• Point defects

• Line Defects - Dislocations

• Surface Defects - Grain Boundaries
• Majority of this chapter is on point
defects.
 Why bother?
• Point defects dictate several properties:
– Diffusion which then determines sintering and
sometimes creep
– Electrical conductivity
– Dielectric constants
– Most dramatic example: YBa2Cu3O7
– Metal oxidation
– Solid electrolytes and SOCF
– Oxygen sensors
Thermodynamics of Point
Defect Formation
Or why vacancies are
unavoidable: a thermodynamic
necessity…

Approach: find an expression for

G of perfect crystal and one for
defective crystal; the one with the
lower (more negative G) wins…
 Perfect Crystal
Gperf = Hperf - T Sperf
S = Scofig + ST
 kT 
ST  3Nkln 1
 hv 

 kT 
Gperf  H perf  TSperf  H perf  3NkTln 1
  hv 
 Defective Crystal
If it costs, hd to form one defect, how much for nv defects

H def  H perf  n hd
 N n 
Sconfig   kN ln  n ln 
 N  n N  n 
Assume all atoms near a vacancy now vibrate with a
 different frequency, ’. Thus

 kT   kT 
ST  kN  n  ln 1 n  kln 1
 h   h ' 
 Gdef  H perf  n hd
  kT   kT  N n 
 kTN  n  ln  1 n  ln  1 N ln  n ln 
  h   h '  n  N n  N 

• Drum roll comes here….

'  N n 
G  Gdef  Gperf  n hd  kTn  ln  kTN ln  n ln 
  n  N n  N 

• Lets plot this function ….. Ignore 2nd

term.
MISI…
 n eq n eq  hd  Tsvib   gd 
  exp  exp 
n eq  N N  kT   kT 

g  hd  T svib
svib  k ln  
Note this is END result. We differentiated the config. entropy
out of the picture to find the EQUILBRIUM concentration
of vacancies.
 Types of Point Defects in Ionic
Solids
• Stoichiometric Defects:
– Do not change the chemistry of crystal.
Egs. Schottky and Frenkel
• Non-stoichiometric Defects
– Change the chemistry of the crystal
• Electronic Defects: electrons and holes
• Extrinsic Defects
– Aka impurities
Point Defects Complicated Because
We Have More than One Sublattice
Kroger-Vink Notation
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
crystallo graphic positio n 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.
 Examples
• Examples: What are defects that can
occur in pure Al2O3….
– Vacancy on Al:
0 3 '''
V Al V Al
– Vacancy of O:

02 
V o V o
 3 0 
• Al interstitials ?
Al i
Al
i
• O interstitials?
2 0 "
Oi
O i
• Add CaCl2 to NaCl
?? 
• Add KCl to NaCl 
Ca Ca
 Na Na
?? 
 K K
  Na Na
 Rules for Defect Reactions
 Mass balance: Mass can not be created or
destroyed. Vacancies have zero mass.
 Electroneutrality or charge bala nce: Charges cannot be
created or destroyed.
 Preservation of regular site ratio: The
ratio between the numbers of regular cation and
anion sites must remain constant and equal to
the ratio of the parent lattice. Thus if a normal
lattice site of one constituent is created or
destroyed, the corresponding number of normal
sites of the other constituent must be
simultaneously created or destroyed so as to
preserve the site ratio of the compound.
 Stoichiometric Defects and Reactions
Stoichiometric defect do NOT
change the chemistry of the crystal

Did site ratio change?

How many cation sites
before and after?
How many anion sites
before and after?


OO  M M
x x
 OO,s
x
 MM,s  VO  VM
x

 Schottky Defect Reaction


OO  M M
x x
 OO,s
x
 MM,s  VO  VM
x

In MOMO oxide:

Null (or perfect crystal)  VM V 

O gS
In M2O3 oxide:

Null (or perfect crystal)  ??V  ??V
'''
Al O

In MOOMOO oxide: 

Null (or perfect crystal) 
V  ??V
??
M O
 For an MaXb compound
aXX  VX   bMM  VM 
MM  VM a

XX  VX b

For example in Al2O3:

 M  V 2
Al Al

XO  VO 3
should always be true even in hell.


 Thermo of Schottky Defects
Ncat  Vcat 1
Nan  Van 2
S  kln  kln 12


 N cat  Vcat !  N an  Van !
 N cat !Vcat !  N an!Van !
 N cat  ncat   N an  nan   1
 •Find minimum in free energy then:
V V eq eq
V Veq eq
 hS  T sS 
  V
an cat
 an cat
 exp 
N an
eq
an V eq
cat  N cat  N an N cat  kT 
 V Veq eq
V Veq eq
 hS  T sS 
an cat
 an cat
 exp 
N an V
eq
an V eq
cat  N cat  N an N cat  kT 

sS  hS 
Va   Vc   exp exp 
2k  2kT 
Temp. independent term
Vcat Van
Vc   Va  
Vcat  N cat Van  N an
Square brackets denote mole
fractions of defects!
They aredimensionless!
 Frenkel Defects
• Frenkel defect for a
trivalent cation:

M M  VM
x
 Mi
Mass balance?
Charge balance?
Site ratio preserved? Did site ratio change?
How many regular cation sites

O O V
x
O
??
??
??
??
before and after?
 TD of Frenkel Defects
N*= total # of inter. sites, ni # of interstitials
*
N ! NT!
1  2 
N  ni !n i!
*
NT  Vcat !Vcat!
S  kln 12
eq
V n eq
 gF  TSF  hF 
cat
 exp
i
 exp exp 
NT N *
 kT  kT  kT 

 T indep. term
 Mass Action Expression

aA + bB = cC + dD ∆G
c
x x d
 G 
C
 exp
D
 K
eq
a
x x
A
b
B  kT 
 Defect Reactions Revisited
M  O  VM  V
x
M
x
O

O


[V ][V ]  gS
'' 
0
x
 exp


M
x

 SK

[O ][M ]
0  kT
M 
V Veq eq
V V eq eq
 hS  T sS 
an cat
 an
 exp
cat

N an V
eq
an V eq
cat  N cat  N an N cat  kT 


Are these two expressions identical?
 Defect Reactions Revisited

x
MM  VM
 Mi

[M ][V ] ''' gF 
i
x
 M
exp 

 
 K F
[M M ]  kT 
eq
V n eq
 gF  TSF  hF 
cat
 exp
i
 exp exp 
NT N *
 kT  kT  kT 
 Are these two expressions identical?
 Anti-structure Defects

CC  SiSi  SiC  CSi

• Impossible in ionic solids.
• Even if they form are not that important
• Can be important in ternary oxides such
as BaTiO3 or other Perovskites
 GAP The Great Divide NO GAP

Semiconductor Metallic conductivity

or insulator Available
energy levels

For all intents &

Conduction band purposes this
situation is same Conduction band
as
Eg = band gap
Full valence band
Full band aka
Valence band 1/2 full band } Partially filled
valence band

also known as
 Electronic Defects

Null  e  h
Write down expression for ∆G…. What is source of entropy (1$)

np  Eg 
 exp  K i
 N N c  kT 
Eg is band gap.
Nv is the effective density of states in
the valence band
Nc is the effective density of states in
the conduction band.
 np  Eg 
 exp  K i
N N c  kT 
The i in Ki stands for ionization.. because that is what you do.

 E g 
[n][ p]  exp  K i
 kT 
In this form you can think of [n] and [p] as a measure of the
fractional occupancy of the valence and conduction bands..
This expression is always true at equilibrium.
 Effective Density of States

2 me* kT 
3/ 2
2 m kT 
* 3/ 2

N c  2  N  2 h

 h 
2
 h 
2

• m*e is effective mass of electrons in

conduction band.
• m*h is effective
 mass of holed in valence
band.
• h is Plank’s constant
• Exercise (hand in): Calculate the density of
states at 1000 K and compare to 300 K.
 Useful Analogies
These 2 equilibrium equations are true at ALL times!

 g   g 
[V ][V ]  exp

 
 K S [M i ][VM''' ]  exp
 
 K F
'' S F
0 M  kT  kT
   
But so are these 2!
 
[OH ][H

]  K 10 14
Isn’t science
wonderful?
 E g 
[n][ p]  exp  K i
 kT 

Every blue moon, they are equal and both equal to 107 = pH 7
Same is true for binary ionic solid; every blue moon [Vo] = [VM]

 Oxygen CANNOT leave with electrons (1 $)

1
O  O2g  VO  2e 
x
O


2
Does site ratio change if you lose oxygen??
 Non-stoichiometric Defect Reactions

By definition result in changes in chemistry

1
O  O2g  VO
x
O
x

2

V  V  e 
x
O O
 
V  V  e 
O O

1
OO  O2g  VO  2e 
Mass B?
x 
Charge B?
2 Site ratio?
 In high oxygen partial pressure
1
O2g  Oi
x

2

O  O
x
i i h

i  O
O i
 h
 1
O2g  O
i 2h


2

 Very Important Reaction

1
O  O 2 g  VO  2e
x
O

gred
2
2
[n] [V ]P  1/ 2  g 
O
x
O2
 exp

 kT
red
 K
 red
[O ] O  
Based on this equation, what happens at low PO2 to
defect concentration???
At the end of the day, does an oxygen vacancy act as a
donor or acceptor ????
 MISI
Placing any oxide in a low oxygen
partial pressure environment at
high temperatures results in the
loss of oxygen…
you get Swiss cheese…

Placing any oxide in a high oxygen partial

pressure environment at high temperatures
results in the gain of oxygen…
You can get Un-swiss cheese… aka Swiss
cheese on the cation sites!
 Redox Reactions
1
O2 g  OO  VFe  2h
x 

2

2Fe  2h  2Fe
2 3

1
O2g  2Fe  2Fe + OO  VFe
2 3 x

2
When you have transition metals
 then the non-stoichiometry can be
 accomodated by simply changing
the oxidation state of the TM.
Defect Equilibrium and Kroger-Vink Diagrams

xCc xDd  G 
 exp  K
eq

 kT 
a b
xA xB

• Assume mass action expression applies

to defects.

• Assume ideality.
• Solve defect reactions, simultaneously.
• Plot defect concentrations vs.
appropriate thermodynamic variables.
• For most cases, latter is PO2.
• Low PO2 x
O
1
O  V  2e  O2g

O
gred
2
[VO ][n]2 PO1/22 gred
x
 K red  exp
[O ]O kT
 
Intermediate PO2 M Ox
M
x
O

 VM VO gs
 [VM][VO ]  gS 
 K S  exp 
x
[MM ][OO ] x
 kT 

1
High PO2 O2g  OxO   2h + VM goxid
2
 [O x ] [V][ p]2 gred
O M
1/ 2
 K oxid  exp -
PO2 kT
 Unknowns?
n, p, VO, VM
How many equations: ??
Can you solve for unknowns?
 Eg 
n  p   K i  exp 
 kT 
Now can you solve for unknowns?
What information do you need?

Electro-neutrality and Brower Approximation

 positive charges  
m 3
 negative charges  
m 3

• Of utmost importance.

p  2V  2VM n
O

Note: In this expression, p, n, Vo and Vm are numbers/m3

• Brower’s idea was simple. In various


oxygen partial pressure regimes,
various defect pairs dominate.
 You tell me
• Low PO2
1
O  V  2e  O2g
x
O

O

p  2V  2VM n
O
2
• Intermediate PO2
 
M  O  VM V
x x
p  2V  2VM n
M
O O O

• High PO2
1
O2g  OO  2h + VM p  2VO  2VM n
x  
2

 Low PO2 regime revisited:

[VO ][n]2 PO1/22

 [VO ][n]2 PO1/22  K red
[O xO ]
n  2V  all other defects

O 
 ]? PO1/?
n  2VO  [2K red  [2K N N 2 1/? 1/?
] P
 2 red an c O2

Intermediate PO2 regime:


[VM][VO ]
x x
 [VM
][V 
O ] = KS
[M M ][O O ]

VO  VM  other defects So what is

PO2 dependence?
 [VM] = [VO ] = K S
  1
log n  log 2V proportional to - log PO2
O
6

n = 2VO VM = VO p = 2VM
Log Defect Concentrations


1
?? √Ks
1
?? √Ki

Low PO2 log PO2 High PO2

 Kroger-Vink Diagram For Ks>>Ki
n = 2VO VM = VO p = 2VM
Log Defect Concentrations

1
6 √Ks
1
4 √Ki

Low PO2 log PO2 High PO2

Kroger-Vink Diagram For Ki>>KS

n = 2VO n=p p = 2VM

Log Defect Concentrations

1 √Ki
6
1
2 √KS

Low PO2 log PO2 High PO2

IMPORTANT NEWS ON UNITS OF KI

• EQUILIBRIUM CONSTANTS ARE

EITHER DIMENSIONLESS
• OR THEY HAVE DIMENSIONS. THE
LATTER TELL YOU THE REST.
• e.g. KS = 1038 cm-6
• OR same Ks = 4x10-7 (dimensionless)
 Another important newsflash
• The crystal looks for a global minimum
in free energy. This is why at equilibrium
all reactions need to be satisfied
simultaneously.
Extrinsic Defect Reactions

In many cases properties are

determined by impurities.
This is especially true of
stoichiometric oxides!!
Bookkeeping Operation for Extrinsic Defects


CaCl 2  Ca Na  VNa
  x
2Cl Cl
2NaCl


CaCl 2  Ca Na  Cli  x
Cl Cl
NaCl
 Bookkeeping Operation for Extrinsic Defects

Procedure: i) Write down multiple formulas of host crystal

ii) Place dopant on host with cations on cation sites and anions
on anion sites.
iii) Repeat till you minimize number of defects.

Al2O3  2AlMg  VMg

  3Ox
O
3MgO


2MgO  2 MgAl  VO  x
2OO
Al 2 O3
Stoichiometric vs. Nonstoichiometric Compounds
 Measuring Nonstoichiometry

Remember; a non-stoichiometric oxide is an oxygen sponge..

 QuickTime™ and a
TIFF (Uncompressed) decompressor
are needed to see this picture.
 The ultimate question
Which defect forms when??
I was afraid somebody would ask that..
The answer is simple in principle:
It is the defect reaction that will result
in the lowest hd - i.e. the cheapest to form -
and the maximum entropy!
In other words the one with will give you
the lowest ∆G ……
TABLE 6.2 Defect formation and migratio n energies for vario us
halides
Crystal Defect hf orm, sf orm, H mig , Smig , in
type kJ/mol in units of R kJ/mol units of R
AgCl Frenkel 140 9.4 R  

28 VAg  
–1.0 VAg
 
1 – 10 Agi  
–3.0 Agi
AgBr Frenkel 110 6.6 R  

30 VAg
 
5 – 20 Agi
BaF2 Frenkel 190 40 – 70 V 
F

60 – 80 Fi
CaF2 Frenkel 270 5.5R  
40 – 70 VF  
1 – 2 VF
80 – 100 Fi 5 Fi
CsCl Schottky 180 10.0 R  
60  VCs
KCl Schottky 250 9.0 R 70  VK  2.4  VK 
LiBr Schottky 180  
40  VLi
LiCl Schottky 210  
40  VLi
LiF Schottky 230 9.6 R  
70  VLi  
1  VLi
LiI Schottky 110  
40  VLi
NaCl Schottky 240 10.0 R  
70  VNa 1 – 3  VNa
 
SrF 2 Frenkel 170 50 – 100  VF 
Source: J. Maier, Angewandte Chemie, 32: 313 –335 (1993).
 QuickTime™ and a
TIFF (Uncompressed) decompressor
are needed to see this picture.
 Line defects or dislocations

Not that
important
in ceramics.

Crucial to
creep
 Surfaces and Interfaces
Cgb Gseg
 exp
Cbulk kT
∆Gseg has 2 components:
Strain energy and electrostatic

r2  r1 r1

2

Cgb zie( int   bulk )
 exp -
Cbulk kT
 Animation of space charge formation

Sheet of Negative Charge

Something
attracts either
cations or anions
to the interface.

Creating a
space charge near that
interface.
 Summary and Conclusions
• Solids are not perfect and contain defects.
• The defects can be: stoichiometric, non-
stoichiometric or extrinsic. Electronic defects are
also very important.
• The Kroger-Vink notation and diagrams are useful
and important.
• There are rules for defect reactions that lead to
equilibrium equations that can in principle be used
to calculate the concentration of defects that in
turn lead to Ch. 7…..