S O L I D S TAT E

PART VIII
15 JULY 2021
IMPERFECTIONS/DEFECTS IN SOLIDS
– Points to remember
Schottky defects are due to missing of equal number of cations
and anions from the lattice site.
Frenkel defects are due to missing of a cation from lattice site
and its presence in some interstitial site.
In Schottky defect, density of the crystal decreases.
In Frenkel defect, the density of the crystal remains the same.
AgBr shows both Schottky and Frenkel defects.
Alkali metal halides do not show Frenkel defects because alkali
metal ions being larger in size cannot fit into interstitial sites.
IMPERFECTIONS/DEFECTS IN SOLIDS

• Points to remember
In stoichiometric defects, the ratio of cations to anions
does not change but in non- stoichiometric defects ,it
changes.
 RECAP QUIZ
1. What are imperfections in solids?
2. What type of stoichiometric defect is shown by :
ZnS
AgBr?
3. Why is Frenkel defect not found in pure alkali metal halides?
4. What is the effect on density of a crystal showing:
Schottky defect
Frenkel defect?
5. Why do stoichiometric defects also called thermodynamic defects?
IMPERFECTIONS/DEFECTS IN SOLIDS
• Non-stoichiometric Defects
– If, as a result of the imperfections in the crystals, the
ratio of the cations to the anions becomes different
from that indicated by the ideal chemical formula,
the defects are called non- stoichiometric defects.
– These defects result in either excess of metal atoms
or deficiency of metal atoms.
– It goes like this:
IMPERFECTIONS/DEFECTS IN SOLIDS
• Metal Excess
– By Anionic Vacancies:
• An anion may be missing from its lattice site, leaving a hole
which is occupied by an electron, thus maintaining electrical
neutrality.
– Alkali halides like NaCl and KCl show this type of defect. When crystals
of NaCl are heated in an atmosphere of sodium vapour, the sodium
atoms are deposited on the surface of the crystal.
– The Cl– ions diffuse to the surface of the crystal and combine with Na
atoms to give NaCl.
– This happens by loss of electron by sodium atoms to form Na+ ions.
IMPERFECTIONS/DEFECTS IN SOLIDS
– The released electrons diffuse into the crystal and occupy
anionic sites . As a result the crystal now has an excess of
sodium.
– The anionic sites occupied by unpaired electrons are called
F-centres (from the German word Farbe for colour centre).
– They impart yellow colour to the crystals of NaCl. The colour
results by excitation of these electrons when they absorb
energy from the visible light falling on the crystals. Similarly,
excess of lithium makes LiCl crystals pink and excess of
potassium makes KCl crystals violet.
IMPERFECTIONS/DEFECTS IN SOLIDS
IMPERFECTIONS/DEFECTS IN SOLIDS
• Metal Excess
• Due to presence of an extra cation in the interstitial site:
– An extra cation is present in some interstitial site and an
electron in another interstitial site to maintain electrical
neutrality e.g.
– Zinc oxide is white in colour at room temperature. On
heating it loses oxygen and turns yellow. The excess Zn2+ ions
move to interstitial sites and the electrons to neighbouring
interstitial sites.
IMPERFECTIONS/DEFECTS IN SOLIDS
IMPERFECTIONS/DEFECTS IN SOLIDS

• Metal Deficiency Defect

– These defects arise when the metal shows variable valency. The defect occurs
due to missing of a cation from a lattice site and presence of a cation having
higher charge in the adjacent site.

– A typical example of this type is FeO which is mostly found with a composition
of Fe0.95O. In crystals of FeO, some Fe2+ cations are missing and the loss of
positive charge is made up by the presence of required number of Fe3+ ions
i.e. for every three missing Fe2+ ions , two Fe3+ ions occupy lattice sites and
hence electrical neutrality is also maintained.
IMPERFECTIONS/DEFECTS IN SOLIDS
IMPERFECTIONS/DEFECTS IN SOLIDS

• Impurity Defects in Ionic solids

– These defects arise when foreign atoms are present at the lattice site in
place of host atoms e.g.

– If molten NaCl containing a little amount of SrCl2 is crystallised, some of

the sites of Na+ ions are occupied by Sr2+. Each Sr2+ replaces two Na+
ions. It occupies the site of one ion and the other site remains vacant.
The cationic vacancies thus produced are equal in number to that of Sr2+
ions. Another similar example is the solid solution of CdCl2 and AgCl.
IMPERFECTIONS/DEFECTS IN SOLIDS

Impurity Defect in NaCl

Na+
Sr+2

Na+
IMPERFECTIONS
IMPERFECTIONS/DEFECTS
/ DEFECTSIN
INSOLIDS
SOLIDS

•Impurity Defects in Covalent solids

– In case of covalent solids, such as Si or Ge( group 14 elements)having 4 valence
electrons, the impurities added may be of elements having more or less than 4
valence electrons. These defects are called electronic defects. Accordingly these are
of two types.
• Doping with electron rich impurities
– Group 14 elements having 4 valence electrons form four covalent bonds with the
neighbouring atoms. When such an atom like Si or Ge is doped with group 15
elements like P or As( which have 5 valence electrons ) one extra electron is left free
and gets delocalized. These delocalized electrons increase the conductivity of Si or
Ge. These are called n-type semiconductors.
IMPERFECTIONS/DEFECTS IN SOLIDS
N- TYPE SEMICONDUCTOR P- TYPE SEMICONDUCTOR
IMPERFECTIONS/DEFECTS IN SOLIDS

• Doping with electron deficient impurities

– Group 14 elements having 4 valence electrons form four covalent bonds
with the neighbouring atoms. When such an atom like Si or Ge is doped
with group 13 elements like B, Al or Ga( which have 3 valence electrons )
one hole is created at a site where fourth electron is missing. This is called
electron hole or electron vacancy. An electron from the neighbouring atom
can jump to fill this hole and a hole is created at that place instead. On
applying electric field, electrons move towards positive plate and holes
towards negative plate, These holes carry positive charge and increase the
conductivity of Si or Ge. These are called p-type semiconductors.
SLIDE TITE
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great year learning
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