures only in stacking order: The stacking sequence ABABABA...
produces an hexagonal crystal (hcp; hexagonal close packed).
The stacking sequence ABCABCA... produces a cubic face-centred fcc crystal.