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Journal of Crystal Growth 207 (1999) 273}277

Defect chemistry in CdTeSInT crystals


P. Fochuk!,*, O. Korovyanko!, I. Turkevych!, O. Panchuk!, P. Si!ert"
!Institute of Inorganic Chemistry, Chernivtsi University, 2 vul. Kotziubinskoho, 274012 Chernivtsi, Ukraine
"PHASE/CNRS, B.P. 20, 67037 Strasbourg Cedex 2, France
Received 3 March 1999; accepted 12 July 1999
Communicated by K.W. Benz

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.

PACS: 61.72.Vv; 72.15.Eb; 82.20.Wt

Keywords: CdTe; In; High-temperature electroconductivity; Defects; Models

1. Introduction tablished. It is this initial defect spectrum that is


responsible for processes which occur during crys-
Cadmium telluride is an important semiconduc- tal cooling: freezing of some QCDR in di!erent
tor used in the production of detector and optoelec- temperature ranges; electron redistribution; decay
tronic devices. Its electrical and optical properties of NPD and FPD solid solutions in the lattice and
are determined mostly by the point defect chem- association processes between certain point defect
istry of the crystal which is usually treated by the species. These latter processes were shown to be
theory of quasi-chemical defect reactions (QCDR) important in self-compensation phenomena and
[1]. Introducing native and/or foreign point defects in determining the properties, for example, of
(respectively NPD and FPD) gives crystals with CdTeSClT crystals [2]. It should be mentioned,
modi"ed properties [2}5]. Though usually the that at respective conditions such associates seem
room-temperature properties are of interest, the to exist even at high-temperature defect equilib-
initial NPD}FPD structure which governs them is rium HTDE [3,5].
formed at much higher (preparation) temperatures In order to establish a correlation between room
during crystal growth and/or annealing, when the temperature properties and cooling procedures,
high-temperature defect equilibrium is quickly es- knowledge of the HTDE spectrum is necessary.
This latter can be studied by means of high-temper-
ature electrical properties (HTEP) measurements.
* Corresponding author. In CdTeSInT these were performed predominantly

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

at "xed ¹ and Cd vapor pressures (P ) near either


C$
to the Cd saturation boundary (P ) [3}6] or
C$,.!9
that of the Te [7].
In this study HTEP versus ¹ data obtained in
CdTeSInT at di!erent deviations from stoichio-
metry (installed by the well-de"ned P values) are
C$
reported and discussed. Compensation phenomena
are analyzed with the aim of comparison experi-
mental data with calculated electron densities using
the proposed point defect structure in CdTe [6].

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).

whereas after a certain P value the In content


C$,#3*5 4
Together with the supplementary full elec- diminishes with increasing P . The P versus
C$ C$,#3*5
troneutrality condition: ¹ dependence is almost linear and can be expressed
by
[e~]#[V~ ]#2[V2~]#[A~ ]#[Te~]
C$ C$ I/2 *
log P "A!B/¹. (16)
"[h`]#2[Cd2`]#2[V2`]#[In` ]. (12) C$,#3*5
* T% C$
Supposing this expression is valid in the 600}
Here, the concentrations of the possible NPD as
973 K range also, [In ] calculations can be made
Te~, Cd` and V` are neglected as minor ones. For 4
* * T% taking into account that
numerical solving of the equation set (1)}(12) both

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

Function Constants Equation

C.!9 K.!9"1.6]1022 at/cm3; (18)


I/ 4
E.!9"0.54 eV
4
C.*/ K.*/"5.9]1021 at/cm3; (19)
I/ 4
E.*/"0.62 eV
4
P A"5.37; B"6692 (16)
C$,#3*5

Fig. 5. Defect concentrations versus reciprocal temperature in


CdTe with 2.2]1017 at/cm3 In (Sample In2) at P "0.001 atm
C$
(points are experimental results, lines are theoretical modeling).

In contents in the sample) and is practically equal


to the di!erence [In` ]![A~]. Raising the tem-
C$ I/
perature does not cause a supplementary In pre-
cipitates dissolution (these are absent contrary to
Sample In1) but causes both [V2~] increase and
C$
[A~ ] decrease, changing the compensation rela-
Fig. 4. Defect concentrations versus reciprocal temperature in I/2
tions. Here the V2~ NPD compensates mainly the
CdTe with 1]1019 at/cm3 In (Sample In1) at P "0.001 atm
C$
C$
In` FPD, causing thus an electron density de-
(points are experimental results, lines are theoretical modeling). C$
crease. At some higher temperatures the installed
P value becomes equal to that of the P (c.s.).
C$ C$
Summarizing, the [In ] values can be calculated Then a temperature increase causes P to rise
4 C$
as a function of ¹ and P . Using the quasi chem- along the P ¹-dependence (see Eq. (14)). This
C$ 505,.*/
ical defect reaction (QDCR) set [6] and the appro- drastically raises the Cd2` contents which partially
*
priate [In ] expression, numerical computations of compensates the negatively charged species and the
4
Eqs. (1)}(12) give the solutions for each NPD electron density becomes higher again.
(FPD), (see Figs. 4 and 5). It can be concluded that computer modeling of
In Fig. 5 lines of di!erent point defects and the the point defect spectrum in doped CdTe, and com-
measured [e~] values are shown. The agreement parison of the model with experimental data on
between the latter and the calculations is generally both dopant contents and free carrier density, fur-
satisfactory. Fig. 4 shows that the [e~] rise upon nish valuable information concerning the compen-
heating Sample In1 is due to an increase of In sation mechanism in CdTe.
solubility with temperature. At the same time the
V2~ content rises also, which results in an increase
C$
in the concentration of the A~ associate. This Acknowledgements
I/2
latter begins to compete with the electrons causing
a decrease in their density at a certain temperature. The research described in this article was made
In Sample In2 (Fig. 5) at lower temperatures the possible in part by a Grant `Copernicusa ER-
electron density is stable (de"ned by the moderate BIC15CT960808 from the European Commission.
P. Fochuk et al. / Journal of Crystal Growth 207 (1999) 273}277 277

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