Chapter 3

SOLID STATE AND MATERIALS SCIENCE

CHARACTERISTICS OF SOLIDS
‘‘A solid is always characterized by its definite shape, volume, in-com-
pressibility, rigidity and mechanical strength.’’ Solid have very short
intermolecular distance and very strong intermolecular force.
CLASSIFICATION OF SOLIDS
Solids can be classified as (i) crystalline and (ii) amorphous, based on their
characteristic properties.
Crystalline Solids
Have well defined geometric structures or shapes due to definite and
orderly arrangement of ions or atoms or molecules in three dimensional
network with long range order.
Example: NaCL(FCC), CsCL(BCC), ZnS(Sphalerite), diamond, quartz etc.
(i) Sharp melting points and (ii) their physical properties electrical,
 
thermal and mechanical etc. are ‘anisotropic’.
Amorphous
Do not exhibit any repetitive pattern or arrangement of atoms (or
molecules) of substance and has in fact, no regular geometrical structure in
three-dimensional space.
(i)No sharp melting points and (ii) that their measured physical properties
are ‘isotropic’.
TYPES OF CRYSTALLINE SOLIDS
Solids are classified based on the nature of the chemical bonding in to
crystalline solids. They are
(a) Ionic crystals NaCl,CsCL,etc.
(b) Covalent crystals Diamond, SiC, etc.
(c) Molecular crystals Ice, solid , etc.
(d) Metallic crystals Cu, Zn, Ag, etc.
 
Ionic Crystals
• Ionic crystals are hard and brittle solids
• They possess high melting points
• They are poor conductors of electricity, but their ability to conduct
increases drastically in melt.
e.g., NaCl : Face centered cubic (AB Type)
CsCl : Body centered cubic (AB Type)
ZnS : Sphalerite (AB Type)
CaF2 or Zr : Face centered cubic ( Type)
BaTi or MgSi (Perovskite) : FCC cubic primitive (AB Type)
MgA : Spinel FCC lattice (AType)
Covalent Crystals
• Covalent crystals are hard solids that possess very high melting points.
• They are poor conductors of electricity.
• In covalent crystals, atoms are held together by covalent bonds.
• Eg - diamond and graphite.
 
Molecular Crystals
• Molecular crystals are very soft solids that possesses low melting points.
• They are poor conductor of electricity.
• They are packed together as closely as their size and shape will allow.
• The attractive forces are mainly van der Waals interactions.
• , CC, and benzene
Metallic Crystals
• Metals are characterised by their tensile strength and the ability to
conduct electricity.
• Both properties are the result of the special nature of the metallic bond.
Bonding electrons in metals are highly delocalised over the entire crystal.
• Metal atoms can be thought of as an array of positive ions immersed in a
sea of the delocalised valence electrons.
• The great cohesive force resulting from the delocalisation is responsible
for the great strength noted in metals.
• The mobility of the delocalised electrons accounts for electrical
conductivity.
• Metal crystals all have a high density which means that they usually have
the hcp or fcc structure.
.
STRUCTURE OF CRYSTALLINE SOLIDS
Closed Packed Structure
The constituent particles in a crystal, these particles are hard spheres of
identical size.
The packing of these spheres takes place in such a way that they occupy the
maximum available space and hence the crystal has maximum density.
This type is close packing.
‘‘A close packed structure is a way of arranging identical atoms in space
such that the available space is filled efficiency.’’
Non-directional forces - based on close packing.
Directional forces - based on linked polyhedral or groups of polyhedral.
Types of Close Packing
(a) When the spheres are placed in horizontal row, touching each other, an
edge of the crystal.
(b) Two-dimensional packing when the rows are combined, touching each
other, crystal plane. The particles when placed in the adjacent rows show
a horizontal as well as vertical alignment and forms square or cubic. This
type of packing is called cubic close packing (ccp).
The particles in every next row are placed in the depressions between the
particles of first row. The particles in the third row will be vertically aligned
with those of in the first row. This type of packing gives a hexagonal pattern
and is called hexagonal close packing (hcp).
 Voids and Holds in a Close Packing
• The stacking of two close packed anion layers produce two types of
voids or holes.
• One set of holes are octahedrally coordinated by 6 anions.
• The second set is tetrahedrally coordinated by 4 anions.
• One octahedral site and two tetrahedral sites are created by each anion in
the close packed layer.
• Which sites are occupied by a given cation. (radius ratio= rcation / ranion)
• How many sites are occupied. (the stoichiometry)
1. If the triangular void in a close-packed layer has a sphere directly over
it, there results a void with four spheres around it, as shown in Fig. 3.
13 (a).
Such as void is called a tetrahedral void since the four spheres
surrounding it are arranged on the corners of a regular tetrahedron Fig. 3.
13. (b). If R denotes the radius of the four spheres surrounding a
tetrahedral void , the radius is 0.225 R.
2. If a triangular void pointing up in one close-packed layer is covered
by a triangular void pointing down in the adjacent layer, then a void
surrounded by six spheres results [Fig.3.14(c)]. Such a void is called an
Octahedral void since the six spheres surrounding it lie at the corners of a
regular octahedron. The radius is 0.414R.
PROPERTIES OF IONIC AND COVALENT CRYSTALS
Radius Ratio Rule for Geometric Types of Ionic Crystals
In Ionic crystal
Co-ordination number- the number of opposite charge ion surrounding
a given ion.
Radius ratio (R) = (r+)/(r-)
Greater R, the larger the size of the cation, greater the coordination
number. Thus the ‘radius ratio’ of ions in crystals can be used to predict the
geometry (or shape) of ionic crystals.
Table3.1 Prediction of crystal geometry from radius ratio and coordination number.
Radius ratio Coordination number Geometry of crystal
-----------------------------------------------------------------------------------------------------------------------------
-
0 – 0.155 2 Linear
0.155-0.225 3 Trigonal planner
0.225-0.414 4 Tetrahedral
0.414-0.732 4 Square planer
0.414-0.732 6 Octahedral
0.732-1.00 8 BCC
1.0 12 Closepacking (hcp or ccp)
Stable bonding Configuration in Ionic Solids
If the cation is larger than the ideal radius ratio value the cation and
anion remain in contact, however the cation forces the anions apart. If the
cation is too small for the site then the cation would ‘rattle’ and would not be
in contact with the surrounding anions. This is an unstable bonding
configuration.
 Ina few rare cases solids too small for their sites, it moves off the centre
of the site and adopt adistorted octahedral coordination. They exhibit
novel properties, ferroelectricity and piezoelectricity.
Covalent Network and Allotropic Forms
Covalent solids - giant molecular solids.
- Low coordination numbers and highly directional
bonding
- very high melting points and boiling points.
Allotropic solids of Carbon
eg- graphite (m.pt-3652°C, b.pt-4200°C), diamond (m.pt-3550°C, b.pt-
4827°C) and Si1600°C.)
Fig (a). The cubic diamond
structure, and (b) The structure of
graphic. The rings are register in
alternate lanes, not adjacent
planes.
CRYSTAL LATTICE AND UNIT CELL
A crystal is solid substance having a definite geometric shape with
flat faces ad share edges.
Cubic crystal is an example of one of the crystal systems.
Ionic crystals are those which exist in a well-defined crystalline
form with their ions arranged in certain definite geometric patterns in the
entire three-dimensional network of the crystal.
Crystal Lattice
Crystal lattice is a geometrical concept in crystalline structure.
(OR)
Crystal lattice is a network of identical points that has the
translational symmetry of a structure. It is highly ordered arrangement of
atoms in crystal.
(OR)
Crystal lattice is a highly ordered three-dimensional structure
formed by its constituent ions (or atoms).
Lattice Point
Lattice point is a point in an array, all of which have identical
surroundings and may also be regarded as an array of indefinite set of
points.
Space Lattices
Space lattice is an array of point, indicating how ions (atoms/
molecules) are arranged at different sites in three- dimensional space.
Unit Cell Lattice
A ‘unit cell lattice’ is the smallest repeating unit in a space lattice
which when repeated over and over again results in a crystal structure of
the substance.
These 14 space lattices of 7 crystal systems are known as “Bravais space
lattices”.
No Crystal System Number of space Lattice Types
Lattices

1. Cube 3 Simple. B.C.C., F.C.C

2. Tetragonal 2 Simple, B.C tetragonal

3. Orthorhombic 4 Simple, B.C, orthorhombic,

F(ABC) central, Face central

4. Monoclinic 2 Simple, face central

5. Triclinic 1 Simple

6. Rhombohedral 1 Rhombobedral

7. Hexagonal 1 Simple
The rule of crystallographic orientation, according to the priority, is that:
• the c-axis is straight up,
• the b-axis is toward the right side
• the a-axis goes toward yourself.
 Types

No Name Stacking Coordinatio Packing No: of atoms Example

n No.(CN) efficiency per unit cell

(2)+3=6 Zn, Mg Be
1 hcp AB AB..... 12 74%
Al, Ni, Cu,
() =4
2 ccp ABC ABC… 12 74% Ag
(=1
3 sc AAA 6 52%
(+1 =2
4 bcc AB AB 8 68% ()+(

5 fcc ABC ABC 12 74%

 
3.11 UNIT CELL SIZE AND DENSITY
The experimental value for the density of nickel is 0.3524 nm.
Determine the type of unit cell for nickel .(Density of
nickel=8.90gc,1cm=nm)
The volume (V) of the unit Cell = = (0.3524nm = 0.04376
= 4.376 x x
= 4.376 x
Mass of an atom of nickel = x
= 9.745 g/atom
The density of the nickel atom, D=m/v
(i) Simple Cubic Structure

(ii) Body-centered Cubic Structure.

 (iii) Face-Centered Cubic Structure

The density of nickel is 8.9 g/. Nickel crystalline in a face-centered cubic

unit cell.
Q. Chromium crystalline in a bcc lattice with an edge measuring 0.288nm.
What is the density of chromium?
(Cr = 51.996, Avogadro const. = 6.022 x
(iv) Estimation of the radius of an atom
Nickel atoms crystallize in a face-centered cubic unit cell with a cell – edge
length of 0.3524nm.
the diagonal across the face of the unit cell =
=
= + = 2 (Pythogorus Theorem)
=
=
= = = 0.1246 nm
 (v)Estimation of the radius of an ion
The cell-edge length in cesium chloride is 0.4123nm. This is desired to
calculate the distance between the centers of the and ions in CsCl.
and ions in the center of the body of the cell. Calculate the radius of cesium
ion. (radius of the chloride ion = 0.18nm)
= +
= + + =3
==
+ = = = 0.3571 nm
+ = 0.3571 nm
+ 0.18 nm = 0.3571 nm
= 0.1771 nm
GEOMETRIC CRYSTALLOGRAPHY
-based on three fundamental laws:
1. The law of constancy of interfacial angles
2. The law of rationality of indices and
3. The law of symmetry.
“The law of constancy the interfacial angles states that for a given
crystal, the corresponding planes forming the external plane of a crystal
intersect a definite angle, called “interfacial angle” and is constant no
matter how the planes develop.”
“The law of rationality of indices of a crystal states that the intercepts
of various planes of a crystal along the crystallographic axes are simple
integral multiples of the intercepts made by the unit plane.”
“The law of symmetry states that unit cells must show the full
symmetry of the structure.”
Steps to Determine Miller Indices d(hkl) of Plane of a Crystal
Miller introduced a set of integers (hkl) to specify a plane of a crystal.
This set of three numbers, (hkl), is known as “Miller Indices” of a
particular plane of a crystal.
The Miller indices (hkl) of a plane of a crystal are inversely
proportional to the intercepts of that plane on the three crystallographic
axes.
The orientation of a surface or a crystal plane may be defined by
considering how the plane (or indeed any parallel plane) intersects the main
crystallographic axes of the solid.
Step 1: Identify the intercepts on the x, y and z axes
-The intercepts on the x- axis, x=a
-The surface is parallel to the y and z axes, intercepts-
-The intercepts on the x, y and z axes, intercepts-a,,
Step 2 : Specify the intercepts in fractional co-ordinates
-Fractional co-ordinates of (x/a, y/b, z/c).
-Fractional intercepts : a/a,/b,/c, i.e. 1,,
Step 3 : Take the reciprocals of the fractional intercepts.
-The Miller indices are also enclosed within standard brackets (…)
-The reciprocals of 1 and  are 1 and 0 respectively,
Miller indices : (100)
Some Examples of Miller Indices
The (110) surface (Fig. 3.38)
(i) Intercept- a, a, 
(ii) Fractional intercepts-1,1, 
(iii) Miller indices : (110)

The (111) surface (Fig 3.39)

(iv) Intercept-a,a,a,
(v) Fractional intercepts : 1, 1, 1
(vi) Miller Indices (111)
The (210) surface (Fig 3.40)
(i) Intercepts-1 ½ a, a, 
(ii) Fractional intercepts ½, 1, 
(iii) Miller Indices : (210)

SYMMETRY OPERATIONS
There are three of symmetry operations:
1. rotation
2. Reflection and
3. Inversion.
1. Rotational symmetry If an object can be rotated about an axis and
repeats itself n times of rotation then it is said to have a axis of n-fold
rotational symmetry. 1-fold (360°), 2-fold (180°), 3-fold (120°), 4-fold
(90°) an 6-fold (60°) rotational symmetry operation systems.
2. Reflection symmetry : Reflection symmetry operation is also called
mirror symmetry operation and it is an imaginary operation that can be
performed to reproduce an object.
3. Rotoinversion summetry : The symmetry operation of rotoinversion is the
combinations of rotation with a center of symmetry.
- Rotoinversion symmetry have an element of symmetry
called a rotoinversion axis. The center symmetry of a crystal is also know 1-
fold rotoinversion axis. 2-fold rotoinversion axis (180°) have a mirror plane.

Types of Energy Bands and Band Gap

1. Overlapping Energy Bands: For a particular crystal type, the higher
energy band of the solid overlaps the lower energy band to some extent.
 2. Non-overlapping Energy Bands: In many solids, the higher empty
energy band does not overlap the lower filled (or half filled) energy level
band and evidently, there is an energy gap between the two bands of energy
levels. This energy gap is known as the forbidden energy gap.
3. Valence Band: A band of stabilized lover energy levels occupied by the
valence electrons of the solid is called the valence band (VB) and obviously
it is the highest filled state of a band.
The valence band of a sold may be either (i) partially or (ii) completed
filled with electron depending on the electronic configuration of the
constituent in the solid.
4. Conduction Band: A band of energy levels above the valence band in
solids is called the conduction band (CB). The conduction = 0 K(empty).
5. Forbidden Energy Gap: A energy gap exists between the VB and CB in
solids of particular types. This energy gap (eV) is called the ‘forbidden
energy gap’.
 PROPERTIES OF CRYSTALLINE SOLIDS
Electrical Properties
- solids are classified into three types:
Conductors-Materials are conductors due to the presence of free or
delocalized electrons at temperature greater than 0°C.
-A material if it possesses either a partially filled valence band
(VB) or a empty conduction band (CB) overlaps with the
filled (VB).
-Resistance - to (at room temperature) -Electrical
conductivities-to (at room temperature).
Semiconductors- Materials between metal and insulators
- Almost filled (VB)
- Empty (CB)
- A very narrow energy gap, Eg, of the order 1-2 e V.
- Resistances- 1 to (at room temperature)
- Electrical conductivity- 1 to (at room temperature)
  Insulators -Bad conductor
-Resistances-greater than (at room temperature)
-VB is completely filled with the valence electrons
-CB is completely empty
-The forbidden energy gap, Eg between VB and CB is very
large, 5-10eV
Fermi Level
‘‘The Fermi level is the highest occupied level in a solid at T = 0’’.
- At T=0,electrons occupy the individual molecular orbital of the band
in accordance with the building-up principle. If each atom supplies one s
electron ,then at T=0 the lowest N orbital are occupied. The highest
occupied orbital at T=0 is called the Fermi Level.
- For metallic conduction is the decrease of electrical conductivity
with increasing temperature.
- The ability of an electron to travel smoothly through the solid in a
conduction band depends on the uniformity of the arrangement of the atom.
- An atom vibrating vigorously at a site is equivalent to an impurity
that disrupt the orderliness of the orbitals.This decrease in uniformity
reduces the ability of the electron to travel from one edge of the solid to the
other, so the conductivity of the solid is less than at T=0.
A metallic conductor is a substance with an electric conductivity that
decreases with increasing temperature.
A semiconductor is a substance with an electric conductivity that increases
with increasing temperature
An insulator is a substance with a very low electrical conductivity, if its
conductivity is measurable, it is found to increase with temperature with
temperature like semiconductor.
Superconductors are a special class of materials that have zero electrical
resistance below a critical temperature.
Magnetic Properties
Materials may be classified by their response to externally applied magnetic
fields as
(a) Paramagnetic (b) Diamagnetic (c) Ferromagnetic
(d) Antiferromagnetic and (e) Ferrimagnetic
These magnetic responses differ greatly in strength.
 
(a) Paramagnetism
Substances which are attracted slightly by magnetic field and do not
retain the magnetic property after removal of magnetic field are called
paramagnetic substances. These unpaired electrons are attracted magnetic
field. For example., , , , Mg, Mo, Li, etc.
(b) Diamagnetism
Diamagnetic substances are just opposite to that of paramagnetic and
diamagnetic substances are magnetized slightly when put under magnetic
field but in opposite direction. Substances which are repelled slightly by
magnetic field are called diamagnetic substances because of presence of
paired electrons and no unpaired electron. Pairing of electrons cancel the
magnetic property. For example; , etc.
(c) Ferromagnetism
Substances that are attracted strongly with magnetic field are called
ferromagnetic substances, such as cobalt, nickel, iron, etc: . Ferromagnetic
substances can be permanently magnetized also. Ferromagnetic substance
act like a magnet.
 Metal ions of ferromagnetic substances are randomly oriented in normal
condition and substances do not act as a magnet, But when metal ions are
grouped together in small regions, called domains. When the ordering of
domains in group persists even after removal of magnetic field a
ferromagnetic substance becomes a permanent magnet.
(d) Antiferromagnetism
Substances in which domain structure are similar to ferromagnetic
substances but also oriented oppositely, which cancel the magnetic property
are called antiferromagnetic substances and this property is called
antiferromagentism.e.g., MnO.
(e) Ferrimagnetism
Substances which are slightly attracted in Magnetic Field and in which
domains are grouped in parallel and anti-parallel direction but in unequal
number, are called ferromagnetic substances and this property is called
ferrimagnetism. E.g., Magnetite (), Ferrite (Mg), etc. Ferromagnetic
substances lose ferrimagnetism on heating and become paramagnetic.
TYPES OF DEFECTS IN CRYSTAL
Atomic Imperfections /Point Defects
If the deviation occurs because of missing atoms, displaced atoms or
extra atoms, the imperfection is named as point defect.
Point defects in a crystal may be classified into three types.
• Stoichiometric defects
• Non-stoichimetry defects
• Impurity defects
Stoichiometric Defects
The compounds in which the number of cation and anions are exactly
in the same ratio as represented by their chemical formula are called
stoichiometric compounds.
The defects that do not disturb the ratio of cations and anions are
called stoichiometric defect.
 
There are of four types of stoichiometric defects.
(i) Vacancy Defect ; When some of the sites are vacant, the crystal is said
to have vacancy defect. This results in decreased in density of the
substance. This defect can also develop when a substance is heated.
(ii) Interstitial Defect ; When some constituent particles (atoms or
molecules) occupy an interstitial site, the crystal is said to have
interstitial defect. This defect increase the density of the substance.
(iii) Schottky Defect ; If in an ionic crystal of the type , , equal number of
cations and anions are missing form their lattice. It is called Schottky
defect. If in an ionic crystal of the type , , equal number of cations
and anions are missing from their lattice. It is called
Schottky defect. This type of defect is shown by highly ionic
compounds which have (a) High Co- ordination
number and (b) Small difference in sizes of cations and anions.
Examples – NaCl, KCl, KBr, and CsCl.
(iv) Frenkel Defect ; If an ion is missing form its correct lattice sites
(causing a vacancy or a hole) and occupies and interstitial site, electrical
neutrality as well as stoichiometry of the compounds are maintained. This
type of defect is called Frenkel defect. Since cations are usually smaller it
is more common to find the cations occupying interstitial sites. This of
defect is present in ionic compounds which have (a) Low co ordinations
number, (b) Larger difference in size of cation and anions. Examples -
AgCl, AgBr, AgI etc.
Non-Stoichiometric Defects
The ratio of number of cation to anion become different from that
indicated by the ideal chemical formula, the defects are called non –
stoichiometric defects. –Due to excess of metal atoms or non-metal atom or
presence of impurities/foreign particle.
(i) Metal Excess Defects (or) The Colour Centres ;
If a crystal of NaCl is heated in sodium vapour, it acquires a yellow
colour. This yellow colour is due to the formation of a non-stoichiometric
compound of sodium chloride in which there is a slight excess of sodium
ions. Some sodium metal gets doped into sodium chloride crystal which,
due to the crystal energy, gets ionised into Na+ and e-. This electron
occupies a site that would otherwise be filled by a chloride ion.
  The extra electron in thus shared between all the six ions which implies
that this electron is not localised at the vacant site. The crystal as a whole
is neutral. Light is absorbed when this delocalized electron makes an easy
transition form its ground state to an excited state. As a result, the non-
stoichiometric form of sodium chloride appears colored. Because of this,
the sites occupied by the extra electrons are known as colour centres. These
also called F-centres.
(ii) Metal Deficiency Defects;
One of the positive ions is missing from its lattice site and the extra
negative charge is balanced by some nearby metal ion acquiring two
charges instead of one.The crystal as a whole is neutral. This type of defects
is generally found amongst the compounds of transition metals which can
exhibit variable valency.
Crystals of FeO, FeS and NiO show this type of defects. The presence of
holes lowers the density as well as the lattice energy or the stability of the
crystals.
 
Synthesis of Superconductors
Yettrium barium cuprate, with composition Y when x is small . The
constituents of this material yettrium, barium and copper are in 1:2:3 molar
stoichiometric ratio and hence, they are called as 1:2:3 superconductors.
1. (2223 compound) is a superconductors material at (=105K)
(i) Synthesis of 1:2:3 superconductor by ceramic method
Y , a 1:2:3 superconductors can be synthesized by solid state ceramic
technique.
(a) Preparation of a homogeneous mixture of three oxides (, Ba in their
molar ratio.
(b) Heating them to obtain oxygen deficient superconductor in muffle
furnace.
(c) Annealing the above compound to room temperature to retain its
composition, structure and superconducting properties.
 CONSEGUENCES OF LATTICE ENTHALPIES
Lattice enthalpy
MX(s)(g) + (g) =(+)ve kJ (endothermic).
For a given lattice type, the lattice enthalpy increases with increasing ion
charge numbers. The lattice enthalpy also increases as the ions come
closer together and the scale of the lattice decreases.
Thermal Stability of Ionic Solids
Mg Ca Sr Ba

) +48.3 +130.4 +183.8 +218.1

) +100.6 +178.3 +234.6 +269.3
+175.0 +160.6 +171.0 +172.1
/ 300 840 1100 1300

Data are for the reaction M(s)MO(s) + (g) at 298 K. is the temperature
required to reach (= 1 bar.
 The decomposition temperatures of thermally unstable compounds (such
as carbonates) increases with cation radius. In general, large cations
stabilize large anions (and vice versa).
The difference in lattice enthalpy between and Mis also magnified by a
larger charge on the cation, as /d ,so the thermal decomposition of a
carbonate will occur at lower temperatures if it contains a higher-charged
cation. This dependence on cation charge is observed in the fact that
alkaline earth carbonates ()tend to decompose at lower temperatures than
the corresponding alkali metal carbonates ().
Solubility of Solids
-Compounds that contain ions with widely different radii are
soluble in water(difference in size favours solubility in water)
-A large anion requires a large cation for precipitated.
-A large anion requires a small cation for solubility.
-Eg –What is the trend in the solubilities of the Group metal
carbonates( Mg to Ra).
  -Relative size of cations and anions .The ( ) anion has a large radius
and has the same magnitude of charge as the cations () of the Group-2
elements. The least soluble carbonate of the group is predicted to be that
of the largest cation,().The most soluble is expected to be the carbonate,it
is still sparingly soluble. -Which can be expected to be more
soluble in water,NaClor KCl
CHARACTERISTIC OF CRYSTALLINE SOLID
Introduction -The characterisation of crystalline materials are done through
a non-destructive technique of X-ray powder diffraction. Traditionally, this
method has been used for phase identification, quantitative analysis and the
determination of structure imperfections. This technique has been extended
to new areas such as the determination of crystal structures and the
extraction of three-dimensional micro-structural properties.
 Bragg Law n=2d
n= an integer
ℷ=the wavelength of the X-rays
d=the interplanar spacing generating the diffraction
=the diffraction angle
ℷ and d are measured in the same units, usually angstroms.