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Ionic defects
Occupy lattice positions
Can be either of vacancies, interstitial ions, impurities and substitutional ions
Electronic defects
Deviations from a ground state electron orbital configuration give rise to such defects
when valence electrons are excited into higher energy orbitals/ levels and lead to
formation of electron or holes.
Defects are present in most oxides and are easily understood. Hence most examples in the
following section use examples of oxides.
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Regular Sites
M m: normal or regular occupied metal or
cation site
Oo : normal or regular occupied oxygen or
anion site
Point Defects (a (dot) means a positive charge and a ' (prime) means a
negative charge)
Oxygen (anion) vacancy
VO
VM
Oi
Mi
Vi
Foreign cation
Mf
on
Mfi
VO or VO
VM ' or VM ''
and anion
VM x or VO x
e' or h
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2.4.1Schottky Disorder
This defect normally forms at the outer or inner surfaces or dislocations. It eventually diffuses
into the crystal unit as equilibrium is reached.
VM ''+ V0
This defect is preferred when cations and anions are of comparable sizes.
Examples are rocksalt structured compounds such as NaCl, MgO, Corundum, Rutite etc..
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VM '' +
Mi
In cases where anions form the disorder, then it is called as Anti-Frenkel. The corresponding
defect reaction in that case would be
0
V0 + O i ''
Examples of compounds showing this defect are AgBr type compounds such as AgBr, AgI
etc.
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VO + O 2 + 2e'
Ionic compensation leads to formation of oxygen vacancies and reduction of metal ions
on their sites.
O0
VO + O 2 + 2M' M
MM
Mi + 4 M' M
OR
Electronic compensation leading to the formation of metal interstitials and free electrons
M
Mi + 4e'
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Creation of holes
Conduction due to holes i.e. a p- type conductor
Examples of oxides showing this characteristics are MnO, NiO, CoO, FeO etc.
P-type conductor
Example can be an oxide like UO 2.
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(i)
ii. Alternatively for a metal deficient oxide MO, creates metal vacancies as
(ii)
iii. For an oxygen deficient oxide, oxygen vacancies are compensated as
(iii)
Reaction (iii) results in the reduction in vacancy concentration, while reactions (i) and (ii) result
in increase in the electron concentration or metal vacancy concentration.
iv. Reaction (i), for a p-type conductor, can be alternatively expressed as following
(iv)
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V M ' + Mi + X X
(2.1)
where SC is the change in configurational entropy and is positive. Equilibrium concentration of
defects is found by minimizing G w. r. t. n i.e. the concentration at which free energy is minimum.
Change in entropy is given by
(2.2)
where W is the number of ways in which defects can be arranged.
Now, as per the defect reaction shown above, number of Frenkel pairs (n) would lead to the
formation equal number of interstitials (n i ) as well as vacancies (n v ) i.e.
(2.3)
Assume that total number of lattice sites = N
Number of ways to arrange the vacancies, W v is
(2.4)
Ways to arrange the interstitials (assuming that N lattice sites are equivalent to N interstitial sites), W i
are
(2.5)
OR
or
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(2.7)
(2.11)
(2.12)
Now we know that G f = H f - TSv where H enthalpy of Frenkel defect formation and Sv =
vibrational entropy change.
Hence Equation (2.12) further simplifies to
(2.13)
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Assuming that exp (Sv /2kT ) ~1 as vibrational entropy change is very small, and hence
(2.14)
(2.15)
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Here, one can see the relation with the melting point that melting point of MgO is
~2825C while it is ~801C for NaCl. So, at any given temperature NaCl will have
much larger defect concentration than MgO. However, at the same homologous
temperature, defect concentrations can be quite similar.
Interestingly, while the highest achievable purity level in MgO is 1 ppm, in NaCl, it is 50
ppm. Typically, these impurities consist of aliovalent cations which give rise to defects,
called extrinsic defects. Thus the concentration of extrinsic defects is much greater than
intrinsic defect concentration in MgO. As a result, defects in NaCl are likely to be
intrinsic but MgO is most likely to contain extrinsic defects.
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(2.16)
where G o
At equilibrium, G o = 0, , hence
(2.19)
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which leads to K = K0 exp (-H 0 /RT), where K0 = S0 and R is the gas constant.
Alternatively,
(2.21)
This is an important outcome as it shows that we can treat the defects in a solid as solutes in a
solvent.
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] [V M '']
(2.22)
where G S is the molar free energy of defect formation and is H S - TSS , where H S is the
enthalpy for defect formation and SS is the entropy change which is mainly vibrational in nature
and can be assumed to be constant. This leads to
(2.23)
(2.24)
which leads to
(2.25)
OR
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=
[M i ] and [V M ''] << MM and MM 1
Thus
[M i ][VM '']=KF
(2.26)
i.e.
[M i ]= [V M ''] = KF1/2
(2.27)
I n a similar manner what we did above for Schottky defects, one can now write
[M i ]= [V M '']
(2.28)
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K=[
(2.29)
Here,we assume that [OO ] = 1. From the above reaction, to maintain the electrical neutrality,
n e = 2 [V O ].
Thus
(2.30)
or
(2.31)
or
(2.32)
and
]=
(2.33)
The relationship between the defect concentration and pO 2 can be seen in the schematic figure
where defect concentration varies as pO 2 -1/6 . This makes sense because concentration of vacancies
will go down as we supply more oxygen to the material.
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Figure 2. 4
Defect concentration vs pO2 in an oxygen
deficient oxide with oxygen vacancy as dominating defect
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(2.34)
ne = 2 [ Mi ]
(2.35)
Thus
OR
ne
(2.36)
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OR
Assuming
(2.37)
(2.38)
= 2[ V O] + 2[ Mi ]
(2.39)
(2.40)
And
(2.41)
i.e.
[ Mi ]
(2.42)
As you can see, under such conditions, [M i ] decreases more rapidly with increasing pO 2 . This is
commonly observed in TiO2 and Nb2 O 5 where [V 0 ] can be 10 10 times higher than [M i ].
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When [M i ] >>[V 0 ]
Following similar exercise as above, we can calculate
[ Mi ] =
(2.43)
and
[
]=
(2.44)
Here, [V 0 ] increases with increasing pO 2 while keep decreasing with increasing pO 2 but at a
different rate.
Figure 2. 5
Defect concentration vs pO2 in
an oxygen deficient oxide with oxygen
vacancy as dominating defect
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(2.45)
If
then
(2.46)
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Equilibrium constant is
(2.48)
If n e = n h ,
(2.49)
Again, one sees that concentration of electron and holes are independent of oxygen pressure.
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+[
] + 2e'
(2.50)
At high pO 2
The defect reaction is
(2.51)
At intermediate pO 2
Stoichiometric defects are likely to prevail i.e. either via intrinsic ionization or Anti-Frenkel
defects.
Intrinsic ionization of electrons and holes
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.[
(2.53)
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(2.55)
(2.56)
Substituting in (2.53)
(2.57)
(2.58)
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(2.60)
(2.61)
]=
(2.62)
(2.63)
Now combining (2.61)-(2.63) and using (2.60), we get an important condition i.e.
(2.64)
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] and
(2.65)
Here both n e and n h are independent of pO 2 while the point defect concentrations are given as from
(2.50)
(2.66)
(2.67)
Now, since
and [
n h are given as
(2.69)
(2.70)
The above equations provide the limiting conditions of oxygen partial pressure separating three
regimes of oxygen pressures with variations of defect concentration vs pO 2 obtained. From this we
can plot a defect concentration vs pO 2 plot, also called as Brouwers Diagram. Such diagrams are
extremely important in defect chemistry to understand the dominating defects which govern the
physical processes.
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Figure 2. 6
Concentration of ionic defects vs pO2 with
Oxygen Frenkel defects dominating at stoichiometric
composition
2.14.2 Intrinsic ionization dominating at stoichiometric composition
Using the proceedure similar to that explained in the previous slide except that in the central region
now n=p as intrinsic ionization dominates at the stoichiometric composition, we obtained the following
figure. There are subtle differences as we can observe by comparing the two figures.
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Figure 2. 7
Concentration of ionic defects vs pO2 with
intrinsic ionization dominating at stoichiometric composition
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It can be seen from the above equations that Kox increases as the temperature increases; i.e. MgO
can be oxidized at high temperatures producing extrinsic Mg vacancies and holes if no other defects
are present.
Further from electrical neutrality condition,
It should be noted that though actual concentrations can be very small but they still do vary with
temperature and oxygen pressure.
For example, at 80% of Tm (2480 K) in air i.e. pO 2 = 0.21 atm
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and
=[
]
MPa.cm-1 .
]=
]=
which is equivalent to a deficiency of x~0.27% in TiO2-x and makes TiO2-x an n-type semiconductor
due to the resulting high electron concentration.
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1.1 eV
NaCl
7.3 eV
Ge
0.7 eV
MgO
7.8 eV
Diamond
5.4 eV
NiO
4.2 eV
GaAs
1.43 eV
FeO
2.0 eV
GaP
2.25 eV
BaTiO3
2.8 eV
BN
4.8 eV
TiO2
3.0 eV
CdTe
1.44 eV
UO 2
5.2 eV
ZnO
3.2 eV
SiO2
8.5 eV
3.1 eV
MgAl2 O 4
7.8 eV
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** Basically, materials having a well defined band gap show conduction band, band of higher energy
and valence band, bands of lower energies with maximum of valence band and minimum of conduction
band separated by the forbidden energy gap i.e. Eg . The position of Fermi energy, EF, lies in this
forbidden gap. At 0 K, all the states in the valence band are filled while the states in the conduction
band are empty. Another way to express this is that all the energy states below EF are filled while
those above EF, are empty at 0 K. It is just that for basic physics reasons, carriers cannot reside in the
forbidden energy gap.
Elementary physics of bands in materials can read from any book related to solid state physics or
electronic properties of materials as listed in the bibliography.
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(2.71)
(2.72)
where N c and N v are defined as effective conduction and valence band density of states and are
expressed as
and
(2.73)
Here me * and mh * are the effective mass of electron and holes respectively, k is the Boltzmanns
constant, h is the Plancks constant and T is the temperature. The value of N c and N v is ~10 19 cm -3
at 300 K.
Electron and hole concentrations in the conduction and valence bands are equal i.e.
(2.74)
Fermi energy is defined as
(2.75)
where
In oxides, me * and mh * are generally 2-10 times larger than the mass of free electron, me . Since,
the atomic density of solids is about 10 23 cm -3 , the density of states is about four order of
magnitude lower than that in semiconductors.
Moreover, if the second term in equation (2.75) is small and is actually zero if me * = mh * , then
Fermi level is quite close to the center of the band gap.
Hence for an intrinsic compound where n e = n h .
(2.76)
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Fermi level usually remains in the middle of the band gap but can shift up or down when materials is
doped. Typically EF moves up, from the center of the bandgap towards EC , for n-type doping and
moves down for p-type doping.
The above expressions have striking similarity to the concentration of lattice defects where
(2.77)
The density of electronic states may be thought of as equivalent to the density of vacancies in the
lattice sites.
The excitation of electrons across the band gap can be depicted by a chemical defect reaction as
follows
(2.78)
At 300K
(2.79)
Here Ki is not unit-less unlike the reaction constant in the defect reactions because n e and n h have
the units of cm -3 .
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2.19 Examples
2.19.1 Intrinsic electronic and ionic defect concentrations in MgO
Consider that a material like MgO usually has Schottky defects with enthalpy of formation (H F) ) of
about 7.7 eV. Its band gap is about 7.65 eV which decreases at a rate of 1 meV per K as MgO is
heated.
The question is that in case of an absolutely pure and stoichiometric MgO, which defects are likely to
be created and present in higher concentrations at a temperature of say 1400C or 1673 K?
We can calculate the Schottky defect concentration as
In MgO,
and
where mo is the mass of free electron and is 9.110 31 kg.
At 1673K, Eg = 7.85 eV (1570*1*10 3 ) eV = 6.28 eV .
Hence, n e = n h = 4.6*10 10 cm 3
Now magnesium vacancy concentration can be calculated as
Hence, at 1400C, despite high energy of Schottky defect formation, the vacancy concentration will be
slightly larger than the electronic carrier concentration due to thermal excitation.
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These energy levels are situated with respect to the conduction and valence band edges in the band
gap.
For example in MgO, Al acts as a donor while Na acts as an acceptor according to the following
reactions:
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(1)
Electronic
compensation
(2)
(3)
Equation (3) shows that as pO 2 increases, oxidation is favored and hence formation of titanium
vacancies is more likely. Similarly, as the temperature reduces, oxidation is again favored.
Thus Nb doping of TiO2 tends to be compensated by VTi '''' if Nb2 O 5 concentration is large, pO 2 is
high and the temperature is low ,whereas the inverse conditions favour the electronic compensation.
In any case, the electrical neutrality condition requires that
(4)
Similar effects are observed in care of titanates such as BaTiO3 .
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(1)
OR
(2)
From (1), oxygen vacancies formed allow ZrO 2 to possess high ionic conductivity as a result cubic
ZrO 2 is used as electrolyte. When CaO in ZrO 2 dissolves substitutionally, it has to be compensated
by creation of a positive charge.
These substitutions also lead to a change in crystal density of ZrO 2 .
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Summary
In this module, we discussed the defect formation in ceramic, with references to oxides. While
defects such as Schottky defects maintain the stoichiometry of the materials, most oxide ceramics
are prone to the non-stoichiometry. This non-stoichiometry results in defects such as ion vacancies
or interstitials and compensating charged defects either via ionic compensation or electronic
compensation. While defect concentration in the intermediate oxygen partial pressure (around
atmospheric conditions) are independent of the partial pressure of oxygen, the defects in nonstoichiotemetric oxides either at high or low pressures are strongly dependent on the partial pressure
of oxygen. This can be effectively understood through the construction of Brower diagrams. Finally,
we looked at the electronic disorder and evaluated the conditions to compare the ionic and electronic
defect concentrations.