Unit I-D: Defects in Solids

Prof.(Dr.) A. A. Ansari
Assistant Director & Head
Environment Division

Northern India Textile Research Association

Sector-23, Raj Nagar, Ghaziabad
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Introduction

• Crystalline solids exhibit a periodic crystal structure;

• the positions of atoms or molecules occur on repeating fixed
distances, determined by the unit cell parameters.

• However, the arrangement of atoms or molecules in most

crystalline materials is not perfect.

• The regular patterns are interrupted by crystallographic defects.

• In general, a defect or imperfection refers to a disruption in the

crystalline order of a solid crystal.

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• A perfect crystal is thermodynamically “impossible”.

• Defects lower the energy of a crystal and make it more stable.

• Defect can be either desirable or undesirable.

• In some cases, defects are undesirable and they should have

crystals as perfect as possible e.g., crystals for optoelectronics.

• In other cases, defects or imperfections are desirable –

e.g.
• Alloys of two randomly mixed metals for greater strength

• Doping of semiconductors to achieve specific electrical

properties
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Classification of Defects

• Defects are classified on the basis of their geometry and shape,

because they are disrupted region in a volume of a solid.

• Defects are-

• 0-Dimensional or Point Defects e.g. vacancy, interstitial,

substitutional, impurities

• 1-Dimensional or Line defects e.g. dislocations

• 2-Dimensional e.g. Surface defects, grain boundaries,

crystal twins, twists, stacking faults

• 3-Dimensional or Volume Defects e.g. pores, cracks, voids,

precipitates
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 0-Dimensional or Point Defects in Solids

• In point defect the perfect order is only disturbed at one or a few

lattice point.

• They are not extended in space in any dimension.

• They may be present in-

• Homogeneous Crystals where all atoms are the same.

e.g. vacancy, self interstitial

• Heterogeneous Crystals where two or more type of atoms are

present.

e.g. interstitial impurity atom, substitution impurity atom

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Vacancy

• There is a vacant atomic site in the structure from which an atom is

missing.

• It is usually created when the solid is formed by cooling the liquid.

• They also occur naturally as a result of thermal excitation.

• These are thermodynamically stable at temperatures greater than

zero.

• Distortion of planes takes place due to the vacancy created.

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• At equilibrium, the number of vacancies present at a given
temperature (T) are given by the equation-

n= N.e(- Q/kT)

Where

n No. of vacancies
N Number of lattice sites
Q Energy required to form a vacancy
k Boltzmann constant = 1.38 ×10-23 J K-1; or 8.62 ×10-5 eV K-1
T Absolute temperature (K)

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Interstitial

• An interstitial atom is an atom that occupies a place outside the

normal lattice position.

• It may be the same type of atom as rest of the atoms surrounding it

(self- interstitial) or a foreign impurity atom.

• Much less likely to form because of large energy required to

squeeze the extra atom in.

• It is most probable if the atomic packing factor is low.

• This also causes distortion of planes.

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Defects in Ionic Crystals

• In ionic crystals, existence of point defects is subjected to the

condition of charge neutrality.

• There are two possibilities for point defects in ionic solids.

• Frenkel Defect

• Schottky Defect

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Frenkel Defect

• An ion is displaced from a regular

position to an interstitial position
creating a vacancy,

• The pair of vacancy-interstitial is

called Frenkel defect.

• This type of defect is shown where

cations and anions have much
difference in their sizes e.g., AgBr,
AgCl, Agl etc.

• Cations are usually smaller and thus

displaced easily than anions.

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• The density remains unaffected because no particle leaves the
crystal.

• Closed packed structures have fewer interstitials and displaced

ions than vacancies.

• Because additional energy is required to force the atoms into the

interstitial positions.

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Schottky Defect

• A pair of cation and anion of equal

valencies can be missing from ionic
crystal, without violating the condition of
charge neutrality.

• The pair of cationic and anionic vacant

sites, thus formed, is called Schottky
defect.

• Ionic substances showing schottky

defects have almost similar sizes of
cations and anions.

• This type of point defect is dominant in

alkali halides., e.g.; NaCl, KCl, KF, etc.

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• Schottkey defect lowers the density of crystal because a pair of
ions are missing from the crystal.

• There are 106 schottky pairs per cm3 at room temperature in NaCl.

• These ion-pair vacancies, like single vacancies, facilitate atomic

diffusion.

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Impurities in Solids

• There are always some impurities in any real material.

• Consider Au with purity of 99.999% (impurities - 0.001%).

• Addition of impurities will lead to a solid solution

• A solid solution is a mixture of two or more elements in the solid

with random distribution.

• The majority atom type is called solvent (also called host atoms)

• The element with lower concentration is called solute.

• Two types of solid solution are possible-

• Substitutional
• Interstitial 14
Substitutional

• A solid solution in which the solvent

(host atoms) are replaced by solute.

• The size of solute is similar to the size

of host atom.

Interstitial

• Solute atoms are located in gaps

between host atoms.

• The size of solute is much smaller

than the size of host atom.

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Hume-Rothery Rules

• A high concentration of solute can only occur in a substitutional

solid solution if

1. Atoms have similar radii

2. Both pure materials have same crystal structure
3. Have similar electronegativity
4. Solute should have higher valence

e.g. Cu and Ni are completely miscible; R(Cu)= 0.128 nm, R(Ni) =

0.125 nm; Both fcc; Electronegativity 1.9 and 1.8

• An interstitial solution can only occur for small impurity atoms.

• Even then there is some strain, so high concentration of solute is

not possible.

e.g. C in Fe (steel)

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