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Abstract
High-temperature electrical measurements are explained in the framework of the theory of quasi-chemical reactions
between defects in solids using solubility data for In in CdTe. The free carrier density is dependent on the solubility of
dopant and the electrons are compensated by both native point defects (Cd vacancies) and the In-containing associate.
Calculated point defect diagrams give electron densities in good agreement with the measured values. ( 1999 Elsevier
Science B.V. All rights reserved.
0022-0248/99/$ - see front matter ( 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 2 4 8 ( 9 9 ) 0 0 3 7 8 - 4
274 P. Fochuk et al. / Journal of Crystal Growth 207 (1999) 273}277
2. Experimental procedure
Fig. 1. Electron concentration versus reciprocal temperature in
CdTe single crystals were grown by the Bridg- Sample In2 with C505"1]1017 at cm~3 (points are experi-
man method using materials and procedures de- I/
mental results, lines are theoretical modeling).
scribed in Ref. [8]. Sample In1 was doped by
introducing In through the vapor phase (1073 K,
24 h, P ), the In contents being 1]1019 at/cm3 these dependencies on the basis of the full elec-
C$,.!9
of In as determined by AAS analysis. Sample In2 troneutrality condition, it is necessary to write the
was cut from an In-doped CdTe Bridgman ingot expressions for the concentration of each NPD and
and contained 2.2]1017 at/cm3 of In. The HTEP FPD as a function of [e~], P and [In ], where
C$ 4
conductivity and Hall e!ect measurements are de- [In ] is the total amount of In dissolved in the
4
scribed in Ref. [9]. The temperature range investi- crystal. Using the QCDR set [6] one obtains thus
gated was 500}1200 K and the P value was for the NPDs:
C$
0.001}1 atm. Computed point defect concentra-
[h`]"K [e~]~1, (1)
tions were obtained using iteration procedures and 1
a set of thermodynamic constants [6] improved [V~ ]"K [e~]P~1, (2)
compared to Ref. [3]. The missing In solubilities in C$ 11 C$
CdTe were constructed from existing data (see text). [V2~]"K [e~]2P~1, (3)
C$ 10 C$
[Cd2`]"K [e~]~2P , (4)
* 6 C$
3. Results and discussion [Te~]"K [e~]P~1, (5)
* 12 C$
Quite di!erent electron concentrations ([e~]) [V2`]"K P [e~]~2. (6)
T% 8 C$
versus reciprocal temperature were obtained for
Samples In1 and In2. At low temperatures in the In conformity with [3,5,6] the existence of a
(In` V2~)~,A~ associate is assumed. For calcu-
moderate doped crystal In2, the [e~] is controlled C$ C$ I/2
by the In content, then passes through a minimum lation of the FPD contents, the following material
and rises in the high-temperature range. In the balance equations are needed:
heavily doped Sample In2, a generally opposing [In` ]#[A~ ]"[In ], (7)
dependence was observed (Figs. 1 and 2). C$ I/2 4
In Fig. 2 it can be observed that the maximal [A~ ]"K [In` ] [V2~]. (8)
I/2 I/2 C$ C$
[e~] values systematically shift towards higher
[In` ]#K [In` ] [V2~]"[In ], (9)
temperatures with increasing P . At low and mod-
C$ C$ I/2 C$ C$ 4
erate temperatures the isobaric dependencies cor- [In` ]"[In ]/(1#K [V2~]), (10)
respond to a 0.4 eV slope in accordance with earlier C$ 4 I/2 C$
published data [6]. For the purpose of modeling [A~ ]"K [V2~][In ]/(1#K [V2~]). (11)
I/2 I/2 C$ 4 I/2 C$
P. Fochuk et al. / Journal of Crystal Growth 207 (1999) 273}277 275
Fig. 2. Electron concentration versus reciprocal temperature in Fig. 3. In solubility isotherms versus P (points are experi-
C$
Sample In1 with C505"1]1019 at/cm3 (points are experimental mental results, lines are theoretical modeling).
I/
results, lines are theoretical modeling).
G H
the [In ]"f (P , ¹) dependencies and the solid C40- (C505*C40-)
4 C$ [In ]" I/ I/ I/ . (17)
CdTe sublimation constant are needed: 4 C505 (C505(C40-)
I/ I/ I/
CdTe(s)%Cd(v)#1/2Te (v)
2 In Eq. (17) C40- is the In solubility in CdTe at
I/
and given ¹ and P , and C505 is the total In amount
C$ I/
in the crystal (including any precipitates). Data in
K47 "P (P 2)1@2. (13)
C$T% C$ T% Fig. 3 shows that along each isotherm at
At congruent sublimation (c.s.) the relation P " P (P the value of In solubility is maximal
C$ C$ C$,#3*5
2P 2 ensures the minimal total pressure P in (C.!9), whereas at P "P it is minimal, de-
T% 505,.*/ I/ C$ C$,.!9
the system and then pending on the temperature only. Then these values
can be expressed by
P (c.s.)"21@3(K47 )2@3. (14)
C$ C$T% C.!9"K.!9 exp(!E.!9/k¹) (P ), (18)
Here in accordance with Ref. [10] I/ 4 4 C$,#3*5
C.*/"K.*/ exp(!E.*//k¹) (P ). (19)
K47 "8.27]1010 exp(!3.01 eV/kT) (atm)3@2. I/ 4 4 C$,.!9
C$T% The mathematical analysis of the data in Fig. 3
(15)
gives the values of constants in Eqs. (18) and (19)
The In solubility data were taken from results shown in Table 1. It remains to calculate the [In ]
4
obtained earlier [11,12]. These are shown as iso- value in the P 'P 'P range. The ne-
C$,.!9 C$ C$,#3*5
thermal P dependencies in Fig. 3. It can be seen cessary dependencies can be obtained using the In
C$
that at low P the [In ] value is P independent, solubility versus P slopes.
C$ 4 C$ C$
276 P. Fochuk et al. / Journal of Crystal Growth 207 (1999) 273}277
Table 1
Thermodynamic data for In solubility in CdTe