Imperfections or defects in Solids :
Crystalline solids have perfectly ordered and regular arrangement of constituents units but actually the arrangement of
constituents units are not perfectly regular in all crystals , thus defects in these crystals are found , Any deviation from
the perfectly ordered arrangement of constituents in crystal is called defect or imperfection. These defects sometimes
called thermodynamic defects because the number of these defects depends on the temperature. Crystals may also
possess additional defect due to the presence of impurities. Defect in crystal are due to following reason
(i) Temperature : At 0 K crystals have lowest energy and do not have any defects, such crystal are known as ideal
crystals, above 0 K deviations starts from ordered arrangement of crystal
(ii) Presence of impurities : - Crystal may be distributed by the presence of impurities
There are commonly two types of defect
1 - electronic defect (2) atomic defect or point defect
(a) Electronic defect / imperfection : Generally, electrons are present in fully occupied lowest energy states. But at
high temperatures, some of the electrons may occupy higher energy state 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 0 K. These electrons are free to move in the crystal and are responsible for 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.
(b) Atomic imperfection or point defects : The defect which are arises due to The irregularity in the arrangement of
atoms or ions are called point defects ,
Point defects arises due to any one of the following causes
(i) Some constituents particle are missing from their normal position and the unoccupied position are called vacancies
(ii) Some of the constituents particle are missing from their position and are shifted to the interstitial site
There are two types of point defects -
1. Stoichiometric Defects :Those compounds in which the number of positive and negative ions are exactly in the ratio
indicated by
their chemical formula are called stoichiometric compounds. eg. NaCl (1 : 1) And defect in such compons are called
Stoichiometric Defects
There are two types of Stoichiometric Defects
(a) Schottky defect (Vacancy defect ) (b) Frenkel Defect (interstitial dfects )
(a) Schottky defect (Vacancy defect) - Schottky in 1930 :
This type of defect is arises when the equal 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
(1)high co-ordination number and (2) size of positive and negative ions are almost
equal ( difference in size is very small).
Ex.- NaCl, KCl, CsCl, KBr . AgBr etc.
-the crystal is to remain electrically neutral
- density of the crystal decreases due to schottky defects
- the no. of schottky defects increases with increase the temperature ,
15 6 o 4 o
Ex- at room temperature NaCl has one defects in 10 lattice site and at one in 10 at 500 C and one in 10 at 800 C
-Ea/2KT
no. of schottky defects(n) present in an ionic crystal containing N ions/c.c at temperature is = Ne
Ea = energy required to creat n schottky defects , K = Boltzmann constant = R / NA
(b) Frenkel Defect (interstitial defects )- Frenkel in 1926 :
This type of defect is arises when an ion is missing from normal lattice site and occupies
an interstitial site between the lattice point , Frenkel defects are common in ionic
compounds which have -
(1) low co-ordination number and (2)there is large difference in size between positive and
negative ions.
eg. ZnS, AgCl, AgBr, AgI etc.
- Crystal remain electrically neutral
- Density of the crystal remain same
1/2 -Ea/2KT
- no of Frenkel defects can be n =( N XN’) e
N = no. Of lattice site N’ = no. Of interstitial site K = Boltzmann constant = R / NA
-As a result of Frenkel defects dielectric constant of medium increases
Due to both defect (Schottky and Frenkel ) stability and lattice energy of crystal decreases
- AgBr shows both defects NaCl does not show Frenkel defects because size of Na is greater than that of Ag which
show frenkel defects
Difference between Schottky and Frenkel defects :
SN. Schottky Defect Frenkel Defect
1 Equal no of cationic and anionic vacancies are Some cation are displaced from normal lattice sites to
present the interstitial sites
2 Density lowered Density remain same
3 Dielectric constant remains same Dielectric constant increases
4 Shown by those ionic compound which have high Shown by those ionic compound which have low CN.
CN. ,
5 Shown by those ionic compound in which size of Shown by those ionic compound in which size of
cation and anion are comparable cation is smaller than size of anion
6 Ex - NaCl, KCl, CsCl, KBr . AgBr etc. Ex- ZnS, AgCl, AgBr, AgI etc.
2 Non Stoichiometric Defect : There are many compound in which the ratio of positive and negative ions present in the
compound differs from that required by ideal formula of the compound. Such compounds are called Non-
stoichiometric compounds. eg. VOx (Where x can vary between 0.6 to 1.3.)
In FeO the ratio of Fe and O is 0.94 : 1
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 following types :
(a)Metal excess defects (b) Metal deficiency defect
(a)Metal excess defects : in these defects , the no, of positive ions are in excess , these may arise due to the following
two ways
(i) By anion vacancies (F-centre) : If negative ion leaves its lattice site creating a hole
which is occupied by an electron to maintain the electrical neutrality the electron
trapped in anion vacancies are called F-Centre, these centre are responsible for the
colour of the compound.
‘F’ – stands for “Farbe” (German word) which means colour
- intensity of colour of crystal increases with increases f-centre
-This type of defects are exhibited by the crystals which are likely to exhibit “ Schottky
Defects .
- these are paramagnetic crystal
Ex -•The excess sodium in NaCl makes it the crystal yellow.
• Excess potassium in KCl makes it violet. • Excess lithium in LiCl makes it Pink.
(ii)By presence of extra cation in interstitial sites :
In this case , there are an extra positive ion occupying an interstitial site. Electrically
neutrality is maintained by the presence of an electron in the another interstitial
site. This type of defects are exhibited by the crystals which are likely to exhibit
“Frenkel defects”.
eg. When ZnO is heated it loses oxygen and form Yellow colour due to following
reaction
ZnO Zn+2 +2 e- + 1/2O2
The excess of Zn+2 ions thus, formed get trapped in vacant interstitial sites and the
electron in neighbouring interstitial sites, these electron give rise to enhanced
electrical conductivity
(b) Metal deficiency defect : These contain less number of positive ion than –ve ions these arises due to two ways
(i) Cation vacancies : When positive ions are missing from their lattice site, the
extra negative charge is balanced by an adjacent ion having higher positive
[Link] type of defects are generally shown by compounds which show
variable oxidation state i.e., transition metals.
Ex. FeO, FeS, NiO etc
(ii)Extra Anion occupying interstitial sites: In this case the extra anion may be occupy interstitial sites the extra
negative charge is balanced by the extra charges (Oxidation number of equal number cation to higher oxidation state)
on the adjacent ion such type of defect is not common because the negative ions are usually very larger and they
cannot easily fit into the interstitial sites
Doping : Addition of foreign particle in small amount in a crystal is called doping
