Point Defects:

Atomic defects are formed with expenditure of energy which is most commonly
thermal, although radiation of various kinds can also displace atoms. Two most
common types of crystalline defects in ionic materials:
Frenkel and Schottky defects.

Stoichiometric defects:
These are defined as ones in which the crystal chemistry, i.e., the ratio of the
cations to anions, does not change, and they include, among others.
Frenkel Defects:
In ionic materials, both the cation and the anion can undergo to displacement
from their position inside a crystal.

Frenkel defect in AgCl.

Schottky defects: The vacancy
must be formed in the stoichiometric
ratio in order to preserve the electrical
neutrality of the crystal. Thus in NaCl
and MgO, One forms a Schottky pair,
while in TiO2 the the Schottky defect
consists of three defects (one titanium
vacancy and two oxygen vacancies).
The total number of lattice sites is
increased by one formula unit upon
formation of Schottky defect, unlike
the the Flenkel defect, which
conserves the number of lattice sites. Schottky defect in NaCl
Nonstoichiometric defects:
 Form by the selective addition or loss of one (or more) of the constituents
and consequently lead to a change in crystal chemistry.
 A material accommodates those changes in composition by selectively
losing one of its constituents to its environment.
 This leads to the idea of nonstoichiometry where the simple ratio between
the numbers of the constituent atoms of a compound breaks down.
 For example, if an oxide were annealed in a high oxygen partial pressure, I
would be fair to assume that the number of oxygen atoms should be
relatively greater than the number of cations. Conversely, if the oxygen
partial pressure were very low, one would expect the cation concentration
to be higher.
Extrinsic defects:
 Defects created as a result of the presence of impurities in the host crystal.

 The remainder of this section attempts to answer, among others, the

following questions: Why do point defects form? What are the different types
of defects that can form? And how is their concentration influenced by
temperature and externally imposed thermodynamic parameters, such as
oxygen partial pressure?

 Before we proceed, however, it is imperative to describe in greater detail the

various defects that can form and to formulate a scheme by which they can
be notated.
Point Defects and Their Notation:
In a pure binary compound, the following lattice defects, shown schematically
in Fig. (next slide):
1. Vacancies: sites where an atom is missing. These can occur on either
sublattice.
2. Interstitial atoms: atoms found in sites that are normally unoccupied.
3. Misplaced atoms: types of atoms found at a site normally occupied by
other types. This defect is only possible in covalent ceramics, however,
where the atoms are not charged.
The following electronic defects also exist:
4. Free electrons: electrons that are in the conduction band of the crystal.
5. Electron holes: positive mobile electronic carriers that are present in the
valence band of the crystal
6. Interstitial and substitutional impurities: As depicted in Fig. these can occur on
either sublattice.
Kroger-Vink notation:
Over the years, several schemes have been proposed to denote defects in
ceramics. The one that is now used almost universally is thus the one adopted
here. In this notation, the defect is represented by a main symbol followed by
a superscript and a subscript.
 Main symbol. The main symbol is either the species involved, i.e.. Chemical
Symbol of an element, or the letter V for vacancy.
 Subscript. The subscript is either the crystallographic position occupied by the
species involved or the letter i for interstitial.
 Superscript. The superscript denotes the effective electric charge on the
defect, defined as the difference between the real charge of the defect
species and that of the species that would have occupied that site in a perfect
crystal. The superscript is a prime for each negative charge, a dot for every
positive charge, or an X for zero effective charge.
 The best way to explain how the notation works is through a series of examples.
After this brief introduction to defects and their notation, it is pertinent to ask why point defects form in the first place. So we
will discuss the simpler situation involving vacancy formation in elemental crystals.

Thermodynamics of Point Defect Formation in Elemental Crystals:

Crystal Energy- Defective Crystal + atom (endothermic)

 So it means it cost energy to form defects ???? Then why do they

form???

 The answer lies in the fact that at equilibrium, it is the free energy rather than the
enthalpy that is minimized.
 In other words, it is only when the entropy changes associated with the formation
of the defects are taken into account that it becomes clear why vacancies are
thermodynamically stable and their equilibrium concentration can be calculated.
 It follows that if it can be shown that at any given temperature, the Gibbs free energy associated with a
perfect crystal Gperf is higher than that of a crystal containing nv defects, i.e.. That Gdef - Gperf < 0, where Gdef is
the free energy of the defective crystal, then the defective crystal has to be more stable. The procedure is
as follows: