Defects in Solids
Defects in solids
An ideally perfect crystal is one of the most fascinating
aspects of solid state science.
An ideally perfect crystal is one which has the same unit cell and
contains the same lattice points throughout the crystal. (perfect
Crystal)
The term imperfection or defect is generally used to describe any
deviation of the ideally perfect crystal from the periodic arrangement
of its constituents.
Any deviation from completely ordered arrangement of constituent
particles in a crystal is called disorder of Defect.
Classification of Defects in solids
Defects in Solids
Point Defects Line Defects
Impurity Stoichiometric Non-Stoichiometric
Defects Defects Defects
Vacancy Interstitial Schottky Frenkel
Defects Defects Defects Defects
Metal Excess Metal Deficiency
Defects Defects
Line Defects
Atomic Imperfections / Point Defects
If the deviation occurs because of missing atoms, displaced atoms
or extra atoms, the imperfection is named as a point defect.
Such defects can be the result of imperfect packing during the
original crystallisation or they may arise from thermal vibrations of
atoms at elevated temperatures because with increase in thermal
energy there is increased probability of individual atoms jumping
out of their positions of lowest energy.
Type of point defects – point defects in a crystal may be classified
into three types
Stoichiometric defects
Non – stoichiometric defects
Impurity defects
Stoichiometry Defects:
The stoichiometic compounds are those which obey law of
constant proportions.
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.
These are of four types
Vacancy Defect
Interstitial Defect
Schottky Defect
Frenkel Defect
Vacancy Defect
When some of the lattice sites are vacant, the crystal is said to
have vacancy defect .
This results in decrease in density of the substance.
This defect can also develop when a substance is heated.
Interstitial Defect
When some constituent particles (atoms or molecules) occupy an
interstitial site, the crystal is said to have interstitial defect
This defect increases the density of the substance.
Schottky Defect
If in an ionic crystal of the type A+ B-, 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
high Co – ordination number and Small difference in the sizes of
cations and anions.
A few examples of ionic compounds exhibiting Schottky defect are
NaCl, KCl, KBr and CsCl.
Consequences of Schottky Defect
As the number of ions decreases as a result of this defect, the
mass decreases whereas the volume remains the same. Hence
density of the solid decreases
The crystal begins to conduct electricity to a small extent by ionic
mechanism
The presence of too many voids lowers lattice energy and the
stability of the crystal
Frenkel Defect
If an ion is missing from its correct lattice sites (causing a vacancy
or a hole) and occupies an 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 type of defect is present in ionic compounds which have
Low co ordinations number
Larger difference in size of cation and anions
Compounds having highly polarising cation and easily polarisable
anion. A few examples of ionic compounds exhibiting this defect are
AgCl, AgBr, AgI, ZnS etc.
Consequences of Frenkel defect
As no ions are missing from the crystal lattice as a whole,
therefore density of the solid remains the same
The closeness of like charges tends to increases the dielectric
constant of the crystal
The crystal conducts electricity to a small extent by ionic
mechanism
Impurity Defects
These defects in ionic crystals arises due to the
presence of some impurity ions at the lattice site or
at the vacant interstitial sites
Non – Stoichiometric Defects
These compounds do not obey law of constant proportions.
Ex; Oxides and Sulphides of Transition Metals
If as a result of imperfection, the ratio of number of cation to anion
becomes different from that indicated by the ideal chemical formula,
the defects are called non – stoichiometric defects.
These defects arise either due to excess of metal atoms or non metal
atom or presence of impurities / foreign particle.
These defects are of two types: (i) Metal excess defect and
(ii) Metal deficiency defect.
Metal Excess Defects
In these defects +ve ions are in excess. It may occur in two different ways
A+ B- A+ B-
In the First way, one of the –ve ion
is missing from its real lattice
B- A+ B- A+
position leaving a vacant site (hole)
which is occupied by an extra
A+ e- A+ B-
electron so that the compound is
neutral. (Schottky defects) (CuS, )
B- A+ B- A+
I F-Centers
It has been observed that 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.
What happens in this case is that 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, as illustrated in figure.
The electron occupying the position vacated by missing anions(Cl-)
are called F-centers.
A+ B- A+ B- In the Second way, an extra +ve ion
A+ occupies a position in the lattice
B- A+ B- A+ interstices and in order to maintain the
e- electrical neutrality of the crystal an
A+ e- A+ B- electron also occupies a position in the
lattice. (Frenkel defects) ( ZnO, CdO,
B- A+ B- A+ Fe2O3 & Cr2O3)
II
Consequences of Metal Excess Defects
1. The crystals with metal excess defect contain free electrons. Since
these free electrons can migrate in an electric field, such crystals
can conduct electricity.
These materials are therefore termed as Semiconductors.
Since current however small is carried by electrons in normal
way, these substance are called n-type semiconductors.
2. The crystal with metal excess defects are generally coloured. This
again due to the presence of free electrons.
Free electrons exited easily to higher energy level – coloured.
Metal Deficiency Defects
There are two possible ways in which metal deficiency defects an occur.
A+ B- A+ B- A+ B- A+ B-
B-
B- B- A+ B- A++ B- A+
A+ B- A++ B- A+ B- A+ B-
B- A+ B- A+ B- A+ B- A+
I II
In the First way, one of the +ve ion may be missing from its lattice site.
The extra –ve charge may be balanced by some near by metal ion by
acquiring and additional +ve charge. (Exhibit variable valency)
Ex: FeO, FeS and NiO
In the Second way, an extra –ve ion may occupy an interstitial position.
The extra –ve charge is balanced again by means of extra charge on
one of the adjacent metal ions (Cations).
Ex: No crystal showing this type of metal deficiency defect.
(-ve Ions usually very large, it is not expected that, they would be able
to fit in to interstitial position)
Consequences:
Crystals with metal deficiency defects can also be semiconductors.
•This property arises from the movement of an electron from one
into another.
•In this way the ion say A+ changes in A++. Thus, the movement of an
electron from A+ ion is an apparent movement of A++ ion.
• This called movement of +ve ‘hole’ and the substance permitting
this type of movement are known as p-type semiconductors.
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