CHEMISTRY PROJECT

solids

BY KRATI PANDEY
XII-B
 IMPERFECTIONS IN SOLIDS

• Any deviation from the perfectly ordered arrangement constitutes a defect or

imperfection. These defects sometimes called thermodynamics defects because the
number of these defects depends on the temperature. Crystals may also possess
additional defects due to the presence of impurities. Imperfection not only modify
the properties of solids but also give rise to new properties.
1. ELECTRONIC IMPERFECTION
• Generally, electrons are present in fully occupied lowest energy states . But at high
temperatures ,some of the electrons may occupy higher energy states depending upon
the temperature. For example, in the crystals of pure Si or Ge some electrons are
released thermally from the covalent bonds at temperature above 0K . These electrons
are free to move in the crystal and are responsible for the electrical conductivity . This
type of conduction is known as intrinsic conduction. The electron deficient bond formed
by the release of an electron is called a hole. In the presence of electric field the positive
holes move in a direction opposite to that of the electrons and conduct electricity.
 2.ATOMIC IMPERFECTION (POINT DEFECTS)

• The compounds in which the number of irregularities present in the

arrangement of atoms or ions are called atomic imperfections. It is
of three types:
 (A) Stoichiometric Defect
• If due to the defect present in the crystal the stoichiometric ratio of cation and anion is not
disturbed then the defect is called stoichiometric defect. It is of two types:
 (I) Schottky Defect:
• This type of defect is created when the number
of positive and negative ion are missing
in the same ratio as in their formula units,
from their respective positions leaving
behind a pair of holes. Schottky Defect is
more common in ionic compounds with high
coordination number and where the size of
positive and negative ions are almost equal.
The presence of large number of Schottky
Defects in crystal results in the significant
decrease in its density. Example- NaCl,KCl,etc.
 (II) Frenkel Defect:
• This type of defect is created when
an ion leaves its correct lattice site and
occupies an interstitial site. Frenkel Defects
are common in ionic compounds which have
low co-ordination number and in which there
is a large difference of size between positive
and negative ions. Example- ZnS, AgCl, AgBr,
AgI, etc. Due to this defect dielectric constant
of the crystal is increased.
 
(B) Non- Stoichiometric Defect
• There are many compounds in which the ratio of positive and negative ions present in the
compound differs from that given by the ideal formula of the compound. Such compounds are
called Non- Stoichiometric compounds. Example- VOx (where x can vary between 0.6 to 1.3). In
these compounds balance of positive and negative charges is maintained by having extra
electrons or extra positive charge on cations. These defects are of the following types:
(I) Metal excess A compound may have excess metal ion if a
defect due to negative ion is absent from its lattice site, leaving a
anion vacancies: hole which is occupied by an electron to maintain
electrical neutrality. The holes occupied by electron
are called F-centers and are responsible for the
colour of he compound. Example:
The excess sodium in NaCl makes the crystal
yellow.
Excess potassium in KCl makes it violet.
Excess lithium in LiCl makes it pink.

Greater the number of F-centers greater is the

intensity of colour. This type of defects are
found in crystal which are likely to possess
Schottky Defect.
 
• It may occur if extra
positive ions is present in an
(II) Metal Excess
interstitial site. Electrical Defect Due To
neutrality is maintained by Interstitial Cations:
the presence of an electron
in the interstitial site. This
type of defect are exhibited
by the crystals which are
likely to exhibit Frenkel
Defects. Example- Yellow
colour of ZnO.
(III) Metal Deficiency Due To Cation Vacancies:

• The non-stoichiometric
compound may have metal
deficiency due to the absence
of a metal ion from its lattice
site. The change is balanced
by an adjacent ion having
higher positive charge . This
type of defect are generally
shown by compounds of
transition metal.
 (C) Impurity Defects
These defects arise when impurities are present at the lattice
site or at the vacant interstitial sites. In the former case we
get substitutional solid solutions while in the latter case we
get interstitial solid solutions.
The introduction of impurities into pure crystal is called
doping.
 (I) Introducing Impurity It In
Defects is of twotypes:
(II) Introducing Impurity
Covalent Solids: Defect In Ionic Solids:
• When group fourteen elements (Si,Ge) is • In ionic solids doping of ions is done
doped with fifteen group elements like As and . If impurity ions are in different
P then there are excess valence electrons in the oxidation state than that of host ions
crystal. The excess electrons give rise to
, vacancies are created. For
electrical conduction. When 14th group element
example, if NaCl is doped with
is doped with 13th group element like Al and
Ga then electron deficiency is created. Such
SrCl2 then for every SrCl2+ ion,
holes also move across the crystal to create two Na+ ions are removed to
conductivity. These doped crystal of Si and Ge maintain the electrical
are called respectively ‘n’ type and ‘p’ type neutrality .Thus one vacancy is
semiconductors. created by each Sr2+ ion.
•