1.

Crystalline Solids
constituents are arranged
The essential featureof crystalline solids is that the constantly
a completely regular three dimensional pattern, which is
In solid has a definite geometrical
repeated. In consequence, the crystalline
thenature of the substance and sharp mnelting
Configuration, characteristic of ata fixed temperature. These
into liquid state
point, i.e., they change abruptly crystalline state, however, is far from
nature. The
Solids are anisotropic in to considerable degree of thermal
seldom perfect due properties of crystalline
Statc and the pattern is Many of the useful
vibrations of the constituent. vibrations of the constituents, the presence of
related to thermal
solids are
of defects.
mpurities and existence
284
Engineering Chemistry 1
2. Amorphous Solids (Pseudo Solids)
The main characteristics of solids is rigidity and resistance to change shape
against mild distorting forces. However there are solids which get
by application of mild distorting forces, such as bending and distorted
forces. These type of solids do not have any definite geometrical comprshapeessinasg
the constituents are arranged randomly and not in an orderly manner. The s
solids are regarded as super cooled liquids. On long standing, they tend to
lose shape and flow under their own weight, e.g., glass, proteins, pitch,rubher
plastics, etc. These solids are called pseudo solids or amorphous solids. On
heating, these types of solids gradually soften over a wide range of
temperature before being changed into the liquid state.
The constituent units of these types of solids actually do not have an
orderly arrangement over along range, but only to short distances in the order
of the magnitude of interionic distances ( 10 cm). These types of solids
are isotropic and do not have sharp melting points (melt gradually over a
long range of temperature). The crystalline materials are therefore considercd
to be true solids.

5.1 IMPERFECTIONS IN SOLIDS

In a crystalline solid there is definite order of arrangement of its constituents.
Likewise in an ionic crystal there is well-defined order of arrangement of
the constituent ions. An ideal crystal, so to say, is one, which has the same
unit cell containing the same lattice points throughout the whole of the crystal.
However, such ideal crystals exist only at absolute zero (0K)temperture.
With increasing temperature, the thermal vibration of ions in their lattice sites
increases and when the vibration becomes large, the ions may jump out from
their original lattice sites. Thus for any temperature above OK, the crystals
have some departure from the complete ordered arrangement. Any deviaton
from completely ordered arrangement in a crystal creates a disorder or detet
Athigh temperature there is a greater probability of the lattice site to be
unoccupied. As these defects depends on the temperature, they are also knowin
as thermodynamic point defects.
The defect may also arise due to presence of impurities. The imperfections
not only change the properties of the crystals, but also give rise to ne
properties. The imperfections are mainly of two types:
1. Atomic imperfections or point defect
2. Electronic imperfection
SolidState
285

5.1.1 Atomic Imperfections or Point Defects

s defects in ionic crystals due to constituent ions or atoms is known as
constituent
point defects. The defects are due to imperfect arrangement of
atoms or 10ns and arises due to
1. missing of constituent (atoms, ions) from their normal positions
causing vacancies,
2. missing of constituents from their own position and shifted to
positions meant for other atoms or ions or to vacant interstitial
positions.
non-stoichiometric
The point defects 0ccur in both stoichiometric and
compounds.

Stoichiometric and Non-Stoichiometric Compounds

constituent atoms or
Compounds in which the numbers of different types of
as indicated by their chemical
ions present exactly in the same ratios
formulae.
composition and are known
These compounds obey the laws of constant also known as Daltonide.
compounds are
as stoichiometric compounds. These
For example, NaCl, NaBr, AgCl, Agl, etc. not obey the laws
Non-stoichiometric compounds on the other hand do
of chemical composition.
They exist over a range number
of constant composition.atoms of one kind to the of atoms of other
The ratio of number of
correspond exactly to the whole number ratio given by the
kind do not known as Berthollide. For example, the
formulae. These compounds are also
elements.
oxides and sulphides of transition Fe: S is l:1.
ZnO the ratios of Fe :O and
In case of FeO or FeS and 0-Fepo0,
shows the chemical composition to be (Fe) 8A
But chemical analysis
might be deficiency or excess of metal ions. The electrical
Fep S) i.e., there
always maintained. The electrical neutrality is maintained
neutrality however is or with change of charge on
in the structure
either by having extra electrons structure irregular, creating defects.
these make the
Some metal ions and

Defects in Stoichiometric Compounds

5.1.1.1 Point
are generally
stoichiometric compounds two types of defects
In case of
observed. These are:
1. Schottky defect
2. Frenkel defect
 286

Schottky Defect
Engine ring ChemisryNI
scientist
This defect was discovered by the German
type of defect arises if some of the
constituent
atoms orSchottkions
y in 1930.
lattice sites. The lattice sites which are are Sut
of a ed aremicsaSlnegd
from their normal
lattice vacancies or holes. Schottky defects thus consistunoccupi
(an anion vacancy and a cation vacancy) in
the crystal par of
lattice,
crystal is to remain electrically neutral, equal number of cations Since the
are missing, the missed ions are found to come to the and
crystal ani o ns
This type of defect is usually observed in highly ionic
surface.
) high coordination number and (i) ions (cations and anions)Compounds
sizes. Example of such compounds are NaCl, CsCI, KCI, KBr, tc,.
off
almosthasimvinilgag
The number of Schottky defects formed per cm² (N) in a crystal is
by given

N=N x e 2KT
where, N =Number of sites per cm left vacant
W= Work necessary to form a Schottky defect
K= Gas constant
T =Absolute temperature.

(M* X

M M (M
M)
wher
(Mx--M)
An ideal crystal The Schottky defect in
Fig. 5.1 crysta
SolidState 287

FrenkelDefect
This defect was discovered by a Russian scientist Frenkel in 1926. Such defect
arises when an ion is missing from its own position and occupies ainterstitial
site between the lattice points. Metal ions are generally smaller that the anions
dhence it is more common to find the positive ions to occupy this
interstitialI position. The vacant lattice site thus created is known as a 'hole'.
The crystal however remains neutral as the number of cations and anions
remains the same.
This type of defect generally occurs in compounds in which the anions
are much large in size than cations and consequently the coordination number
is low (4 or 6).

M (M
M
M

--
(M- M
--
An ideal crystal TheFrenkel defect in crystal
Fig, 5.2

Examples of this type of defects are AgC1, AgBr, Ag, ZnS, etc.
The number of Frenkel defects formed per cm3
(N) is given by
W
N,= VNN 2KT

where, N = Number of sites per cm° that could be left vacant.

N' = Number of alternative interstitial position per cm
W,=Work necessary to form a Frenkel defect
K= Gas constant
T=
Absolute temperature.
Ihe energy needed to form eithera Schottky Defect or aFrenkel Defect
depends on the work needed to form the defect, and on the
temperature. In
 288
Engineering Chemist
a given compound one type generally predominates. In
such as AgBr, both Schottky and Frenkel defects occur. certain
ionic solids
Consequences of Schottky and Frenkel Defects
The defects in crystals lead to some interesting
consequences, such
1. Due to the defect, the electrical conductivity increases. Under a
gradient, a nearby ion moves from its lattice site to occupy ahole. potential
This
in turn creates a new hole and another nearby ion moves
process continues and a hole moves from one end to the
into it. The
other end and
electricity is conducted across the crystal.
2. Due to presence of holes in case of the Schottky defect the A.
decreases.
3. Due to hole there is a possibilityof partial collapse of the crystal.
4. The closeness of similar charges in Frenkel defects tends to increase the
dielectric constant of the crystal.

Table 5.1 Difference between Frenkel defect and Schottky defect.

Frenkel defect Schottky defect
1. Frenkel defect occurs when an ion 1. Schottky defect occurs due to
migrates from its regular lattice site migration of equal number of
to an interstitial site. cations and anions from the lattice
sites to the surface.
2. Overall density of the crystalline2. Due to default the overall density
substance does not change. of crystalline substance changes
(decreases).
3. Due to Frenkel defect dielectric 3. Due to Schottky defect dielectric
constant of the crystal increases. constant of the crystal remains
almost unaffected.
4. Frenkel defect generally occurs in4. Schottky defect generally occurs in
solids having anions much larger in highly ionic compounds having
size than cations, e.g., AgCl, Agl, almost similar sizes of cations and
ZnS, etc. anions and high coordination number,
e.g., NaCI, KCI, KBr, etc.

5.1.1.2 Point Defects in Non-stoichiometric Compounds

In case of non-stoichiometric compounds, there exist two types of defects
depending upon whether positive 1ons are in excess or the negative ions.
5.2.1 Metals
All metals are exXceptionally good conductors of heatand electricity. Electrical
Conduction arises due to the movements of electrons. The conductivities of
metals are explained on the basis of Band theory'.
Band Theory
IMetals are usually crystalline with most common coordination numbers of
twelve. When one atom is surrounded by so many atoms the covalency as
found in non-nmetals does not take place due to paucity of electrons.
Solid State
295

In metals the atoms are linked by a special type of bond known as

bond'. It is assumed that the atoms in ametal lose their valence-shell
'Metallic
electrons
and become positive ions. The electrons thus released are not bound up
with
any particular metal ion, i.e., the matrix of positive ions remains
in a sea of mobile electrons. The conductance of metals is due to
embedded
these mobile
electrons. The band theory explains the positions of these mobile electrons
and the mechanism of electrical conduction. In atoms, the
electrons occupy
sharp and definite energy levels and are same for all individual atoms. But
in a crystal lattice, when the atoms take up definite
positions, the electrons
are subjected to a non-uniform electric field: the electrons are
influenced by
several 'number of adjacent nuclei and the sharply defined energy levels no
longer exist, and are instead rendered into closely spaced bands. The electrons
may now take positions in the band. The bands are however not
continuous,
but separated by forbidden zones.
In case of metals, due to a high coordination number the
valence shell
electrons are not sufficient for pairing with all surrounding atoms to form
covalent bonding. Hence, the lower bands are filled up first, but the upper
bands are farthest from the nucleus are empty or partially filled with
due to insufficiency of electrons. The lower energy band is called theelectrons
valence
band and the higher energy band is termed as conduction band. Such
of energy levels in metals or in general in solid, is known as band
approach
theory.
The electrical conduction in metals will take place for valence shell to be
partly full, or the valence and conduction bands overlap. In case the valence
shell is completely filled and there is overlap between valence band and
conduction band on application of a potential, the valence band electrons will
not move and acceptance of electrons will also be forbidden: neither it will
violate the Pauliexclusion principle.In such a case however, the unfilled or
partially filled electrons in the conduction band may shift to a slightly higher
level in the same band. Thus there becomes the possibility of the transfer of
electrons from one atom tO another, ie., electrical conductance would occur.

Energy Energy
:Conductjo bai
band': Energy
Cönduçtion band;
:Conductjon baid:
:Valnc Band: :Valen Ban;:
:(prtjally: flled):: (Completçly filledr (Cóipletly filld;:
Fig. 5.8 Three ways of conduction in a conductor
 Metats are pod condtors of eleAcity as 1hey allrn

In case of insulatos(on metals) every

neest s9onding atoms and henve the valene har is nnpletelytleA
nd petbations within the hand are impossihle, and ayain there is
Hpprisble differee in eneey (hand ap) betWCEH1he alcns ta1d ar4
the next pty band, ie, onuction band, Electrons therefts Catuua b
prmoted and if very high electieal potential be applid there will beruthre
of the crystal instead of conduetion The clectrical omdutivity ís of the nder

ifyndyetm ban|

Valcice byij:
:0illed):
Fiy. 5,9 Ilnsulator
In case ol
scmi-conductor a small amount of
tOOmtempcraturc. "The clectrical electric current can flow l
temperature lies betwcen that of conductivity of a semi-conductorat roofm
the vange of 10' to 10 ohm em yood conductor and an insulator, i.e., in
5.2.2 Somi-conductors
Semi-conductors
nd iosulators,
are Nolids in which the
On the basis of conductivity is in bctween a metal
ol twotypes: mechanism conduction
of
I.
semiconductors
av
Intrinsie semi-conductors
In semi
(senmi
conductor dhere is asmall
conduction band
-conductors due to thermal effects):
energy gap between the valence band and
lie in the lowestkown as band gap. I cooled to
pOssible enerpy absolute Zero the clectrons
(onduction band is empty and the levcls, i.e., in the valence band. The
nomal temperature, some (very material behaves as an insulator. But at
the valence band to the few) electrons are Cxcited from
GemaniumBoth conduction
(Ge) and silicon band and thusthermally clectricity.
(Si) are conduct
conductors, the crystals huve a the most important class of silicon semi-
diamond-like structure. Atoms of
duetß

Table5.2 Difference between n-type semi-conductor and p-type semi-conductor.

n-ype semi-conductor p-type semi-conductor

1.This type of semi-conductor is 1. It is produced due to mnetal

anoduced due to metal excess deficiency defect.
defect.
of semi-conductor can 2. Such type of semi-conductor can
2. Suuch type o
be produced by doping extremely be produced by doping extremely
pure silicon (Si) orgermanium (Ge) pure silicon (Si)or germanium (Ge)
with a pentavalent impurity (e.g. P, with atrivalent impurity (e.g. B, Al,
As, etc.) Ga, In, etc.)
3. Such a semi-conductor has an 3. Such a semi-conductor has missing
excess of electrons. electrons (positive holes).
4. Conduction in this type of 4. Conduction in this type of
semi-conductor is due to movement semi-conductor is due to movement
of free electrons. of free positive holes.
5. In this type of semi-conductor the 5. In this type of semi-conductor the
conduction is due to movement of conduction is due to mnovement of
negative electric charge. positive electric charge.
 284

(Pseudo Solids)
Engineering Chemistny
2. Amorphous Solids
rigidity and resistance to
The main characteristics of solids is
against mild distorting forces.
However there are solids which get sh change
by application of mild distorting forces,
such as bending and istotea
forces. These type of solids do not
have any definite geometrical
the constituents are arranged randomly and not in an orderly
mannex ComprsehsaSpIeng as
solids are regarded as super cooled liquids. On long standing, they
they tend
t y
glass, proteins,
lose shape and flow under their own weight, e.g., pitch, rubbe,
amorphous solid
plastics, etc. These solids are called pseudo solids or
wide ran e
heating, these types of solids gradually soften over a
state.
temperature before being changed into the liquid
not hava .
The constituent units of these types of solids actually do
distances in the ord.
orderly arrangement over a long range, but only toshort
sok,
of the magnitude of interionic distances ( 10 cm). These types of solids
are isotropic and do not have sharp melting points (melt gradually over a 1
considerei
therefore
long rangeof temperature). The crystalline materials are
f
to be true solids.

5.1 IMPERFECTIONS IN SOLIDS

In acrystalline solid there is definite order of arrangement of its constituents.

Likewise in an ionic crystal there is well-defined order of arrangement of
the constituent ions. An ideal crystal, so to say, is one, which has the same
unit cell containing the same lattice points throughout the whole of the crystal.
However, such ideal crystals exist only at absolute zero (0K) temperatur.
With increasing temperature, the thermal vibration of ions in their lattice sites
from
increases and when the vibration becomes large, the ions may jump out
their original lattice sites. Thus for any temperature above 0K, the crystals
deviation
have some departure from the complete ordered arrangement. Any
from completely ordered arrangement in acrystal creates a disorder or defect.
At high temperature there is a greater probability of the lattice site tobe
unoccupied. As these defects depends on the temperature, they are also known
as thermodynamic point defects.
The defect may also arise due to presence of impurities. The imperfections
not only change the properties of the crystals, but also give rise to new
properties. The imperfections are mainly of two types:
1. Atomic imperfections or point defect
Electronic imperfection