MIT 3.

022
Microstructural Evolution in Materials

7: Ionic Defects

Juejun (JJ) Hu
hujuejun@mit.edu
 Gas Fuel
sensor cell

Defects are not

always bad

Solid state The Midas

battery touch
Charge neutrality
Macroscopic electroneutrality
Consider a sphere made of
sodium with radius R = 1 cm.
What is the energy needed to
remove 0.01% of valence
electrons from the sphere?
N Na 1.06 10 23
Q 0.01% e N Na 1.7 C
Site ratio conservation
The ratio of the number of
regular cation sites to the
number of regular anion sites
remains constant
MgO crystal
# Mg #O

C 4 0 R 1.1 pF

Q2
E 1.3 1012 Joule
2C
Ionic defect types

A. Schottky defect
A
(vacancy)

C B. Frenkel defect (self-

interstitial)
C. Substitutional atom
B
D. Foreign interstitial

D
Kroger-Vink notation
C
General form: M L
M atom type; V denotes vacancy
L site in the original perfect lattice; i denotes interstitial
C effective charge (or relative charge), equaling to the
difference in valence between the species on the site L and
the atom that occupies the site in a perfect crystal
Positive effective charge
Negative effective charge /
Neutral defect
/
Quasi-free electron is denoted by e ; hole is denoted by h
Square brackets denotes defect concentration, e.g. O

V
Examples of Kroger-Vink notation
Frenkel defect
Ag Ag Agi VAg/

Schottky defect
null VMg
//
VO null 2VAl/ // 3VO
Substitutional atom
2 MgO 2 Mg Al/ 2OO VO

Foreign interstitial # Al : #O 2 : 3
3MgO 3Mgi 3OO 2VAl/ / /
Concentration of Frenkel defects
Configurational entropy
N! N!
Assume that there is one
N n !n ! N n !n ! interstitial per lattice site

Dislodge n atoms Place the atoms

from their sites into n interstitials
N!
Sc 2k ln 2 Nkx f ln x f
N n !n !
Gibbs free energy G Nx f G f 2 NkTx f ln x f
Equilibrium concentration
G G f
0 x f exp
x f 2 kT
Equilibrium constant of defect reactions
Frenkel defect formation
G f
Ag Ag Ag V i
/
Ag x f Ag

i
V
/
Ag exp
2 kT
G f
K Ag V

i
/
Ag exp
kT
General defect reactions
G

null Ai M i K Mi
Ai
exp
i i kT
e.g. 3MgO 3Mgi 3OO 2VAl/ / /
3 2 G
G: Gibbs free energy of
K Mg V

i
///
Al exp defect formation minus the
kT configurational entropy term
Charge compensation in ionic solids
List all possible defect reactions when TiO2 is doped into
Al2O3 and determine the defect concentrations
1) List all charged species

Native vacancies: VO VAl/ / /

Foreign substitutional atom: TiAl

Interstitials: Ali Tii

2) List defect reactions based on charge compensation pairs

VO VAl/ / / null 2VAl/ / / 3VO Schottky defect

exp G1 kT
2 3
K1 V V
///
Al O

Charge compensation in ionic solids (contd)
2) List defect reactions based on charge compensation pairs
TiAl VAl/ / /
3TiO2 3TiAl VAl/ / / 6OO Foreign substitution

exp G2 kT
3
K 2 Ti V Al/ / /

Al

Ali VAl/ / /
Al Al Ali VAl/ / / Frenkel defect

K 3 Ali V Al/ / / exp G3 kT

Tii VAl/ / / 3TiO2 3Tii 4VAl/ / / 6OO Foreign interstitial

exp G4 kT
3 4
K 4 Ti V
i
///
Al
Charge compensation in ionic solids (contd)
3) Combine all equations along with the overall charge neutrality
condition to solve defect concentrations
exp G1 kT
2 3
K1 V V
///
Al O

exp G2 kT
3
K 2 TiAl

V Al/ / / 5 equations,
5 unknown
K 3 Ali V Al/ / / exp G3 kT variables: a
unique
exp G4 kT
3 4
K 4 Ti V
i
///
Al
solution set

2 VO Ti Al

3 Ali 4 Tii
3 VAl/ / /

Question: is mass conservation taken into account?

Charge compensation in non-stoichiometric solids
List all possible defect reactions in non-stoichiometric TiO2
and determine the defect concentrations
1) List all charged species
////
Native vacancies: VO VTi
/
Electrons and holes: e h
2) List defect reactions based on charge compensation pairs
null VTi/ / / / 2VO (1) null e / h (2)

2OO 4e / 2VO O2 (3) O2 VTi/ / / / 2OO 4h (4)

Not all reactions are independent: (4) = (1) + 4 (2) (3)

Charge compensation in non-stoichiometric solids
3) Combine all equations along with the overall charge neutrality
condition to solve defect concentrations
exp G1 kT
2
K1 VTi/ / / / V O

K 2 n p exp G2 kT
N C NV exp Eg kT Non-degenerate semiconductors

exp
G3 kT
2
K 3 n V
4
O

PO2

p 2 VO n 4 VTi / / / /

The defect concentration depends on oxygen partial pressure

Charge carrier concentration: examples
Schottky defect Frenkel defect Electron-hole pair
H (eV) H (eV) Eg (eV)
MgO 6.6 CaF2 2.8 Si 1.11
CaO 6.1 SrF2 2.3 Ge 0.67
LiF 2.34 BaF2 1.9 MgO 7.8
LiCl 2.12 AgCl 1.6 CaO 7.1
LiBr 1.8 AgBr 1.2 ZnO 3.2
LiI 1.3 -AgI 0.7 -TiO2 3.0

Gs N ~ 1023 cm3
ns Nxs N exp
2kT For MgO at 1,000K: ns ~ 3 10
6
cm3
Charge carrier concentration: examples
Schottky defect Frenkel defect Electron-hole pair
H (eV) H (eV) Eg (eV)
MgO 6.6 CaF2 2.8 Si 1.11
CaO 6.1 SrF2 2.3 Ge 0.67
LiF 2.34 BaF2 1.9 MgO 7.8
LiCl 2.12 AgCl 1.6 CaO 7.1
LiBr 1.8 AgBr 1.2 ZnO 3.2
LiI 1.3 -AgI 0.7 -TiO2 3.0

NC NV
12
Eg ~ 1019 cm3
n N C NV
12
exp
2kT For MgO at 1,000K: n ~ 0.4 cm ns
3
The Brouwer approximation
One charged defect of each sign dominates over all others
Example: charge compensation in undoped MgO
null VMg
//
VO null e / h 2OO 4e / 2VO O2

Regime 1: 2 VMg p
//
High oxygen partial pressure

Regime 2: n 2 VO

Low oxygen partial pressure

Regime 3: VMg
V O
//
Schottky compensation

Regime 4: n p Electronic compensation

Solve the charge carrier concentrations in each regime

at one specific temperature
The Brouwer approximation (contd)
Equilibrium constants
2
K1 VMg
//
V O K 2 n p K 3 V O

n 4 PO2

High oxygen partial pressure regime: 2 VMg

//
p

VMg
//
V O K1 VO 2 K1 p

n p K 2 n K 2 p

2
K 3 V
O

n PO2
4

1 2 2 1 2 1 1 1

V
O

2 K1 K 2 K 3 PO2
3 3 3 6 1 6
n 2 K1 K 2 K 3 PO21 6
3 3 3 6
The Brouwer approximation (contd)
Low oxygen partial pressure regime: n 2 VO
n 2 VO 16 16
K K
VO
3
PO21 6 n 2 3 PO21 6
K 3 VO
2
n 4 PO2 16 16

Schottky compensation regime (intermediate oxygen

partial pressure):
VMg
//

V O

VO

K1 1

K 3 4
V V
//
Mg O

K1 n
1 4
PO2
K1
2
K 3 V

n 4 PO2
O
 VO PO21 6 VO K1 VO PO21 6

n 2 VO n PO21 4 n PO21 6
VMg
//
VO K1 VMg
//
VO VMg
//
VO K1
log (defect concentration)

pn K 2 pn K 2 p 2 VMg
//

log PO2
Brouwer diagram for doped crystals
Example: Al-doped stoichiometric MgO
Neglect electronic carriers
The primary defect in intrinsic MgO is Schottky defect
Al-substitution of Mg dominates over interstitial formation
null VMg
//
VO (1)
Al2O3 2 AlMg VMg
//
3OO (2)
Charge compensation regimes (dependent on Al
concentration)
Regime 1 (intrinsic): V / /
Mg V O
Regime 2 (extrinsic):
2 VMg
//
Al Mg

 AlMg


log (defect concentration)

2 VMg
//
AlMg


VO VMg
//
K1

VMg
//
VO K1

Intrinsic Extrinsic

log AlMg


You can see ionic defects: F-centers
F-centers in NaCl crystal:
electron trapped at an
anion (halide) vacancy

Na Cl

Cl

e/ NaCl KCl KBr

http://education.mrsec.wisc.edu/background/F_center
Q & A about -ray irradiated table salt
Is it still edible?
Yes. First of all, I tried it. Tastes just like regular table salt.
Secondly, irradiated salt only contains a small fraction of
vacancy defects [in the order of 1017 cm-3 according to J. Appl.
Phys. 31, 1688 (1960)]. Since the crystal will ionize when
dissolved, these point defects dont make a difference.
Lastly, -radiation normally does not trigger nuclear reactions
[Nelson et al. Gamma-Ray Interactions with Matter], so we
dont need to worry about induced radioactivity.
Okay, it is fun but why should we care?
Table salt and doped salt are useful materials for radiation
dosimetry. See for example: Radiat. Meas. 46, 1856 (2011).
 Understanding defect reactions

Site ratio Charge Equilibrium

conservation neutrality constant

Kroger-Vink notation Frenkel & Schottky

concentrations

Doping & non-

stoichiometric defects Defect
concentration

Brouwer
approximation

Brouwer diagram