SOLID STATE

2.0 INTRODUCTION
Solids are characterized by incompressibility, rigidity and mechanical strength. There are
two types of solids namely amorphous solids and crystalline solids. The following are the
important differences between them.
Crystalline Solids Amorphous solids
1. In crystalline solids the structural units are In amorphous solids the structural units are
orderly arranged and they have definite not orderly arranged eg. Glass, plastic.
geometrical configurations. eg. Sugar, NaCl
2. They have sharp melting point They do not have sharp melting point.
3. They have well defined faces and shapes They do not have well defined faces &
shapes.
4. They are anisotropic ie. they exhibit They are isotropic. ie. They exhibit same
different physical properties in all physical properties in all the directions.
directions.
5. They have characteristic heats of fusion. They do not have characteristic heats of
fusion.
6. They are generally incompressible. They may be compressed to an extent.
7. They give a regular cut when cut with a They give irregular cut.
sharp edged knife.
8. They are regarded as true solids. They are regarded as super cooled liquids or
pseudo solids.
IMPORTANT TERMS USED IN SOLID STATE
Space Lattice
An infinite three dimensional array of points showing how atoms or molecules are
arranged in a crystal is known as space lattice. The points are known as lattice points.
Unit cell
It is defined as the smallest fundamental portion of a crystal lattice when repeated in three
dimensions will generate the crystal.
Totally there are 7 classes of unit cells. (a) cubic (b) Triclinic (c) monoclinic (d) orthorhombic (e)
tetragonal (f) hexagonal and (g) rhombohedral

Characteristic parameters of a unit cell

i) Crystallographic axes:- 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.
ii) Interfacial angles:- The angles between the three crystallographic axes are known as
interfacial angles.
iii) Primitives:- The three sides a,b & c of a unit cell are known as primitives or characteristic
intercepts.
Crystallograpic axes OX, OY, OZ Interfacial angles : α, β, γ, Primitives : a, b, c.
Cubic System
Crystals belonging to this system are built upon three equal axes at right angles to one
another. There are three types of cubic lattices.
(i) Simple cubic crystal (SC) : In this the atoms are present only at the corners. In a simple cubic
structure, each corner atom is shared by eight surrounding cubes, it contributes for 1/8 of an atom.
Thus each simple cube has (8 x 1/8) = 1 atom per unit cell in a crystalline solid.

(ii) Body Centred Cubic Crystal (BCC)

A BCC structure possess 8 corner atoms along with one body centre atom. Eight corner
atoms contribute 1 atom per unit cell. The centre atom also contributes one per unit cell. Hence the
number of atoms per unit cell is 2.

(iii) Face Centred Cubic Crystals (FCC)

A FCC structure posses 8 corner atoms along with 6 atoms, one each at the centre of each
face. The 8 corner atoms contribute for 1/8 of an atom and thus only one atom per unit cell. Each
of six face centred atom is shared by two adjacent unit cells and so it contributes ½ of its share for
each unit cell. ie. a total of 6 x ½ = 3 atoms per unit cell. Hence, the number of atoms per unit cell
in FCC structure are (i) 3 face centred and (ii) 1 corner atom ie. 4 atoms per unit cell.
 SEVEN CRYSTAL SYSTEMS

Elements of Bravais lattice

S.No Crystal System Axes and angles Examples
Symmetry Nos. Types

1 Cubic A=b=c Centre 1 NaCl, KCl 3 1. Simple cube

Α = β = γ = 90o Plane 9 CsCl, ZnS, Pb2 2. Face centered cube
Axes 13 diamond 3. Body centered cube
2 Hexagonal A=b≠c Centre 1 ZnO, CdS, HgS, 1 Hexagonal prism
o
α = β = 90 Plane 7 Ice, urea, graphite
γ = 120o Axes 7
3 Tetragonal A=b≠c Centre 1 SnO2 , Ti O2, Sn 2 1. Tetragonal prism
Α = β = γ = 90o Plane 5 2. Body centered tetragonal prism
Axes 5
4 Orthorhombic a≠b≠c Centre 1 KNO3, K2SO4 BaSO4, 4 1. Rectangular prism
α = β = γ = 90o Plane 3 rhombic sulphur 2. Body centered rectangular prism
Axis 3 3. Rhombic prism
4. Body centered rhombic prism
5 Monoclinic a≠b≠c Centre 1 Monoclinic sulphur, 2 1. Monoclinic parallel epiped
α = γ = 90o Plane 1 CaSO4 . 2H2O, NaSO4 2. Monoclinic one face centered
β ≠ 90o Axis 1 10H2O
6 Triclinic a≠b≠c Centre 1 CuSO4 5H2O 1 Triclinic parallel epiped
α ≠ β≠ γ ≠ 90o K2Cr2O7, H3BO3
7 Rhombohedral a=b=c Centre 1 CaCO3 , NaNO3 quartz 1 Rhombohedron
α = β= γ = ≠ 90o Plane 3
Axes 4
Co-ordination number
Coordination number is defined as the number of nearest neighbours that an atom has in a unit cell.
Co.No.
a) Simple cubic structure 6
b) Body centred cubic structure 8
c) Face centred cubic structure 12
Characteristic of cubic lattices
Simple Body centred Face centred
Characteristics
cube cube cube
1. Unit cell volume a3 a3 a3
2. Lattice points per unit cell 1 2 4
3. Nearest neighbour distance a

4. Coordination number 6
8 12
5. Second nearest neighbour
a a
distance
6. Number of second neighbours
12 6 6

Close packing arrangements (hcp, ccp)

The close packing arrangements describe how the atoms are closely arranged in a crystal occupying
minimum amount of space.
First layer is formed by placing a number of spheres in such away that each sphere is in contact with
six other spheres of the same layer. In such an arrangement obviously depressions will be formed in between
the spheres. The second layer is formed by placing the spheres in the depressions on the top of the first layer.
Again in the second layer also, each sphere is in contact with six other sphere of the same layer.

There are two ways in which the third layer can be arranged on the top of the second layer. If the
spheres in the third layer are arranged exactly above the spheres in the first layer, the arrangement is known
as hexagonal close packing hcp arrangement. This arrangement is also known as ABABAB….. arrangement
. If the spheres in the third layer are arranged not exactly above the spheres in the first layer but in a position
different from the position of spheres in the first and second layer, such an arrangement is called cubic close
packing ccp or face centred cubic, fcc arrangement. This arrangement is also known as ABCABC…..
arrangement

Arrangement of third layer in hcp & ccp

Packing Fraction or Packing Efficiency

It is defined as the fraction of the total volume occupied by the molecules in a crystal system.
Packing density = υ / V
Let us calculate the packing fraction for simple cube, body centred and fcc systems.

Packing density of simple cubic structure (SC)

Let ‘a’ be the cube edge of unit cell and ‘γ’ the atomic radius. In SC structure, the unit cell contains
one atom on the average.
Volume of atoms in unit cell (V) = 1 x 4/3 π γ3
For SC structure
γ = a/2 V = 4/3 π (a/2) 3 = π a3 /6
Volume of unit cell = V = a3

This reveals that 52% of the unit cell is occupied by atoms and 48% is empty.
Packing density of body Centred cubic structure (BCC)
The unit cell of bcc structure contains 2 atoms on the average.
Volume of atoms in the unit cell (V) = 2 x 4 / 3 π r3

Volume of unit cell V = a3

Thus reveals that 68% of the unit cell is occupied by atoms and 32% is empty.
Packing density of face centred cubic structure (FCC)
The unit cell of fcc structure contains 4 atoms on the average.
Volume of atoms in the unit cell V = 4 x 4 / 3 π r3

Volume of unit cell V = a3

This reveals that 74% of unit cell is occupied by atoms and 26% is empty.
Radius Ratio
The radius ratio is the ratio of the radius of smaller ion, usually cation to that of larger ion, usually
anion. It is given by
P=r+/r–
The limiting radius ratio that can tolerate a given coordination number is listed below.
Coordination number Geometry Limiting radius
(CN) ratio
2 Linear 0.0 – 0.15
3 Triangular 0.15 – 0.22
4 Tetrahedral 0.22 – 0.414
4 Square planar 0.22 – 0.414
6 Octahedral 0.414 – 0.73
8 Cubic 0.73 – 1.0

Goldschmidt radius ratio

Every compound can be identified by a unique arrangement of the atoms in the crystal structure,
which determines the inter–atomic distances and the compositional ratios and thus helps understanding
specific material properties. For this reason, crystal structure determination and analysis are essential not
only from a mere crystallographic viewpoint, but also for numerous fields of materials research, chemistry,
physics and life sciences.

Goldschmidt's radius ratio (or) tolerance factor is an indicator for the stability and distortion of
crystal structures. It was originally only used to describe perovskite structure, but now tolerance factors are
also used for ilmenite. Alternatively the tolerance factor can be used to calculate the compatibility of an ion
with a crystal structure. The first description of the tolerance factor for perovskite was made by Victor
Moritz Goldschmidt in 1926. The evaluation of crystal structures can be facilitated by various tools and
indicators. For instance, Goldschmidt tolerance factor (T ) of perovskite compounds ABX3 (A and B: metal
cations, X: chalcogen or halogen group) is widely used to assess the geometric stability and distortion of
crystal structures in terms of the constituent ionic packing.

Mathematical expression
The Goldschmidt tolerance factor (t) is a dimensionless number that is calculated from the ratio of
the ionic radii.

√ ( )

rA is the radius of the A-cation.

rB is the radius of the B-cation.
r0 is the radius of the anion (usually oxygen).

In an ideal cubic perovskite structure the axis of the unit cell (a) can be described with the following
equation:
√ ( ) ( )
Goldschm
idt
Structure Explanation Example Example lattice
tolerance
factor (t)
A ion too big
Hexagonal or
>1 or B ion too BaNiO3 -
Tetragonal
small.

A and B ions
SrTiO3
0.9-1 Cubic have ideal
BaTiO3
size.

A ions too GdFeO3 (Ort

Orthorhombic/ small to fit horhombic)
0.71 - 0.9
Rhombohedral into B ion CaTiO3 (Orth
interstices. orhombic)

A ions and B Ilmenite,

Different
<0.71 have similar FeTiO3 (Trig -
structures
ionic radii. onal) [3]

The T is defined by ratios of constituent ionic radii of A, B and X as T = (RA + RX)/√2(RB + RX),

where RA, RB and RX are the ionic radii of A, B and X, respectively.

From the following figure, the ideal perovskite compounds adopt a cubic close packed structure
with T = 1. When the ratio of the ionic radii deviates from the ideal value (T ≠ 1), a geometric strain and
crystal distortions arise. As the deviation from T = 1 becomes greater, the crystal adopts structures of lower
symmetry than the cubic one. Thus by calculating T, the crystalline structure can be predicted and its
geometric strain and stability evaluated. At the same time, the T can be used to estimate the compatibility of
different ions with a crystalline structure. Because of its simplicity and practicality, the T is used extensively
in a wide variety of fundamental and applied studies
 (a) concept of T, (b) loosely packed crystal structure with a small radius of A with T < 1 and tightly
packed crystal structure with a large radius of A with T > 1, and (c) concept of the IFF in an ideal cubic
perovskite structure with a lattice constant a and Z = 1 (purple sphere: A; lime spheres: B; black spheres: X;
Grey cuboid: Vunit/Z; purple + lime + 3 × black spheres: Vion). The IFF shows spherical ionic volume fraction
in the crystal structure (grey cuboid).