Inorganic Materials, Vol. 36, No. 7, 2000, pp. 641-652. Translated frora Neorganicheskie MateriaO; VoL 36, No.

7, 2000, pp. 775-78Z

Original Russian Text Copyright 9 2000 by Glazov, Pashinkin, Fedorov.

Phase Equilibria in the Cu-Se System

V. M. Glazov*, A. S. Pashinkin*, and V. A. Fedorov**
* Moscow State Institute of Electronic Engineering (Technical University),
Zelenograd, Moscow, 103498 Russia
** Kurnakov Institute of General and Inorganic Chemistt% Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 117907 Russia
ReceivedApril28, 1999;in finalform,September3, 1999

Abstract--The available phase-diagram data for the Cu-Se system are critically evaluated, and the T-x and
p-T phase diagrams are optimized. The thermodynamic properties and polymorphism of copper selenides are
analyzed.

INTRODUCTION somewhat lower accuracy. The results reported in [3,

In this paper, we present a critical evaluation of
available T-x and p - T phase-diagram data for the
Cu-Se system and summarize the thermodynamic and
structural properties of the intermediate phases in this
system. Earlier, the phase equilibria in the Cu-Se sys-
tem were summarized by Chakrabarti and Laughlin in
1981 [ 1]. However, new data have since been published
which are of key importance for the characterization of
the Cu-Se system and intermediate phases and are
given a great deal of attention in this review. The Cu-Se
system is interesting in that copper(I) selenide, Cu2Se,
retains its semiconducting properties in the molten state
[2]. Practical application of this compound, however,
still depends on the ability to prepare single-phase
material [3]. Of key importance in this context are
phase-diagram data for CuESe: location of the liquidus
and composition stability limits. The Cu-Se system is
also of considerable interest in the context of the char-
acterization of cupriferous electrolyte slime and sele-
nium extraction [4].
T-x PHASE DIAGRAM OF THE Cu-Se SYSTEM
In most phase-diagram studies, Cu-Se alloys were
prepared from selenium of semiconductor purity and
electrolytically refined copper and were characterized
by thermal analysis, x-ray diffraction (XRD), and
microstructural analysis.
Liquidus and binodais. The liquidus in the compo-
sition range between Cu and Cu2Se has not yet been
studied in sufficient detail [5, 6]. Liquidus data for the
range 32.5-50 at. % Se were reported in [3, 6-8]. The
highest temperature portion of the liquidus line, in the
vicinity of Cu2Se, was constructed in [3] (32.5-35.6 at. %
Se, 19 data points) using precision differential thermal
analysis (DTA) with an accuracy of +1 K. The liquidus
between 38 and 50 at. % Se was located in [6-8] with a
6-8] agree well and, hence, provide reliable informa-
tion about the liquidus in the composition range
32.5-50 at. % Se (Fig. 1).
The most detailed data on the miscibility gap
between Cu and Cu2Se (Fig. 1) was obtained in [9] by
measuring the ultrasound velocity in the melt. Samples
were prepared by heating Cu-Se melts at 1450 K for
4 h with vigorous mechanical stirring. Phase separation
in the melt manifested itself in a sharp change in ultra-
sound velocity when one of the transducers was shifted
vertically. Acoustic bonds between the transducer buff-
ers and the specimen were made with a thin layer of
boric anhydride. The critical point of the L 1 + L2 misci-
bility gap was found to lie at 28 at. % Se and 1699 K.
Burylev et al. [10] studied liquid immiscibility in
the Cu-Se system by examining quenched materials.
According to their results, the miscibility gap is
bounded by essentially parallel lines. The most likely
reason for the discordance between the results in ques-
tion is that, in the study by Burylev et al. [10], the melt
was equilibrated for an insufficient time; therefore,
their data should be left out of consideration in con-
structing the equilibrium phase diagram.
The liquid miscibility gap in the Se-rich region is
characterized by a high Se vapor pressure. For this rea-
son, there is only one data point (98.2 at. % Se, 1236 K)
on the Se-rich side of the binodal [6]. The low-selenium
side of the L3 + L4 miscibility gap was tentatively
mapped out in [7, 8, 11]. The results reported in [7]
appear more reliable, since they fall between those
obtained in [8] and [11].
Intermediate phases. The system contains four
intermediate phases, of which only Cu2Se melts con-
gruently. In early studies, the melting temperature of
Cu2Se was determined to be 1386 + 10, 1403, or 1423 +
5 K [5, 8, 12]. The melting points obtained in [5, 8]
were considered the most reliable in many reviews and
handbooks [1, 13-21].

0020-1685/00/3607-0641525.009 2000 MAIK"Nauka/lnterperiodica"

642 GLAZOV et al.

T,K
1699 .I
1700 x2
03
D4
=5
L 1 + L2 +6
1500 VIII

/ 7" 1380
*" L 1 + [~-Cu2Se
1300 1336 + 5 X
I
I
L3 + L4 I

1100
iI
I
I
I
900 I
Cu + I~-Cu2Se ~-Cu2_xSe I
I 7~ •

700 I~-Cu 2 _xSe + L 4

652.7
,/ /605
13-Cu2_~Se+
y-C.uSe CuSe2 + L4
500 T-CuSe + T-CuSe2
tl3Se 2 + ~ - C u S e '494 "1"1
396 + 15 410
13-CuSe + CuSe2 CuSe2 + Se
326.8
Cu + ~ i t(~lV ~l _V__[_vv VII i i
Cu 20 It Ill Cu3Se2 CuSe 60 CuSe2 80 Se
at. %
Fig. 1. T-x phase diagram of the Cu-Se system: (1) [3], (2) [6], (3) [7], (4) [8], (5) [9], (6) [11]; (i) Cu + LI, (li) ~t-Cu2_xSe,
(Ill) ot-Cu2_xSe + ~-Cu 2_xSe, (IV) ~-Cu 2_xSe + Cu3Se2, (V) I~-Cu2 _xSe + ~-CuSe, (VI) Cu3Se 2 + 0t-CuSe, (VII) ot-CuSe +
CuSe2, (VIII) L 2 + I~-Cu2Se.

Recently, precision measurements of the liquidus
temperature in the vicinity of Cu2Se [3] have shown
that the congruently melting composition of copper
selenide is Cul.994Se, with a melting point of 1421 +
1 K. Stoichiometric Cu2Se melts at 1419 + 1 K. The
results obtained in [3] and [12] agree within the exper-
imental error. Clearly, the melting temperature deter-
mined in [3] is more reliable.
In the study by Glazov et al. [3], the liquidus line in
the composition range 32.5-36.6 at. % Se was fitted
with cubic splines. The results were used to determine
the radius of curvature, p, of the liquidus at the congru-
ent composition, which characterizes the degree of melt
dissociation. The data thus obtained show that the dis-
sociation of liquid Cu2Se occurs in two steps:
Cu2Se, 9 CuSe+Cu,
CuSe, - C u + S e .
The degree of dissociation is related to Pmaxby [22]
(_~)4 Vseabs RT 2
0~max = -- Vcu(aVc,se + bVc,) AmH Pmax, (3)
where AmHis the heat of fusion; m and n are the stoichi-
ometric coefficients of the compound; s is the number
of moles of the decomposing compound; Vcuseand Vcu
are the stoichiometric coefficients of reaction (1), yield-
ing an intermediate associate; and a and b are the num-
bers of associates evaluated with consideration for the
degree of dissociation of Cu2Se and CuSe associates.
According to calculations, o~(1) = 0.0377 and 0~(2 ) ----
0.00358 [3]. Therefore, the predominant associate
(molecular form) in the copper selenide melt is C u 2 S e .
With increasing Se concentration, the relative content
of CuSe associates rises.
(1) The heat of fusion of Cu2Se was reported to be 18.0
[23] or 9.06 kJ/mol [24]. Glazov and Mendelevich [23]
(2) determined the heat of fusion by quantitative thermal

INORGANIC MATERIALS Vol. 36 No. 7 2000

 PHASE EQUILIBRIA IN THE Cu-Se SYSTEM 643

analysis, using Cu2S as a high-precision reference sub- AmS, J/(mol K)

stance [14, 25]. According to their data, the heat of
fusion rises systematically in going from CUES to
CuETe. The plot in Fig. 2 illustrates the correlation
between the fusion entropy and bond ionicity for cop-
per(I) chalcogenides [23]. These results provide further
evidence for the reliability of the heats of fusion
obtained in [23]. At the same time, the heats of fusion
of CUES,Cu2Se, and CuETe determined by Biachnik and
Gunia [24] using drop calorimetry do not correlate with
bond ionicity. In addition, the data on the steplike dis-
sociation of CuESe at the melting point, obtained using
the heat of fusion determined in [23], were utilized to
calculate the composition dependence of Se activity in
Cu-Se melts in the range 31-39 at. % Se at 1420 K [3].
The calculated activities were in reasonable agreement
with the data obtained by vapor pressure measurements
[26]. Thus, the above observations confirm the reliabil-
ity of the heat of fusion of Cu2Se determined in [23].
The stoichiometry range of the high-temperature
form ~-Cu2_xSe (antifluorite structure) is fairly wide.
Below the eutectic temperature, the copper-rich stabil-
ity limit of copper selenide is essentially temperature-
independent down to the tx 9 , 13 phase transition
(Table 1) and is close to the CuESe stoichiometry [1].
More detailed studies show however that, in the range
873-573 K, the stability limit shifts to more Se-rich
compositions. According to coulometric titration data,
the Cu-rich phase boundary of copper selenide lies at
Cul.9975Se [27] or CUl.9956Se [28]. Based on coulomet-
ric titration data and emf measurements, Konev et al.
[29] showed that, below 773 K, the stability limit shifts
to more Se-rich compositions, so that the Se concentra-
tion on the phase boundary rises with decreasing tem-
perature. Similar results were obtained in [30], where
stoichiometric Cu2Se samples prepared by melting and
quenched from 10-40 K below the melting point were
20
O~.,~Cu2Te
15 Ag2Te~ A g 2 S e
10 ~CUES
AgES "~
5
I I I
0 5 10 15
~,%
Fig. 2. Correlationbetweenthe fusion entropy and bond
ionicityof copperand silverchalcogenides.
single-phase, whereas the samples quenched from
50-70 K above the melting point were two-phase and
contained needlelike Cu precipitates.
The highest content of superstoichiometric Se is
=3 at. %. The Se-rich phase boundary of CUE_xSe is
shown in Fig. 1. Note that, according to phase-diagram
studies [5, 7, 31 ], this boundary is essentially vertical in
the range 410-796 K. Below the temperature of the
o~ 9 9 13transformation and the peritectoid decomposi-
tion of Cu3Se 2, the composition stability limit of
13-Cu2_xSe has not been determined with certainty
(Fig. 1). The reported composition stability limits of
13-CUE_xSeat room temperature are summarized in [1].
Analysis of those data indicates that the Cu-rich phase
boundary of copper selenide is at 35.3 + 0.9 at. % Se
and the Se-rich boundary is at 36.4 + 1.7 at. % Se. The
major reason for the large uncertainties in these values
is that low-temperature equilibration requires rather

Table 1. Crystal structures of intermediate phases in the Cu-Se system

Phase at. % Se ~K Structure Sp. gr. a, nm b, nm c, nm 13 Reference
~-CUE_xSe -~33.3-33.8 298.15 Monoclinic 1.4087 2.0481 0.4145 90023, [1, 21]
~-CuESe = 33.3-36.4 298.15 Antifluorite Fm3m 0.5860 - - [1,21]

Cu3SeE 40.0 298.15 Tetragonal P421 m 0.6385 0.4271 - [I, 21]

tx-CuSe 50.0 298.15 Hexagonal 1.4203 1.7255 - [34]
I]-CuSe 50.0 353 Orthorhombic Cmcm 0.3954 0.6856 1.7238 - [34]
y-CuSe 50.0 485 Hexagonal CuS P63/mmc 0.3983 1.7260 - [34, 36]
CuSeE-I* 66.7 298.15 Marcasite Pnnm 0.50046 0.61822 0.37397 - [1, 21]
CuSeE-II** 66.7 298.15 Pyrite Pa3 0.6616 - - [1,21]

Note: ot-CuSe(Z = 6) differsfromy-CuSe(covellitestructure,Z = 78) by an a-axis superstructurewitha' = a..~ [34, 36].

* Low-pressurephase.

** High-pressurephase stable at atmosphericpressure.

INORGANIC MATERIALS Vol. 36 No. 7 2000

644 GLAZOV et al.
long times. In view of this, the low-temperature phase
boundaries of 13-Cu2_xSeare shown by dashed lines.
~-Cu2_xSe decomposes by the peritectoid reaction
(~-Cu 2 _xSe) . 9 (o~-Cu2Se) + (Cu3Se2) (4)
at a relatively low temperature, which is difficult to
accurately determine. According to DTA data [31 ], the
peritectoid temperature is =253 K. Based on conduc-
tivity measurements, the eutectoid temperature was
determined to be 170 + 7 K [32]. The eutectoid was
reported to occur at 35.7 [31] or 35.1 at. % Se [32].
Cu3Se2. This compound forms by a peritectoid
reaction at a relatively low temperature (Fig. 1) and,
accordingly, at a slow rate. The reaction rate can be
raised by applying high pressure. Full conversion can
also be achieved by thoroughly grinding the reaction
mixture [1, 11]. The rate of Cu3Se2 decomposition is
notably higher. The peritectoid temperature was
reported to be 408--448 K [6, 8, 31, 33]; a somewhat
lower temperature of 393 K was obtained in high-tem-
perature XRD studies [33]. The most detailed studies of
Cu3Se2 decomposition were carried out by Murray and
Heyding [11 ], who recorded DTA curves using a differ-
ential scanning calorimeter (DSC). They assessed the
effect of the heating rate on the decomposition temper-
ature. At heating rates of 10 and 5 K/min, the transfor-
mation occurred at 404 and 398 K, respectively. When
the sample was heated at 8 K/h in a Guinier-Lennet
high-temperature chamber, the decomposition temper-
ature was 386 K. This decomposition temperature was
probably determined under more equilibrium condi-
tions and appears to be the most accurate [1].
CuSe. Copper monoselenide forms by the peritectic
reaction between ~-Cu2Se and a Se-rich melt. Since the
rate of CuSe formation is slower than the rate of
decomposition, the incongruent melting temperatures
determined from heating curves appear to be more
accurate. The reported decomposition temperatures of
CuSe fall in the range 657-673 K [6, 8, 31]. According
to the latest studies by precision step-heating adiabatic
calorimetry, CuSe decomposes at 652.7 K [34]. DTA
and DSC measurements yield 655 and 650 K, respec-
tively [7, 11]. The decomposition temperature reported
in [34] appears to be the most accurate.
CuSe exists in three different polymorphs. Accord-
ing to the heat capacity measurements in [34], the tem-
perature of the t z , , [3 phase transition is 326.8 K, in
agreement with earlier data [7, 11]. The 13 - " )' transi-
tion cannot be detected by thermal analysis. According
to high-temperature XRD studies [ 11, 33], the temper-
ature of this transition is 393 K. Stolen et al. [34] deter-
mined the transition temperature from XRD data
(=410 K) and heat capacity measurements (410 K).
Their data appear to be more reliable. The 13 . , ),
phase transition is accompanied by an insignificant heat
effect [11, 34, 35]: the Cp(T) curve shows a small, broad
lambda-type anomaly and a well-defined step above
410 K [34]. The 13.---'- ~/transition is assumed to be sec-
ond-order [34]. Both the tz, - 13and 13, " )'transfor-
mations are not kinetically hindered.
The heat of the tx 9 - [3 phase transition is 0.885 +
0.002 kJ/mol [34]. The heat of the peritectic CuSe
decomposition determined in [34] is 11.80 +
0.03 kJ/mol, which agrees within the experimental
error with earlier data (14 + 3.5 kJ/mol I11]).
CuSe 2. Copper diselenide forms by the pedtectic
reaction between ~/-CuSe and an Se-rich melt at a very
slow rate. The reverse reaction occurs at a somewhat
faster rate and can be detected in heating curves. In
most studies, the incongruent melting temperature of
CuSe2 was found to lie in the range 605--620 K [6, 7,
11]. A rough estimate of =673 K was reported in [35].
Murray and Heyding [11], using DSC, determined the
9incongruent melting point of CuSe2 to be 605 K. This
result appears to be the most accurate. Babitsyna et al. [8]
failed to obtain CuSe2, probably because the annealing
time in their studies was too short.
The heat of the peritectic decomposition of CuSe2
was determined in [6, 7] by quantitative DTA and in
[11] by DSC. The results are in reasonable agreement:
10.9, 12.1 + 2.9, and 9.6 + 4.0 kJ/mol, respectively.
The crystallographic data for the copper selenides
are summarized in Table 1.
Cu- and Se.based sofid solutions. The available
data on the extent of the Cu-based solid solution were
summarized in [1]. From these data, we derived the
equation of the solvus line for the solubility of ~-Cu2Se
in Cu from 773 to 1336 K, the melting point of the
eutectic between Cu and ~-Cu2Se (Table 2). The solu-
bility of ~-Cu2Se in Cu rises from 0.0004 mol % at
773 K to 0.021 mol % at 1336 K. The equation of the
solvus line has the form
logx (mol % Cu2Se )
(5)
= - (3184.5 + 24.8)T + 0.684 + 0.025.
From this equation, the heat of solution of ~-Cu2Se in
Cu is 61.0 + 0.5 kJ/mol in the range 773-1336 K.
The solid solubility of CuSe 2 in Se has not been
determined experimentally. Since the temperature of
the invariant equilibrium
L 4 9 " CuSe 2 + Se (6)
coincides with the melting point of Se [6-8, 11, 31] to
within the error of determination (+1-5 K), the solid
solubility of CuSe 2 in Se can be considered negligible.
Invariant three-phase equilibria. The tempera-
tures and compositions of the invariant equilibria in the
Cu-Se systenv-incongruent melting of CuSe and
CuSe2, peritectoid decomposition of Cu3Se2, polymor-
phic transformations of CuSe, and eutectic reaction (6)--
were mentioned above.
Note that the available data on the invariant equilib-
ria involving tx-CuSe, [3-CuSe, and v-CuSe are insuffi-
cient to ascertain whether a eutectoid or peritectoid
INORGANIC MATERIALS Vol. 36 No. 7 2000
 PHASE EQUILIBRIA IN THE Cu-Se SYSTEM 645

Table 2. Three-phase equilibria in the Cu-Se system

Compositions Of the phases T,K Type Reference
Equilibrium
involved (at. % Se)

L2 9 . L 1 + ~-Cu2Se 31.5 =4 33.3 1380 Monotectic [1,5,9,21]

L 1 9 . (Cu) + I~-Cu2Se =1.8 0.021 33.3 1336+5 Eutectic [1, 5, 6, 21, 31]
L 3 9 . (~-Cu2Se) +L 4 52.5 36.5 =99.6 796 + 1 i Monotectic [1,7, 11,21]
(~-CuESe) + L4 ~ )'-CuSe 36.5 =100 50.0 652.7 Peritectic [34]
~/-CuSe + L4 " , CuSe2 50.0 = 100 66.7 605 Peritectic [1, 11,21]
L4" , Cu2Se+Se =100 66.7 100 494 + 1 Eutectic [1,7, 11, 15]
(~-Cu2Se);)'-CuSe; ~-CuSe* 36.5 50.0 50.0 410 Peritectoid or eutectoid [34]
H
T-CuSe; I]-CuSe; CuSe 2 50.0 50.0 66.7 410 [34]

(Cu) + ~-Cu2Se " , o~-Cu2Se ---4 x 10-8 =33.3 =33.3 396 + 15 Pentectoid [1,11,21]
([~-Cu2Se) + ~-CuSe " 9 Cu3Se2 =36.3 50.0 40.0 386 [1,11,21]
Cu3Se2; ~-CuSe; ot-CuSe* 40.0 50.0 50.0 326.8 Peritectoid or eutectoid [341

l]-CuSe; ~-CuSe; CuSe~ 50.0 50.0 66.7 326.8 [341

(~-Cu2Se) - , (ot-Cu2Se) + Cu3Se2 =35.4 234 40.0 <253 Eutectoid [32, 33]
Note: Parentheseslabel solid solutions based on the indicated phases.
* Since the nature of the invariantequilibrium is not determined unambiguously,only the set of the phases involvedis indicated, as
in the handbook edited by Massalski [21].

reaction occurs [1, 21]. These equilibria are analyzed
below (Table 2).
The temperature of the eutectic equilibrium involv-
ing the melt, Cu-based solid solution, and ~-Cu2Se was
reported to be 1336 + 5 K [5, 6, 31]. The eutectic tem-
perature of 1321 K reported by Babytsina et al. [8] is
clearly too low. The eutectic composition (-1.8 at. %
Se) was determined only in [5] by thermal and micro-
structural analyses.
The temperature of the monotectic equilibrium in
the Cu-rich region was reported to be 1380 [5] or
1373 K [8]. The former temperature appears to be more
accurate, since the melting point of Cu determined
in [5] differs by as little as ---2 K from the reference
value given in [14] (1358 K). The melting point of Cu
determined in [8] is somewhat lower (1346 K), suggest-
ing that the monotectic temperature might also be
underestimated. The commonly accepted temperature
of this equilibrium is 1380 K [1, 21]. The composition
range of this monotectic equilibrium (Table 2) was
determined in a recent study [9].
The temperature of the monotectic equilibrium in
the Se-rich region was determined to be 796 K [6, 7, 11,
31] with an accuracy of +1-5 K. The temperature of
813 K reported in [8] appears to be too high. The mono-
tectic extends to the ]]-Cu2_/Se phase field. The Se-rich
boundary of the monotectic was tentatively located at
-~99.6 at. % Se [6]. Phase separation in this composi-
tion range was observed visually by Babitsyna et al. [8].
The polymorphic transformation of Cu2Se was stud-
ied in most detail by Murray and Heyding [11] using
precision high-temperature XRD and DTA. According
to their XRD data, the temperature of the t~, - l] trans-
formation in stoichiometric Cu2Se is 396 + 3 K. At the
same time, they observed a shift of diffraction peaks in
the range 350-396 K, which could not be accounted for
by thermal expansion only. The DTA curve of the same
sample showed a broad peak in the range 373-415 K,
centered at 409 K. According to enthalpy measure-
ments by drop calorimetry, the transition temperature is
395 K [24]. In heat capacity measurements in an adia-
batic calorimeter [37], the transition temperature was
determined to be 395 K. However, Kubaschewski and
Nolting [37] pointed out that the heat capacity varied
anomalously in the range 293-393 K, which was not
detected by Blachnik and Gunia [24], probably because
of the relatively small number of data points in this
temperature range. The observed anomaly in heat
capacity was attributed to the formation of Frenkel
defects on Cu sites [37]. In our opinion, this conclusion
needs further verification.
The available data on the transition temperature of
Cu2Se were analyzed in [1, 11]. Proper attention was
given to the substantial scatter in the DTA and XRD
data, from 350 to 415 K, and the diffuse character of the
transformation. According to Murray and Heyding
[ 11 ], both the shape of the DTA peak and the maximum
peak temperature remained unchanged upon a tenfold
increase in the heating rate. In the cooling curves, the

INORGANIC MATERIALS Vol. 36 No. 7 2000

646 GLAZOV et al.

T,K Earlier, the T-x phase diagram of the Cu-Se system

% was studied at 2 GPa in the composition range
%
"-% 818 25-70 at. % Se [11], using a DTA cell designed to
800 ~779 withstand high pressures at temperatures up to 850 K.
The tentative phase diagram mapped out in [11],
including some of the phase-equilibrium temperatures,
700i is displayed in Fig. 3. The salient feature of this phase
diagram is the absence of the intermediate phase CuSe,
o which decomposes even at room temperature and pres-
600 sures slightly below 1 GPa by the reaction
4CuSe - Cu3Se2 + CuSe 2. (7)
500 There is no liquid immiscibility in the Se-rich
region; copper diselenide, having the pyrite structure at
elevated pressures (Table 1), melts congruently. The
pyrite structure also persists at atmospheric pressure.
~l i'- 9On cooling, pyrite CuSe 2 undergoes a superconducting
ll
I!
transition at 2.30-2.45 K, preceded by a second-order
300 magnetic transition at 31 K [1, 41].
I I I I I I I The high-pressure transformations of Cu2Se were
30 Cu2Se Cu3Se2 50 60 CuSe:70 considered in [17, 41].
at. % Se
Fig. 3. Partial T-x phase diagram of the Cu-Se system at p-T PHASE DIAGRAM
2.0 GPa. OF THE Cu-Se SYSTEM
Experimental data on the p-T phase diagram of the
peak was centered at 407 K. Bernardini et al. [6] Cu-Se system in wide ranges of compositions and tem-
reported that the transition temperature of a two-phase peratures were obtained by Ran and Rabenau [42]. The
sample containing Cu was slightly higher than that of SIS2V and SLV heterogeneous equilibria were studied
single-phase material: the temperature of the r - 13 by different techniques, depending on the nature of the
transformation was 403 K for stoichiometric Cu2Se and equilibrium and Se vapor pressure.
421 K for the sample containing 8.3 at. % Se. During The equilibrium
cooling, the transition temperature was 414-416 K, 2Cu2Se(s) = = 4Cu(s) +Se2(g ) (8)
independent of phase composition. The nature of this
effect is not yet fully understood. The recommended was studied in flowing hydrogen between 933 and
temperature of the polymorphic transformation in 1273 K. To calculate the dissociation pressure of Se2 in
question, inferred from XRD data [11], is 396 K [1]. equilibrium (8), use was made of earlier data on the
The uncertainty related to the effects of the measure- heat of formation of H2Se(g) [43].
ment procedure and phase composition of the sample The dissociation pressures of CuSe2 and ),-CuSe
was estimated at +15 K [1]. The results obtained in [6, were determined by the flow method. The associated
7, 31, 38] also fall within these accuracy limits. Thus, equilibria correspond to the sequence of transforma-
the recommended transition temperature is 396 + 15 K. tions
The heat of the polymorphic transformation in CuSe 2 ,, ~/-CuSe ,. Cu2_xSe. (9)
Cu2Se was determined by drop calorimetry [24], adia-
batic calorimetry [37], DTA [7], and DSC [11]. The The Se vapor pressure in the three-phase equilib-
respective values are 6.48 + 0.12, 6.83 + 0.2, 20.5 + 4.0, rium Cu2_xSe(s)-melt-vapor was determined with a
and 6.4 kJ/mol. Based on early work, Kelley [39] rec- membrane manometer.
ommended a value of 4.85 kJ/mol. Comparison of the Since the Se2 partial pressure is equal to the total Se
above results demonstrates that the most consistent pressure only above 1050 K, Ps~ was calculated with
data are those obtained in [11, 24, 37].
consideration for the constants of Se, dissociation into
Table 2 summarizes data on the invariant equilibria Se2 [44], which were evaluated under the assumption
in the Cu-Se system. that the composition of selenium vapor is governed by
T-x phase diagram of the Cu-Se system. Based the equilibrium between Ses, Se6, Se4, and Se2. Zlo-
on available phase-diagram data, including those pub- manov and Novoselova [45] carried our a detailed anal-
lished in 1996, we constructed the T-x phase diagram ysis of the results obtained in [42] from the viewpoint
of the Cu-Se system (Fig. 1). The melting points of Cu of the representation of three-phase equilibria in p-T
and Se were taken from [14, 40]. diagrams and proposed a more clear interpretation of

INORGANIC MATERIALS Vol. 36 No. 7 2000

 PHASE EQUILIBRIA IN THE Cu-Se SYSTEM 647

the three-phase equilibria studied in [42]: A B , B"C, CD, logp [kPa]

D F , FH, DE, and F I (Fig. 4). U
Pashinkin et al. [46] calculated the Se2 partial pres-
2 Ne c' [ R s r
sure at point C and four points of the three-phase equi-
librium B " C (Fig. 4). A procedure for calculating the
p i - T phase diagrams of systems containing a congru-
ently melting compound was proposed in [47]. The key
features of this procedure are the use of data on the dis- B" If
sociation constant derived from the curvature of the liq-
uidus at the melting point [22] and the ideal associated -2
solution model. The Se 2 partial pressure was calculated
using the equations considered below [46]. Use was
made of a simplified scheme of Cu2Se dissociation in -4
the melt: t

Cu2Se , '- 2Cu + Se. (10) -6

The dissociation constant of CuESe at the melting point
is given by [22, 47]
-8 ol
D2
(n*eln*)(n~uln*) 2
K = (11)
,4 I I
(n~u2se/n* )
1.0 1.5 2.0
where n* is the number of moles of all species per mole 1031T, K -l
of the melt, and nc,2s~*, ns~*,and n*~ are the numbers of Fig. 4. p---Tphasediagramof the Cu-Se system; three-phase
moles of Cu2Se, monomeric Se, and Cu in the melts. equilibria:AB ScuS~.eu2S e V, BB' = L I S~.cu2s e V , B'B" =
=

The dissociation constant of Cu2Se was assumed to be

temperature-independent. This assumption is justified
since the dissociation constant determined as described
above is sufficiently small. The actual melt composition
(x) for a particular initial composition was calculated
with the use of expressions describing the law of con-
servation of mass in the melt [22]:
* e,
n~e = 1 - X - ncu2s (12)
n~u = X - 2 n c u*2 s e, (13)
n* = 1 - 2ncu2s~. (14)
Next, the Se 2 partial pressure was calculated using the
relation
0 , ,.2
Pse~ = Pse2tXs~) , (15)
where Ps~ is the Se 2 partial pressure in Cu-Se vapor at
equilibrium, p~ is the Se 2 partial pressure over molten
Se at a given temperature, and x~'e =
n*o
~-; is the mole
fraction of monomeric Se in the Cu-Se melt at a given
temperature. The Se partial pressures thus calculated
agree reasonably well with earlier data [42].
Using the results obtained in [42] and their interpre-
tation in [45], we recalculated the p - T phase diagram of
the Cu-Se system in three steps. First, we calculated
the ScuScu2se V equilibrium (Fig. 4, line A B ) and the
L2SI~_Cu2SeV, B"C = SI~.Cu2seL3V,CD = SI3.Cu2seL4V,
CC = LaL4V, DF = &t.CuSeL4V, FH =Scuse 2L4V, HJ =
Souse2SseV (or the two-phase equilibrium SSeV), DE =
S~.Cu2SeSy_cuseV, FI = Sy.cuseScuse 2 V, BL = ScuLIE
BQ= ScuLi Sf~.Cu2Se, B'N = LIL2SI3_Cu2Se, CU =
Sl~_Cu2_xsuL3L4, DR = Scu2_xseSY_CuseL4, SF =
Sr_CuSeScuse2L4, HT = Scuse2L4Sse (or the two-phase
equilibrium SseL); two-phaseequilibria:LM = ScuV, KL =
Lcu V, LP = ScuL, B"O = Scu2seL; invariant four-phase
points: B = ScuLlSi~.Cu2SeV, B' = LIL2SI~.Cu2Se V, C =
Si3_Cu2SeL3L4V, D = Sl~.Cu2SeSy.cuseL4V, F =
Sy_CuSeSCuSe2L4V, H =Scuse 2 L4VSse (or the three-phase
point SseLV); invariant three-phase points: L = ScuLcu V,
B"= SCu2SeL2V; (1) calculation results [46], (2) data
from [55].
lines of Cu sublimation and vaporization (Fig. 4, K L M ) .
Point B corresponds to the eutectic temperature of
1336 K (Table 2). The vapor in the Sc.Scu2se V equilib-
rium has a complex composition because of the rela-
tively high temperature (900 K and above). According
to the data obtained in [42], equilibrium (8) corre-
sponds to a "nominal" Se 2 vapor pressure. It is neces-
sary to take into account Se2 dissociation,
Se2(g) ~ " 2Se(g) (16)

INORGANIC MATERIALS Vol. 36 No. 7 2000

648 GLAZOV et al.
and the pressure of the Cu vapor resulting from the
thermal dissociation of Cu2Se. The vapor phase is also
known to contain CuSe [16]. The CuSe(g) partial pres-
sure can be evaluated by considering the equilibrium
Cu2Se(s) = Cu(s) + CuSe(g). (17)
To calculate equilibrium (16), we used the thermo-
dynamic data given in [ 16, 40, 48]. The partial pressure
of monatomic Se was found to be low and to rise with
temperature, attaining 3-10% of the total Se vapor
pressure.
In calculating the Cu vapor pressure, we used the
results obtained in [49, 50], which correlate well.
Slightly above 1200 K, the Cu partial pressure in equi-
librium AB (Fig. 4) exceeds the Se2(g) + Se(g) pressure.
The vapor pressures over solid and liquid Cu are shown
in Fig. 4 by lines LM and KL.
The CuSe partial pressure in the Sc"Sc,,2se Vequilib-
rium can be estimated only roughly because of the large
uncertainty in the heat of formation of CuSe vapor [14,
16, 51]. This pressure, however, amounts to no more
than 2-3% of the total vapor pressure in the equilibrium
in question. Since the Pso~/Pc. ratio varies significantly
with temperature, line AB, representing the Sc"Sc"2s~ V
equilibrium in the plot of logp vs. liT(Fig. 4), upturns
slightly at high temperatures.
The SC"LIV equilibrium (Fig. 4, line BL) was evalu-
ated graphically.
In the second step, we calculated the total selenium
pressure for the equilibria in which the Se vapor consists
of species more complex than Se2 (Fig. 4, lines B"C, CH,
HJ, DE, FI). To this end, we again used the results
reported in [42], the temperature-dependent equilib-
rium constants of the reactions
Se,. - Se2, n = 4, 6, 8, (18)
determined in [44], and the raw data obtained in [42].
Since the vapor pressure in the temperature range
494-796 K (Fig. 4, line HC) is determined by that over
liquid Se, also measured in [44], we could compare our
results with those obtained in [44] for the same temper-
ature range. The largest discrepancy in p~t~ was found
to be 6.6%, indicating a high accuracy in our p--T cal-
culations [52]. Similar calculations were performed
using the data reported in [46].
Note, however, that, throughout the temperature and
pressure ranges of interest, the real vapor consists of
both even and odd species, from Se2 to Sea [52]. At the
same time, it was shown by Rusin et al. [52] that,
although the vapor composition and, hence, equilib-
rium constants determined in [44] were not quite exact,
the results obtained in [44], as well as the closely simi-
lar data reported in [53], ensure the best agreement
between the Se2 partial pressure and the total selenium
pressure. The same is evidenced by the calculations
performed in [54].
Esirkegenov and Valiev [55], using static weighing,
determined the vapor pressure over the CuSe and
CuSe2 melts in the range 667-973 K. To evaluate the
vapor pressure, they used mass spectrometric data on
the composition of selenium vapor for all the species
from Se2 to Ses [56]. The weighing method is com-
monly used to study p--T-x phase diagrams [57]. By
analyzing the results obtained in [55], we assigned
some of them to the line of the three-phase equilibrium
CD and located the beginning of the line representing
the three-phase equilibrium LaL4V (Fig. 4, line CC').
Piacente and Scardala [58] determined the dissocia-
tion pressure of 7-CuSe by torsion Knudsen measure-
ments in the range 554-628.5 K. Their results agree
well with those obtained in [42] and recalculated as
described above, but the accuracy in their measure-
ments was fairly low.
In the third step, we constructed the lines of the two-
and three-phase equilibria involving no vapor phase. It
is well known that the melting points of Cu, Se, and
13-Cu2Se rise with pressure; however, on the scale of
Fig. 4, the slope of these lines is negligible. Information
about the pressure effects on the other monovariant
three-phase equilibria is missing, and the correspond-
ing temperatures were considered constant (Fig. 4).
The p-T data obtained by interpolation or approxi-
mate extrapolation are shown in Fig. 4 by dashed lines.
The temperatures of all the invariant points in Fig. 4
correspond to those of the invariant three-phase equi-
libria (Fig. 1, Table 2).
The p-T diagram of the Cu-Se system constructed
by Levinskii [61] with the use of the data reported in
[17, 42, 49, 50, 55] differs somewhat from ours. Exper-
imental T-x data for the Cu-Se system (Fig. 1) demon-
strate that the eutectic between CuSe2 and Se is degen-
erate and, therefore, point H in the p-T phase diagram
represents both the triple point of Se and the point
describing the Sc"s~2L4VSse equilibrium (Fig. 4). The
available experimental p-T [42] and T-x [6--8, 11, 31 ]
data give no grounds to draw these points apart, as was
done by Levinskii [61], whose phase diagram lacks
detail in this region. According to Levinskii [61], the
line of the three-phase equilibrium L3L4Vterminates at
the critical point of the immiscibility curve (-1073 K).
This point, however, was not located experimentally;
its position was estimated roughly from the position of
the binodal bounding the L 3 + L4 liquid immiscibility
region in the T-x phase diagram [48]. In view of this,
only a portion of the line representing this three-phase
equilibrium (CC), constructed using the data obtained
in [55], is shown in Fig. 4. The line of the three-phase
equilibrium LIL2V was tentatively constructed in [61].
However, since there are no experimental data on the
vapor pressure over the Ll +/-,2 immiscibility region, we
INORGANIC MATERIALS Vol. 36 No. 7 2000
 PHASE EQUILIBRIA IN THE Cu-Se SYSTEM 649

did not draw this line, which would begin at point B' at. % Se
(Fig. 4). 25 50 75 100
I I I

THERMODYNAMIC CHARACTERIZATION
OF COPPER SELENIDES -5 CuS:
Table 3 summarizes the standard formation enthalp- ~t-CuSe
ies [14] and entropies of copper selenides.
Cu~Se2
For all the selenides, except tx-CuSe [34], the accu- -10
racy in the standard entropies is fairy low. The standard - 2Se
entropy of I~-CUl.sSe is unknown. Using the available
experimental data on the thermodynamic properties of -15
copper selenides, we determined the composition
dependence of the Gibbs energy of formation.
, /
i
In constructing a AfG-x diagram, a necessary condi- -20
tion is its consistency with the T-x diagram over a wide
temperature range [62]. Because of the limited infor- J
mation on the temperature dependences of the thermo- -25
dynamic functions of copper selenides, we restricted AfG, kJ/mol;
ourselves to constructing the AfG-x diagram at
298.15 K. The phase relations in the Cu-Se system at Fig. 5. AfG-x diagramof the Cu-Se systemat 298.15 K.
this temperature are known with a high degree of reli-
ability (Fig. 1). In view of this, using data on the num-
ber, stability, and thermodynamic properties of inter- The corrected values are believed to be more accurate
mediate phases at the standard temperature (Table 3) than those given in [16]. Since the standard entropy of
and introducing some corrections into the standard 13-Cul.sSe is unknown, this phase was left out of
entropies of t~-Cu2Se, Cu3Se 2, and CuSez, given in [16] account, which is expected to have little effect on the
with a low accuracy, we constructed the AfG-x diagram AfG-x diagram, because Cu2Se and ~-Cul.sSe are close
of the Cu-Se system at 298.15 K. in composition.
In constructing such a diagram, account should be The thermodynamic properties of copper selenides
taken not only of the possibility of formation of all the assessed in [64] from emf data cannot be used as the
intermediate phases from the corresponding compo- basis for reference data because of their insufficient
nents but also of their relative stability, which is quan- accuracy.
titatively measured by the relative values of AfG for two Heat capacity at constant pressure was measured
neighboring phases [63]. Thus, for all the intermediate only for Cu2Se and CuSe, each existing in a number of
phases in the Cu-Se system, AfG298is negative not only polymorphs (Table 1).
for the formation from Cu and Se but also for the for-
mation from the corresponding neighboring phases. Heat capacity data for tx- and 13-Cu2Se were
The 298.15-K AtG-x diagram (Fig. 5) consistent with reported in [24, 37]. Kubaschewski and Nolting [37]
the T-x diagram (Fig. 1) could be constructed by determined the heat capacity of tx-Cu2Se between 193
changing, within the accuracy limits, the standard and 325 K by adiabatic calorimetry. Their results were
entropies of o~-Cu2Se, Cu3Se 2, and CuSe2 (Table 3). used later to derive the equation of heat capacity as a

Table 3. Standard formation enthalpies and standard entropies of copper selenides

0
Compound -Afn~298,kJ/mol [ 13] 5298, J/(mol K)

~-Cu2Se 65.86 + 0.53* 129.7 +4.2 [14, 32]; 125.5"*

I~-CUl.sSe 55.35 + 0.33
Cu3Se2 98.91 + 0.54 207.11 + 21 [14]; 228.1'*
tx-CuSe 39.54 + 0.42 79.36 + 0.06 [28]
CuSe2 43.10 + 7.1 107.5 + 10.5 [14]; 118.0"*
* Calculatedfromthe standardheat of formationof 13-Cu2Se[13] and the heat of the ~ - ~ transformationin Cu2Se [11, 18, 31].
** Standardentropiesused in constructingthe ,~298-X diagrammatchedwiththe T-x diagramof the Cu-Se system.

INORGANIC MATERIALS Vol. 36 No. 7 2000

650 GLAZOV et al.
Table 4. Coefficients in the least square equations for the heat capacities of tx-Cu2Se and CuSe polymorphs, Cp = a + b T -
cT -2 + dT, J/(mol K)
Polymorph AT, K a b x 103
~-Cu2Se 193-325 58.6
~-CuSe 200-327 72.384
~-CuSe 327--410 51.396
~CuSe 410--652.7 106.473
function of temperature (Table 4) [ 1]. Above 325 K, the
heat capacity of Cu2Se varies nonmonotonically on
account of the t~, , ~ transformation [37]. Blachnik
and Gunia [24] measured the heat capacity of ~-Cu2Se
at three temperatures between 300 and 395 K using
drop calorimetry. Therefore, the data obtained in [37]
between 193 and 325 K appear more reliable.
The heat capacity of I]-Cu2Se was measured from
400 to 1390 K in [24] and from 403 to 773 K in [37] by
the same methods as in the case of t~-Cu2Se. The results
are in good agreement. The heat capacity of ~-Cu2Se
was found to be a weak function of temperature, with a
poorly defined minimum in the range 650-800 K. The
average Cp of 13-Cu2Se in the temperature range studied
is 82.9 + 1.7 J/(mol K). This value can be recommended
for thermochemical and thermodynamic calculations.
The heat capacity of CuSe was measured using adi-
abatic calorimetry in the range 5.7--652.7 K [34]. The
low-temperature data were used to calculate the stan-
dard entropy of o~-CuSe (Table 3). The least squares
equations for the temperature-dependent heat capaci-
ties of o~-Cu2Se and o~-, ~-, and ),-CuSe within their
temperature stability limits are given in Table 4. The
equations for the CuSe polymorphs were derived from
the smoothed heat capacity data reported in [34].
ACKNOWLEDGMENTS
This work was supported in part through the project
Database of Phase-Diagram Data for Semiconductor
Systems (Baikov Institute of Metallurgy and Materials
Research, Russian Academy of Sciences; Institute of
Chemical Problems of Microelectronics).
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