2.

Point Defects
R. Krause-Rehberg
2. Point Defects
2.1 Introduction
2.2 Classification
2.3 Notation
2.4 Examples
2.5 Peculiarities in Semiconductors
2.6 Determination of Structure and Concentration
2.7 Vacancies in thermodynamic Equilibrium
2.8 Irradiation-induced Point Defects
2.9 Aspects of Defect Chemistry
(F-center in NaCl)
2.1 Introduction
point defects: vacancies, interstitials, impurities, antisite
defects, and their complexes
many physical properties are governed by point defects:
Conductivity and conduction type
Color
Transparency
Diffusion
Mechanical properties
Formation of precipitation
without vacancies: with 0.001% vacancies
transparent opaque
1 defect in 100000 atoms!
Galliumphosphide
1 cm
2.2 Classification
Types of Point Defects:
Vacancies
Interstitials
wrong species at
regular lattice site
Schottky defect
Frenkel pair
self-interstitial
impurity at interstitial Position
antisite atom
impurity at regular lattice position
Another way of Classification
point defects
native
induced extrinsic
intrinsic
native: defects in crystal after growth (intrinsic and extrinsic defects)
induced: generated in crystal after growth (e.g. by irradiation and plastic
deformation, or diffusion, precipitation growth)
intrinsic: self-defects of crystal without impurities (e.g. V
Ga
, Ga
As
, As
i
in
GaAs)
ext rinsic: defects including impurities (e.g. B
-
acceptor and V-O defect in Si;
Si
Ga
-V
Ga
in GaAs)
however, this notation is not used uniformly in literature
Still another Classification
Point Defects
Equilibrium Defects Excess Defects
thermal
vacancies
structural
defects
electronically
induced
i r radiation plastic
deformation
vacancies
in metals close
to melting point
As
Ga
in LT-GaAs
Hg vacancies
in CdHgTe
Si
Ga
-V
Ga
in
n-doped GaAs
electron irradiation
ion implantation
cold-rolled metals
high-T deformed Si
lubrication
Vacancies
vacancy of Schottky type Frenkel pair
(here: close Frenkel pair)
note: relaxation of lattice at vacancy
vacancies: - dominating defect at high temperature
- most important (primary) irradiation defect
- generated during plastic deformation (but often not stable)
in compounds and intermetallic phases: two different types of vacancies with
different properties
Vacancies
defect reactions lead to defect complexes:
formation of divacancies and vacancy clusters
V
Al
-Mg
Al
in Al-Mg-alloys
Te
As
-V
Ga
in GaAs:Te
V-O
i
in Cz-Si (so-called A center)
Interstitials
a) and b) interstitial in octahedral and tetrahedral position in a bcc crystal
(bcc. body centered cubic)
c) interstitial as dumbbell (deutsch: Hantel)
interstitial atoms are often small (e.g. B, C, N, O in metals)
often built-in in octahedral position (C in Fe): lattice distortion leads to
increased hardness
H is always built-in as interstitial
Interstitials
important defect in silicon: O
i
[O] is about 10
18
cm
-3
in Cz-Si
O
i
has six equivalent positions
during annealing: formation of O-
precipitates; important for gettering of
impurities
self-interstitials often in dumbbell
conIiguration, i.e. a 'molecule oI two
identical atoms shares a regular lattice
site
Oxygen forms varies defect complexes in Si
with Si interstitials and Si vacancies
proposed structure of the I-O
2
complex in Si
Impurities
important defect in semiconductors (but also in metals, remember C in Fe)
intentionally used as dopants for the generation of carriers in high-resistive material
(Si, GaAs)
important acceptors: B in Si Zn or C in GaAs
important donors: P and As in Si Te, Si in GaAs
effect of a donor dopant
dopant levels in bandgap of Si
Antisite Defects
prerequisite: ordered structure
in compound semiconductors and
intermetallic compounds
antisite defects compensate partly
deviations from stoichiometry
superlattice in system Au-Cu
a) (100)-plane in ordered Cu
3
Au
b) same plane at T > 390C
in existence region: deviation compensated
by point defects; outside: formation of
different phases, starting with small
precipitations
maximum deviation in compound
semiconductors very small at room
temperature
in LT-GaAs (grown at 200C): up to 1% of
point defects (mainly As
Ga
) extremely high
concentration
0.50000 0.50004 0.50008 0.50012
900
1000
1100
1200
1300
T
F
Melt
GaAs
s
GaAs
s
+ Ga(As)
l
GaAs
s
+ As(Ga)
l
solidus line
liquidus line
p
EAs
= 0.1 1 3 6 9 12 18 bar
T

/

o
C
x
As
2.3 Notation of Point Defects
twofold negatively charged As vacancy
2
As
V
0
Ga
As
i
Si

Si
B
neutral As antisite defect
Si atom at interstitial position
negatively charged boron atom at Si position
2
As
V
species
charge
position
often used in defect chemistry: .U|JHUVQRWDWLRQ
A

A' A'' acceptor neutral, negative, twofold negative

donor neutral, positive, twofold positive

D D D

e' electron in conduction band

'deIect electron or hole in valence band

h
2.4 Examples: Color Centers
alkali halogenides (NaCl, KCl, .) are clear and transparent
coloring is obtained by point defects: color centers
possible defects: chemical impurities, excess metallic ions (e.g. Na
+
in NaCl)
so-called F-bands: optical
absorption as function of wave
length; a part of optical
spectrum is cut, so the crystal
appears colored
the simple anion vacancy with a bound electron is the
F-center (absorption in UV region)
absorption: electric dipole transition to a bound exited
state of the defect
missing anion acts as positive charge and binds a
valence electron (which was delocalized before)
other Color Centers
the F
A
-center in KCl; one of six K
+
ions is replaced by another alkali ion
(here Na
+
)
the M-center consists of two F-centers
the R-center consists of three F-centers
which are in an [111] plane of the NaCl
structure
EL2 in GaAs: important antisite defect
probably the most frequently studied point defect in semiconductors: EL2 in GaAs
EL2 = electrical active defect II (as found in DLTS measurements)
used to obtain semi-insulating GaAs (auto-compensation of unwanted impurities)
self-compensation works only when [EL2] > [shallow acceptors] > [shallow donors]
step 3 needs too high temperature, thus all carriers are compensated at 'normal temperatures
condition can be fulfilled in pure semi-insulating GaAs by 'doping with C
EL2 in GaAs: important Antisite Defect
interesting feature: EL2 exhibits metastability
illumination at low temperature properties changes (e.g. no IR absorption any more)
many structural models were discussed
Dabrowski/Scheffler and Chadi/Chang: EL2 is isolated As
Ga
and in metastable state the
antisite atom moves outward and leaves a V
Ga
Metastability is lost during warming-up to 115 K
EL2 in GaAs: important Antisite Defect
positron annihilation is a method to detect
vacancy-type defects in solids
before annihilation, diffusing positrons can be
trapped by such defects
as a consequence: positron lifetime increases due
to the reduced electron density in the vacancy
experiment shows the existence of a Ga vacancy
in the metastable state of GaAs, which does not
exist in stable ground state
was prove of As
Ga
model of EL2
R. Krause, K. Saarinen, P. Hautojrvi, A. Polity, G. Grtner, and C. Corbel
Observation of a monovacancy in the metastable state of the E L2 defect
in GaAs by positron annihilation
Phys. Rev. Lett. 65 (26), 3329-32 (1990).
DX Center in GaAlSb
defect appears in doped quasi-ternary III-V compound
semiconductors (e.g. Al
x
Ga
1-x
As, Al
x
Ga
1-x
Sb)
is complex: donor-? (so-called DX center)
also shows metastable state at low temperatures
model of Dabrowski/Scheffler predicted vacancy in
stable state and the disappearance of this vacancy in
metastable state
also proved by positron annihilation
Ga Ga Al Al
Te
Te
Sb Sb
metastable stable

I
l
l
u
m
i
n
a
t
i
o
n
I
l
l
u
m
i
n
a
t
i
o
n
10
2
10
3
10
4
10
5
P
h
o
t
o
c
o
n
d
u
c
t
i
v
i
t
y

[
S
]
279
278
277
276
275
274
A
v
e
r
a
g
e

p
o
s
i
t
r
o
n

l
i
f
e
t
i
m
e

[
p
s
]
20 40 60 80 100 120
Annealing temperature [K]
GaAlSb: Te
R. Krause-Rehberg et al., Phys. Rev. B 48 (1993) 11723
Compensating Defects in GaAs:Te
Te is typical donor in GaAs
is built-in only as Te
As
experimental finding: with increasing
donor doping concentration
acceptor density simultaneously
increases
'selI-compensation
degree of compensation about 25%
confirmed model:
donor acceptor
Te
As
+
V
Ga
Te
As
-
driving force for generation of defect
clusters: so-called 'Fermi-level eIIect
it is energetically favorable to form
additional acceptors in n-type GaAs
result of Hall-effect measurements
Compensating Defects in GaAs:Si
Si is also often used as donor in GaAs
Si is built-in as Si
Ga
+
and also as Si
As
-
(amphoteric behavior)
thus: situation is different from GaAs:Te
degree of compensation not constant, but
growing
result: doping only possible up to 10
19
cm
-3
at higher Si content: almost complete auto-
compensation
model for additional compensating center
(acceptor): V
Ga
Si
Ga
-
result of positron annihilation spectroscopy (by K. Saarinen et. al, Helsinki UT)
Compensating Defects in GaAs:Si
model was proven by correlated STM and positron experiments
STM shows at cleavage planes of GaAs:Si the V
Ga
Si
Ga
-
defect (but possibly formed
during cleavage)
positron annihilation found the same number of vacancies in the volume of the identical
crystals
conclusion: both methods detect the identical defects
J. Gebauer et al.
Phys. Rev. Lett. 78 (1997) 3334
22
1 2 3 4 5 6 7 8 9
0.0
0.1
0.2
1 2 3 4 5 6 7 8 9
lattice spacing in [110] direction
H
e
i
g
h
t

[
n
m
]
-2.0 V +1.4 V
occupied empty states
Scanning tunneling microscopy at GaAs (110)-
cleavages planes (by Ph. Ebert, Jlich)
Defect complex identified as V
Ga
-Si
Ga
10
18
10
19
10
17
10
18
10
19
Si concentration (cm
-3
)
Positrons - c
vac

STM - [Si
Ga
-V
Ga
]
D
e
f
e
c
t

c
o
n
c
e
n
t
r
a
t
i
o
n

(
c
m
-
3
)
Quantification Agreement
Mono-vacancies in GaAs:Si are V
Ga
- Si
Ga
-complexes
Identification of V
Ga
-Si
Ga
-Complexes in GaAs:Si
Gebauer et al., Phys. Rev. Lett. 78 (1997) 3334
two-zone-furnace: Control of
sample temperature and As
partial pressure in quartz tube
T
As
: determines As-partial
pressure
navigate freely in phase diagram
(existence area of compound)
T
sample
: 1100 C
GaAs: annealing under defined As-partial pressure
Jurisch, Wenzl; 2002
0.50000 0.50004 0.50008 0.50012
900
1000
1100
1200
1300
T
F
Melt
GaAs
s
GaAs
s
+ Ga(As)
l
GaAs
s
+ As(Ga)
l
solidus line
liquidus line
p
EAs
= 0.1 1 3 6 9 12 18 bar
T

/

o
C
x
As
Equilibrium Phase Diagram of GaAs
0,01 0,1 1 10
10
17
GaAs:Si

Linear fit
V
a
c
a
n
c
y

c
o
n
c
e
n
t
r
a
t
i
o
n

(
c
m
-
3
)

Arsenic pressure (bar)
0,1 1 10
10
16
10
17
10
18
[Te] in cm
-3
9x10
16
4x10
17

6x10
18
2x10
18
231
GaAs:Te
250
235
240
245
t
a
v


a
t


5
5
0

K

(
p
s
)

V
a
c
a
n
c
y

c
o
n
c
e
n
t
r
a
t
i
o
n

(
c
m
-
3
)
Arsenic pressure (bar)
Si
Ga
-V
Ga
Te
As
-V
Ga
Fit: [V
Ga
-Dopant] ~ p
As
n
n = 1/4
Thermodynamic reaction:
1/4 As
4
gas
As
As
+ V
Ga
Mass action law:
[V
Ga
] = K
VG
p
As
1/4
J. Gebauer et al.,
Physica B 273-274, 705 (1999)
GaAs: Annealing under defined As pressure
Thermodynamic reaction:
As
As
V
As
+ 1/4As
4
gas
Mass action law:
[V
As
] = K
VAs
p
As
-1/4
Fit: [V-complex] ~ p
As
n
n = -1/4
undoped GaAs: As vacancy
Comparison of doped and undoped GaAs
Bondarenko et al., 2003
2.5 Peculiarities in Semiconductors
defects in semiconductors can be
charged (e.g.: +, 0, -)
charge depends on position of
Fermi level
electronic configuration and
structure of a defect depend on
charge state
a different charge leads to
different lattice distortions
is so-called 'Jahn-Teller Effect
thus: distortion energy depends
on charge state
influence may be so strong that
normal charge sequence (2-, -, 0,
, 2) is changed: 'negative-U
behavior
electron configuration of V
0
in Si
negative-U behavior
example: theoretical calculations of
ionization levels
a) to c) are calculated without lattice
relaxation
calculations g) to h): lattice distortion
was taken into account
Jahn-Teller Effect is frequently found
in semiconductors
Defects in I nP
Ga
As
in GaAs
relaxed unrelaxed
relaxed
2.6 Determination of structure and concentration
range of concentration: about 10
10
cm
-3
(metallic impurities in Si)
> 10
20
cm
-3
(some dopants in Si, As
Ga
in LT-GaAs)
defect identification difficult due to large variety of species
in GaAs: 6 intrinsic defects in many charge states; they form defect complexes; in
addition: they can form complexes with impurities
there is no universal method many methods give information about ionization levels in
band gap, but no structural information (e.g. DLTS, Hall, IR absorption)
other methods have structural information, but can only be applied to a restricted number
of defects or materials (e.g. EPR, Positron Annihilation)
topic of lectures in next course!
2.7 Vacancies in thermodynamic equilibrium
V V V
S T W N F A = A
! )! (
!
!
) 1 ( ) 1 (
V V V
V
N N N
N
N
N N N N
G

=
+
=
! )! (
!
ln ln
V V
B B V
N N N
N
k G k S

= = A
statistical considerations
change of free enthalpy during formation of N
V
Schottky-type vacancies (N .. number of
atoms; W
V
. vacancy Iormation energy)
(positive energy term can be compensated by gain of entropy!)
AS
V
is entropy gain; is calculated in the following (from statistics: S = k
B
ln G):
probability G to form N
V
vacancies in N atoms is equal to probability to
choose N
V
atoms out of N atoms (numerator):
The factor N
V
! (speak: factorial) in the denominator excludes those cases which differ only
by the different order of pick-out of atoms.
using the Boltzmann-Equation and the Sti rling approximation:
x x x x ~ ln ! ln
! )! (
!
ln ln
V V
B B V
N N N
N
k G k S

= = A
x x x x ~ ln ! ln
T k
W
N N
N
B
V
V
V
=

ln
] ln ) ln( ) ( ln [
V V V V B V
N N N N N N N N k S = A
0 ln =

=
|
|
.
|

\
|
c
A c
V
V
B V
T
V
N
N N
T k W
N
F
it follows:
in thermal equilibrium: AF is extreme value (minimum)
in the lattice: N
V
<< N (in real crystal even at melting point: N/N
V
> 10
3
)
|
|
.
|

\
|
=
T k
W
N N
B
V
V
exp
thus: vacancies must exist in an ideal crystal at T>0 !
[1]
V V V
S T W N F A = A
!
example: T=1000K and W
V
= 1 eV N
V
/N 10
-5
T=1000K and W
V
= 3 eV N
V
/N 10
-15
not detectable
real example: vacancies in Au: W
V
= 0.98 eV, but in Si: W
V
> 3.6 eV
vacancy concentration is slightly larger compared to Eq. [1]
further factors to be taken into account:
- interaction of vacancies
- influence of point defects to AS
- volume work for dilatation of lattice
- electronic effects
defect density often much larger: crystal far from being in thermal equilibrium
excess vacancies due to e.g. i r radiation by fast particles
also: vacancies can be quenched-in by very fast quenching
quenching rate must be about 10
4
Ks
-1
, then a large fraction of thermal vacancies remain
during slow warming-up: vacancies become mobile (migration energy required <
formation energy)
experimental results
positron annihilation detects vacancies in
thermal equilibrium
increase of peak height H/H
0
of angular
correlation is due to increasing number of
vacancies
slope of Ar rhenius plot gives vacancy
formation enthalpy H
1V-F
only possible in metals
in semiconductors: H
1V-F
is too large, so
number of thermal vacancies is too small to
be detected by this technique
V
B
V
N 1
L
N T
W
og
k
=
|
|
.
|

\
|
=
T k
W
N N
B
V
V
exp
Multiple vacancies in thermal equilibrium
There is a small probability to form
divacancies and even triple vacancies in
thermal equilibrium close to T
M
Number of interstitials in thermal
equilibrium is rather small
Figure shows quenching experiment in Au
Fast cooling 800C to RT in - 25 ms
Calculated concentration of mono-vacancies
(C
L
), di- (C
D
) and triple-vacancies (C
T
) are
shown during fast cooling
C = C
L
+ 2C
D
+ 3C
T
is total number of
vacancies
Relative fraction of multiple vacancies
increases during quenching
dashed lines: no dislocations as sink for
migrating vacancies
2.8 Irradiation-induced point defects
2.8.1 Generation of defects
generation often done by electron i r radiation
displacement energy in metals and
semiconductors is about 10 . 30 eV
electron threshold energy about 500 keV
reason: only a small fraction of electron energy
can be transferred to atom (collision law)
maximum transfer during central collision:
incident
2
2 1
2 1
) (
4
E
m m
m m
T
m

+
=
T
m
. Wigner Energy
example: m
1
= m
e
= 9.110
-31
kg; m
2
= m
Cu
= 1.0610
-25
kg
T
m
= 4m
e
/m
Cu
E
incident
= 8.6 10
-6
E
incident
(relativistic corrections are still required)
using electrons up to several MeV, mostly Frenkel pairs are generated
computer-simulated impact of an electron (1 MeV)
in Cu (T
m
~ 40 eV); generated vacancy is only
stable when outside of spontaneous recombination
volume
[2]
Dynamic simulation of
atomic movements
after electron impact
with 40 eV energy
transfer at the atom A
Energy just enough for
generation of a single
Frenkel pair A-D
Energy comparable to
1-MeV electron
irradiation in Cu or Au
Figure shows snapshot
after short time after
impact
2.8.1 Generation of defects
Ion implantation is most important doping method in semiconductor technology
mass m
1
and m
2
in Eq. 2 are comparable (situation like billiard balls)
however: penetration depth for ions of 100 keV is about 1 m (1 MeV electrons > 0.5mm)
ions produce extended defect cascades; energy large enough for 10
4
displacement events
however: only a few defects survive (stationary state reached after 1 ps)
also larger point defect clusters are generated
computer-simulated defect cascade in {100} plane of Cu. T=250 eV, t
a
= 0.06 ps, t
b
= 0.35 ps, t
c
= 1.5 ps
stationary result after 1.5 ps: 5 vacancies and 5 interstitials
ion implantation
important dopant species in Si are As and B
in order to obtain homogenous doping depth profiles: multiple implantation steps with
different energy
depth distribution of implanted B
(As) atoms in silicon
depth distribution of displaced
atoms in B-implanted Si
when implantation dose large enough: lattice becomes amorphous
amorphisation dose is function of ion mass, target species, and temperature
Simulation with Iree code 'SRIM (www.srim.org) 'The Stopping and Range oI Ions in
Matter
projected range R
p
Example of SRIM simulation
temperature dependence of amorphisation
dose for different ions in Si
Doping by ion-implantation
has many advantages . but
defects must be annealed
temperature dependence of
amorphisation dose is strong
at elevated temperature:
defects anneal during
irradiation
at room temperature: boron
implantation will not lead to
amorphisation at all
in technology: defects must be
annealed
often: rapid thermal annealing
(RTA)
in Si: 30s at 950C
done by light illumination by
strong halogen lamps (few
kW)
Rutherford Backscattering
classical method to investigate ion implantation defects:
Rutherford Backscattering
probe atoms (H, He) penetrate into the sample into low-
index directions (channels)
defects which are present scatter the probe atoms and raise
the backscattered intensity
defect depth profiles can be determined
41
FLA = Flash Lamp Annealing
short light pulses of Xe flash lamps may melt surface of Si
heating period some ms
RTA-Annealing (Rapid thermal annealing) of semiconductors after ion
implantation
Problem: measurement of temperature
42
Pre-heating of sample by halogen lamps and then:
light pulse by flash lamps
Pulse-forming network (PFN).
Ground switch
Xenon flash-lamps
Pulse-forming network (PFN).
Ground switch
Xenon flash-lamps
Temperature up to 2000C electrical power: 12 MW (for 20ms)
Pre-heating necessary
temperature gradient: 510
5
K/s
2.8.2 Annealing of excess point defects
irradiation defects far from thermal equilibrium but still stable (frozen-in)
increasing temperature: defects start migration
energy migration ... exp
0 m
B
m
E
T k
E
N N
|
|
.
|

\
|
=
e
l
e
c
t
r
i
c
a
l

r
e
s
i
s
t
a
n
c
e
annealing of irradiation defects in Cu
electrical residual resistance at low temperature: sensitive for defects (electrons are
scattered during movement in electric field)
Annealing of excess point defects
annealing starts at very low temperatures (in metals: interstitials have smallest migration energy)
many annealing stages; during annealing: defect reaction (e.g. formation of vacancy clusters)
often: several mechanisms lead to
disappearance of same defect: vacancies
vanish due to migration of interstitials and
vacancies itself
several stages (A-E) for interstitials: close
Frenkel pairs (A-C) and separated interstitials
(D+E)
curve b: electron irradiation
curve k: plastic deformation
curve a: quenched sample
stage I + II: interstitial annealing
stage III: vacancy annealing
isochronal annealing curve of Cu after 3-
MeV-electron irradiation (T
irr
=4.5 K)
Annealing of excess point defects
example: defects after electron irradiation in
Ge (E
e-
=2 MeV, T
irr
=4K)
distinct annealing stage at 200K
sample with highest dose: formation of
divacancies during annealing (they anneal at
about 400K)
formation of divacancies prove: it is no
movement of interstitials but vacancies
this is further supported by the fact that the
vacancies disappear completely in this stage;
interstitial stage always incomplete
(Polity et al., 1997)
Positron study of defect annealing after 4K-
electron irradiation of Cz-Si
Monovacancies disappear around room
temperature and divacancies are formed
Annealing is more complex: several stages
in intensity
Cz-Si contains about 10
18
cm
-3
oxygen
Oxygen-vacancy complexes are formed
which can be transferred into more
complex defects during course of annealing
Defect reactions occur
(Polity et al., 1998)
Defect annealing in electron irradiated Si
2.8.3 Defect reactions
defect reactions during annealing sequence is a normal
effect
defect complexes could be rather complicated
typical example: defect annealing in Cz-Si after low-
temperature electron irradiation
Cz-Si contains about 10
18
cm
-3
oxygen
many different oxygen-vacancy complexes are formed
most simple defect is the
so-called A-center (VO)
during annealing:
sequence of different
V
x
O
y
complexes are
formed
defects stable up to
800C, although an
isolated monovacancy
anneals at about 200K
oxygen stabilizes the
defects
V-O complex (A-center)
2.9 Aspects of defect chemistry
chemical or defect reaction

+
=
+ +
i
D C B A
D C B A

: index reaction
moles of QXPEHU
D C

prior to reaction: = 0 ; complete reaction = 1

in thermodynamic equilibrium: 0 < < 1
equilibrium condition:
T,p
G
0 minimum of free entalphy G

c
=
c
reaction runs spontaneously only when:
0

,
<
c
c
p T
G
The mass action law
D C B A +

+ chemical or defect reaction

k
1
k
2
k
i
... reaction velocity coefficients
c
i
... concentrations
B A
B A
c c k
dt
dc
dt
dc
= =
1 D C
D C
c c k
dt
dc
dt
dc
= =
2
and for return reaction:
in case of thermodynamic equilibrium: velocity in both directions identical
dt
dc
dt
dc
C A
=
and thus:
m equilibriu in ion concentrat ...
2
1
i
B A
D C
c k
k
k
c c
c c
= =

equation is called mass action law

not only for chemical reactions: intrinsic conductivity in semiconductors
k
N
p n
p n =

: law action mass 0

N ... number of all electrons
and thus:
' k p n =
Example: Defect chemistry in HgCdTe
HgCdTe is used as infrared detector; dominating defect is V
Hg
2-
(twofold ionized acceptor)
vacancies are in equilibrium with vapor p
Hg
over crystal
Hg Hg
Hg gas Hg h V
h e
+ +
+
+
+
) ( 2
0
2
electrical conductivity is sum of intrinsic
conduction and ionization of V
Hg
acceptors
n . number oI Iree electrons
h. number oI Iree holes
mass action laws:
(1)
] [
v
2 2
k p h V
k h n
Hg Hg
i
=
=

(2) 0 ] [ 2
2
= +

Hg
V h n
neutrality condition: intrinsic part
extrinsic part
(3) ] [ 2
2
h V
Hg
=

ratures) high tempe (at h n =

technical use at T < 100K (no intrinsic conduction); combination of (1) to (3) gives:
(4) 0
2
2
2
v
77
2
77
v
2
3
77
= +

Hg
K i K
Hg i
K
p
k
h k h
k
p k
h
Defect chemistry in HgCdTe
is equation which defines
correlation between Hg partial
pressure and concentration of
Hg vacancies in crystal
(because h
77K
= 2 [V
Hg
])
constants k
i
and k
v
were
determined by electrical
measurements (Hall effect)
lines in figure: result of
simulation by eq. (4);
measured points: experimental
data of Hg vacancy
concentration obtained by
positron annihilation
(4) 0
2
2
2
v
77
2
77
v
2
3
77
= +

Hg
K i K
Hg i
K
p
k
h k h
k
p k
h
Defect chemistry
treatment of quasi-ternary compounds
becomes rather difficult
very large number of intrinsic defects
but in special regions: only a few
defects dominate
calculation of the dominating defects
requires the knowledge of
thermodynamic constants which are
usually only roughly known
diagram only valid for a constant
temperature
CuI nSe
2
References
1. Ch. Weimantel, C. Hamann: ,Grundlagen der
Festkrperphysik
2. Bergmann, SchIer: ,Lehrbuch der
Experimentalphysik'; Bd. 6: ,Festkrper'
3. J. Bourgoin, M. Lanoo: ,Point DeIects in
Semiconductors'; Springer-Verlag, Teil II
4. M. Arnold: 'Physikalische Chemie der Halbleiter';
Akademie-Verlag Berlin 1978
5. F. Vollertsen, S. Vogel; ,WerkstoIIeigenschaIten und
Mikrostruktur'; Hanser Studienbcher, Mnchen
1989
6. R.M. Barrer: ,DiIIusion in and through Solids';
Cambridge Univ. Press, 1951
7. R. Krause-Rehberg, H.S. Leipner: ,Positron
Annihilation in Semiconductors', Springer-Verlag,
Berlin 1999