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Imperfections in Solids

There are three main types of imperfections in solids: electronic, atomic, and impurity defects. Electronic imperfections occur when electrons occupy higher energy states at high temperatures, enabling electrical conductivity. Atomic imperfections include point defects like Schottky defects, Frenkel defects, and non-stoichiometric defects that involve cation/anion vacancies or interstitials. Impurity defects arise from substituting impurity ions into lattice sites or interstitial sites during doping processes.

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78 views4 pages

Imperfections in Solids

There are three main types of imperfections in solids: electronic, atomic, and impurity defects. Electronic imperfections occur when electrons occupy higher energy states at high temperatures, enabling electrical conductivity. Atomic imperfections include point defects like Schottky defects, Frenkel defects, and non-stoichiometric defects that involve cation/anion vacancies or interstitials. Impurity defects arise from substituting impurity ions into lattice sites or interstitial sites during doping processes.

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Krati Pandey
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© © All Rights Reserved
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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,CsCl,KBr,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 defect due to anion vacancies:

A compound may have excess metal ion if a negative ion is absent from its lattice site, leaving a 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.
(II) Metal Excess Defect Due To Interstitial Cations:

It may occur if extra positive ions is present in an interstitial site. Electrical neutrality is maintained by
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. It is of two types:

(I) Introducing Impurity Defects In Covalent Solids:

When group fourteen elements (Si,Ge) is doped with fifteen group elements like As and P then there are
excess valence electrons in the crystal. The excess electrons give rise to electrical conduction. When 14 th
group element is doped with 13th group element like Al and Ga then electron deficiency is created. Such
holes also move across the crystal to create conductivity. These doped crystal of Si and Ge are called
respectively ‘n’ type and ‘p’ type semiconductors.

(II) Introducing Impurity Defect In Ionic Solids:

In ionic solids doping of ions is done . If impurity ions are in different oxidation state than that of host
ions , vacancies are created. For example, if NaCl is doped with SrCl2 then for every SrCl2+ ion, two Na+
ions are removed to maintain the electrical neutrality .Thus one vacancy is created by each Sr2+ ion.

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