Microstructural Evolution in Materials, 3.022 M.J.

Cima, MIT
10-1 Release 1.0

Lecture 10
CHARGED DEFECTS IN IONIC SOLIDS
(Additional Reading: Ragone Vol. II 3.5, 3.6, 3.7)

Here we will be concerned with the motion of charged defects under the influence of an
electric field. Charged point defects occur commonly in ionic solids and are of two types;
Frenkel defects and Schottky defects.

The prototypical defect in any crystal is the Frenkel defect, which is formed when an atom is
displaced from its normal lattice site onto an interstitial position. A vacancy and an interstitial
are formed by such an event. Frenkel defects can occur in ionic solids with either the cation
or/and the anion. Lets consider the example of AgCl and the formation of a cation Frenkel
defect. This reaction is written in Kroger-Vink notation as

+ =

Ag i
x
Ag
V Ag Ag (10.1)
where the subscript describes the relevant lattice site and the superscript describes the charge
of the defect with respect to the lattice. The interstitial Ag cation is positive since no atom
would normally exist at that location. The vacancy at the silver site is negative since a silver
atom would normally exist there. We can estimate the concentration of Frenkel defects (see
equations 14.25 through 14.36) in exactly analogous fashion to what we did for the
equilibrium concentration of a vacancy alone. The only difference is that we need to consider
the formation of both a vacancy and an interstitial atom. In general, we have the cation
reaction,

+ =

A i
x
A
V A A (10.2)
with corresponding enthalpy and entropy of formation, H and S. This entropy does not
include the configurational enthropy, S
c
, arising from the many ways the interstitial and
vacancy can be arranged on the lattice. Thus, the total Gibbs energy of a crystal with n
Frenkel defect pair is

c f
S T g n G G + =
0
(10.3)
Microstructural Evolution in Materials, 3.022 M.J. Cima, MIT
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where G
0
is the Gibbs Energy of the perfect crystal and g
f
is the Gibbs Energy of formation
per defect pair.

The configurational entropy is given by S
c
= k ln where is the number of distinct ways
the defects can be arranged. If we assume that there is only one interstitial site per lattice site
then the number of ways interstitials can be arranged is

( ) ! !
!
i i
i
n n N
N

= (10.4)
where N is the number of lattice sites (equal to the number of interstitial sites) and n
i
is the
number of ways vacancies can be arranged is

( ) ! !
!
v v
v
n n N
N

= (10.5)
The total configurational entropy is therefore,

( ) ( )
|
|
.
|

\
|

|
|
.
|

\
|

=
! !
!
! !
!
ln
v v i
c
n n N
N
n n N
N
k S (10.6)
or, since the defects are formed in pairs with n = n
i
= n
v


( )
( ) ( ) | | n n n N n N N N k
n n N
N
k S
c
ln ln ln 2
! !
!
ln 2 =
|
|
.
|

\
|

= (10.7)

(

|
.
|

\
|
+
|
.
|

\
|

=
n
n N
n
n N
N
N k S
c
ln ln 2 (10.8)
Substitution in the equation for the Gibbs Energy of the crystal gives

(

|
.
|

\
|
+
|
.
|

\
|

+ =
n
n N
n
n N
N
N kT g n G G
f
ln ln 2
0
(10.9)
The equilibrium defect concentration is obtained by differentiating and equating to zero. This
results in (with N - n N)

|
|
.
|

\
|
=
kT
g
N
n
f eq
2
exp (10.10)
Schottky defects are unique to ionic compounds since they are formed by the simultaneous
creation of both cation and anion vacancies. You can see why both types of vacancies are
Microstructural Evolution in Materials, 3.022 M.J. Cima, MIT
10-3 Release 1.0

required by considering a simple example. A negatively charged vacancy is created if you
were to create a vacancy on a cation site by removing a cation from within the crystal and
creating a new cation site on the surface of the crystal. Electroneutrality demands that
positive vacancy or vacancies be created on an anion site by moving an anion to the surface.
Thus, one has a chloride vacancy for every sodium vacancy in NaCl and two oxygen
vacancies for every titanium vacancy in TiO
2
.

The reactions forming Schottky defects are written in a funny way. The cases of NaCl and
TiO
2
are
null =

Cl Na
V V (10.11)
null =

+

0
2V V
Ti
(10.12)
The word null refers to the fact that these defects are being created from a perfect lattice.
Exactly as before, the equilibrium concentration of Schottky defects can be obtained by using
the cofigurational enthropy for the reaction in question. Thus, for the case of NaCl we have
|
.
|

\
|
= =

kT
g
N
n
N
n
S
V V
Cl Na
2
exp
'
(10.13)
where g
S
is the Schottky formation energy.

Lets now consider the incorporation of solute into an ionic crystal. Several cases exist.
Sustitutional solutes with the same valence as the host involve no charged defects. For
example, introduction of LiCl into NaCl gives

x
Cl
x
Na
Cl Li LiCl + = (10.14)
Aliovalent solutes (ions of differing charge than the host) must be somehow charge
compensated. There are two ways to do this. Either additional charged defects must be
created or electronic defects (such as conduction electrons or holes) need to be created. For
now we will only discuss ionic compensation. Say for example, that Al
2
O
3
is dissolved in
MgO in a substitutional manner. Aluminum ions are +3 while magnesium ions are +2. Thus,
each Al
Mg
defect will have a positive charge with respect to the lattice. Electroneutrality
Microstructural Evolution in Materials, 3.022 M.J. Cima, MIT
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demands that some other defect be present to compensate for the charge. Restricting
discussion to only ionic compensation says that negatively charge vacancies on magnesium
sites are required. This is written

+ + =

Mg
x
0 Mg 3 2
V 3O 2Al O Al (10.15)
Note that the net charge on the right-hand side is zero and the sites are in the same ratio as the
host MgO crystal.
The situation is really more complicated even when restricted to only ionic compensation.
Consider the alternative example of MgO solute in a Al
2
O
3
crystal. The Mg ion is sufficient
size and the Al
2
O
3
is open enough that the Mg ion can be substitutional or interstitial. One
possible substitutional reaction is


+ + =
O
x
O Al
V O g M MgO 2 2 2 (10.16)
Note that the site ratio on the right is 2:3 as it should be for Al
2
O
3
. An interstitial reaction is

Al
2 3 3 3 V O Mg MgO
x
O i
+ + =

(10.17)
The existence of interstitial Mg, however, introduces another way that substitutional Mg can
be compensated.

x
O i Al
O Mg g M MgO 3 2 3 + + =

(10.18)
Here we see that interstitial Mg ion is compensating the charge on substitutional Mg ion. This
is called self compensation. The reactions 10.16, 10.17, and 10.18 each have their own
equilibrium constant and are simultaneously satisfied
| | | |
|
.
|

\
|
= =

RT
G
V g M K
A
O Al A
exp
2
(10.19)
| | | |
|
.
|

\
|
= =

RT
G
V Mg K
B
Al i B
exp
2
3
(10.20)
| | | | |
.
|

\
|
= =

RT
G
Mg g M K
C
i Al C
exp
2
(10.21)
Assuming that one knows G
A
, G
B
, and G
C
, then there are four unknows to deal with;
[Mg
A

], [V
O

], [Mg
i

], and [V
Al

]. The additional equation needed to solve for these

concentrations is given by the electroneutrality requirement.
Microstructural Evolution in Materials, 3.022 M.J. Cima, MIT
10-5 Release 1.0

| | | | | | | |

+ = +
i O Al Al
Mg V V Mg 2 2 3
' ' ' '
(10.22)
Thus, the solution of four equations above is a method to determine the concentrations of the
various defects. The next lecture will describe a method which simplifies the solution to these
equations. First lets consider the possible contributions of electronic defects.

We can begin to relax the assumption of ionic compensation by considering the reactions of
conduction electrons and holes with defects. Intrinsic conduction electrons in materials with a
band gap arise by a valence electron with sufficient energy to exist in the conduction band.
Excitation across that gap, however, leaves a hole in the valence band. This reaction can be
viewed as
null =

+ h e (10.23)
with equilibrium constant | || | . np h e K
el
= =

Note these electronic defects are free and are
therefore, not attached to a specific lattice site. One can envision a situation, however, when
electronic defects encounter ionic defects. Say, for example, the encounter between a
conduction electron and an oxygen vacancy. If the electron becomes trapped at the vacancy,
then the vacancy is no longer doubly charged with respect to the lattice.


= +
O O
V e V (10.24)
Effectively, the vacancy has taken on a different valency, just as the multiple valence states of
transition metal ions. Iron, for example, exists in the +2 and +3 oxidation state when
dissolved in oxides. Thus, in an MgO lattice it can exist as either Fe
Mg
x
or Fe
Mg

. The same
defect, but two different charges.

The most common way the electronic defects interact with ionic defects is through reactions
involving equilibrium with an ambient gas. One case is the equilibrium of an oxide crystal
and the ambient oxygen environment. The relevant reaction is
( ) e V g O O
O
x
O
+ + =

2
2
1
2
(10.25)
Microstructural Evolution in Materials, 3.022 M.J. Cima, MIT
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Note that the oxygen vacancy introduced by removal of oxygen to form O
2
is charge
compensated introduction of two conduction electrons. We call this a reduction reaction since
it involves removal of oxygen from the crystal.

An oxidation reaction is one in which oxygen is introduced to the lattice. For example,
gaseous oxygen can react with oxygen vacancies by
( )

+ = + h O V g O
x
O O
2
2
1
2
(10.26)
Obviously, the last two reactions can not be independent, since one must some how be the
reverse of the other. To see this, just add the two reaction equations together
( )

+ = + h O V g O
x
O O
2
2
1
2
(10.27)
( ) e V g O O
O
x
O
+ + = +

2
2
1

2
(10.28)
( ) ( ) e h O V g O O V g O
x
O O
x
O O
+ + + + = + +

2 2
2
1
2
1
2 2
(10.29)
null = e h +

2 2 (10.30)
null = e h +

(10.31)
Just what is the concentration of intrinsic conduction electrons? These electrons are fermions
and are, therefore, governed by Fermi-Dirac statistics. Thus, the concentration of electrons
with energy E is
( ) ( ) ( ) E F E N E n = (10.32)
where N(E) is the density of states and F(E) is the Fermi-Dirac Function.
( )
(

+
=
kT
E
E F

exp 1
1
(10.33)
with being the Fermi Energy.

Band theory predicts that the density of states in the conduction and valence bands,
respectively, near the band edge are given by
Microstructural Evolution in Materials, 3.022 M.J. Cima, MIT
10-7 Release 1.0


3 19
2 3
2
*
10
2
2

(
(

= cm
h
kT m
N
e
C

at 300K (10.34)

3 19
2 3
2
*
10
2
2

(
(

= cm
h
kT m
N
h
v

at 300K (10.35)
where m
e
*
and m
h
*
are the effective mass of conduction electrons and holes, respectively.
These masses in oxides are 2 to 10 times larger than the mass of a free electron. Note that the
density of states are 10
4
smaller than typical atom densities of 10
23
/cm
3
.

When the energy gap is large with respect to the Fermi energy (E->>kT) then the Fermi-
Dirac equation can be approximated by the Boltzmann function
( ) ( ) | | kT E E F / exp (10.36)
Thus, with this restriction we have
|
.
|

\
|
=
kT
E
N
n
c
c
e

exp (10.37)
|
.
|

\
|
=
kT
E
N
n
v
v
h

exp (10.38)
What is the Fermi energy? To determine its value, just note that we require that an intrinsic
semiconductor have n
e
= n
h
because of charge neutrality

kT
E
v
kT
E
c
v c
e N e N

=

(10.39)

kT
E
N
kT
E
N
v
v
c
c

=

ln ln (10.40)

v c
v
c
E E
N
N
kT + = ln (10.41)

v
c
v c
N
N
kT E E ln 2 + = (10.42)

c
v v c
N
N kT E E
ln
2 2
+
+
= (10.43)
Microstructural Evolution in Materials, 3.022 M.J. Cima, MIT
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but
2 3
*
*
|
|
.
|

\
|
=
e
h
c
v
m
m
N
N
(10.44)
so the Fermi level in an intrinsic semiconductor is approximately

|
|
.
|

\
|
+
+
=
*
*
ln
4
3
2
e
h v c
m
m
kT
E E
(10.45)
The second term is usually small compared with the first. Thus,
E
c
E
v
E
g



Returning to the question of the concentration of conduction electrons and holes we see that,
for the condition of E- >> kT, we have

(

=
kT
E
N n
c
c e

exp (10.46)
but with
2
v c
E E +
(10.47)

2
2
2
v c c v c
c c
E E E E E
E E

=
+
(10.48)

2 2
g
v c
c
E
E E
E =

(10.49)

(

kT
E
N n
g
c e
2
exp (10.50)
Likewise

(

kT
E
N n
g
v h
2
exp (10.51)
The equilibrium constant for the reaction
null

+ h e (10.52)
is therefore
Microstructural Evolution in Materials, 3.022 M.J. Cima, MIT
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(

= =
kT
E
N N n n K
g
v c h e i
exp (10.53)
or since n
e
= n
h
for the intrinsic semiconductor we have
( )
(

=
kT
E
N N n
g
v c e
2
exp
2 1
(10.54)
Thus, for Si (E
g
= 1.1 eV)
( )
(

5
3 19
10 62 . 8 298 2
1 . 1
exp 10
x
cm n
e
(10.55)

3 9
10 5

cm x n
e
(10.56)

For ZnO (E
g
= 3.2 eV) with a larger band gap
| |
(
(
(
(

K atom
eV
x K
atom eV
cm n
e
5
3 19
10 62 . 8 298 2
2 . 3
exp 10 (10.57)

3 9
10 9 . 8

cm x n
e
(10.58)
Also for MgO at 1000K
( ) ( )
3 5 . 4 3 19
5
3 19
4 . 0 10
10 62 . 8 1000 2
7 . 7
exp 10

= =
(

cm e cm
x
cm n
e
(10.59)
what about defect concentrations? Lets consider Schottky defects in MgO at 1000K.
null =

+
O Mg
V V eV h
s
7 . 7 (10.60)

(

=
kT
h
kT
g
N
n
s s s
2
exp
2
exp (10.61)

20
5
10 4
10 62 . 8 1000 2
7 . 7
exp

=
(

= x
x N
n
s
(10.62)
The density of atoms in solids is approximately 10
23


3 23 20
4000 10 10 4

= = cm x n
s
(10.63)
Thus, for MgO we expect that n
s
>> n
e
at stoichiometric conditions.

Microstructural Evolution in Materials, 3.022 M.J. Cima, MIT
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Thus far we have neglected any contribution that electronic defects make in balancing the
charge on an aliovalent doping. The previous examples have all considered only ionic
compensation. The addition of niobium pentoxide, Nb
2
O
5
, to titanium dioxide, TiO
2
, for
example, creates singly charged niobium defects, Nb
Ti

. The charge on this defect may be

compensated by the formation of another charged ionic defect or the formation of an
electronic defect. Ionic compensation can be written

Ti
x
O Ti
TiO
V O Nb O Nb + + =

10 4 2
2
5 2
(10.64)
The negatively charged titanium vacancy is demanded by the charged balance and the
requirement that the site ratio be maintained at the ratio of 1:2 as in TiO
2
. Electronic
compensation requires that e be introduced rather than V
Ti
. Thus, the relevant reaction is
( ) g O O e Nb O Nb
x
O Ti
TiO
2 5 2
8 4 4 2
2
+ + + =

(10.65)
Here the requirement of the 1:2 site balance ratio demands that one mole of oxygen gas be
produced for every four moles of conduction electrons formed. Subtracting the last two
equations gives
( )
Ti
x
O
TiO
V O e g O + = + 2 4
2
2
(10.66)
which is the simple oxidation/reduction of the TiO
2
crystal.

One should note that other possible ionic defects can compensate the charge on Nb
Ti

, since Ti
is found in a number of possible valence states. Examples are Ti
+3
and Ti
+2
which correspond
to defects Ti
Ti
and Ti
Ti
, respectively.

Clearly, the prevailing compensation mechanism (electronic or ionic) will depend on
temperature, solute concentration, and oxygen partial pressure.