Materials Research Bulletin, Vol. 30, No. 12, pp.

1495-1504, 1995
Copyright 0 1995 Elsevier Science Ltd
Printed in the USA. All rights reserved
002%5408/95 $9.50 + .I0

00255408(95)00155-7

SYNTHESIS OF BINARY COPPER CHALCOGENIDES BY

MECHANICAL ALLOYING

T. Ohtani, M. Motoki, K. Koh, and K. Ohshima

Laboratory for Solid State Chemistry, Okayama University of Science, Ridai-cho l-l,
Okayama 700, Japan

(Received June 12,1995; Communicated by M. Koizumi)

ABSTRACT
Copper sulfides (tetragonal Cut.g2S-Cut.ggS, rhombohedral cU1.71s-cU1.Bgs,
CuS), selenides (l3 Cq_se, CySe2, y CuSe, CuSeZ), and tellurides (Cu2_XTe,
Cu3Te2) were prepared from mixtures of the elements by mechanical alloying
(MA), using a high-energy ball mill. The compounds were obtained by 60-120
min of MA. It is notable that two metastable high-pressure phases were obtained
by MA: tetragonal Cu2,S and pyrite-type CuSe2. The tetragonal phase
gradually transformed to the stable phase of djurleite when kept at room
temperature. Cu1,7lS-Cu1.89s also formed a metastable rhombohedml phase.

MATERIAL INDEX: Copper, Sulfur, Selenium, Tellurium

Introduction

Mechanical alloying (MA) is a high-energy ball milling process which was originally
developed for preparation of nickel-based superalloys by Benjamin (1). This method has been
applied to prepare alloys comprising a high melting and a low melting metal which are hard to
produce by melting due to the separation of low melting metal during solidification. MA is
now proved to be a versatile technique for synthesizing unique microstructures; e.g.,
amorphized intermetalics (2,3), nonequilibrium solid solutions (4), and metastable alloys (5).
Only a limited number of metal chalcogenides have been prepared by this method, e.g., Ni-S,
FeS, ZnS (6,7), and Fe-S (8). Here we report the preparation of copper chalcogenides by an
MA technique; i.e., copper sulfides (tetragonal Cut.g#-Cut.wS, hexagonal Cu1.7tS-Cu1.89!$
and CuS), copper selenides (B Cuz_.$e, CujSe2, y CuSe, and CuSeZ), and copper tellurides
(Ct&Te and CujTe2).

ExDerimental

The compounds were synthesized by milling mixtures with desired ratios of elemental
powders in air: The starting elements were copper (Katayama Chemical, 99.9% in purity, 300
mesh), sulfur (Nakalai Tesque, 99.999% in purity), selenium (Wako Pure Chemical, 99.999%
149.5
1496 T. OHTANI et al. Vol. 30, No. 12

in purity), and tellurium (Wako Pure Chemical, 99.m in purity). The mixtures were milled
in a planetary ball mill (FRITSCH, P-7) under the following conditions: vial and ball material,
agate; inner volume of vial, 10 ml; ball charge, 4 balls with 12 mm diameter; weight of starting
mixture, 1.0 g; rotational speed of planet carrier, 2,800 rpm; milling time, 60 -120 min. X-my
diffraction (XRD) measurements were carried out on RAD-B (Rigaku Denki Co.) using Cu-Ka
radiation Several samples were pressed into pellets and were used for electrical resistivity
measurements from room temperature to 2 K.

Results and Discussion

Comer sulfides

Figure 1 gives the XRD pattern of Cut,%S prepared by milling for 60 min. X-ray analysis
revealed that the reactions were completed after 45-60 min of MA. The pattern is identical with
that of metastable tetragonal CL&S; the structure is based on slightly distorted cubic closest
packing of sulfur atoms, with copper atoms in trigonal coordination and the space group is
P43212 (9). X-ray analysis revealed that the single phase region extends from Cut.g$ to
Cut.@. The lattice parameters of the tetragonal Cul.& were calculated to be a = 4.007 A and
c = 11.273 A, which are quite consistent with literature values (9). The parameters showed a
little variation with composition; the value of c/a decreases slightly with decreasing Cu content.
All the products were obtained as black powders. Electrical resistivity p of the tetragonal
Cu2_$ (2-x = 1.95 and l.%) is shown in Fig. 2. The resistivity shows an increasing
tendency with decreasing temperature down to 2 K, indicative of semiconductive behavior,
while the values of p were relatively low and varied almost linearly with temperature.

E
5
4 a=4.cmA.c=1m3A)
m
x
.z

s
+

10 20 30 40 M 60 70 80
28 (degrees)
FIG.l.
XRD pattern of tetragonaf Cut.& prepared by 60 min of MA.

It is well known that the stable phase of Cut.g& is djurleite which was first prepared by
Djurle (10). Potter found that the stability range of djurleite extends from Cut.g& to
Cul.g& below 93 f 2°C (11). The range is close to that of the tetragonal phase obtained in
the present study. To confirm the metastability of the obtained samples, they were kept at room
temperature for long time under a vacuum. Figure 3 (a) shows the XRD pattern of Cut.%S
after aging the tetragonal phase at room temperature for 6 months. The extra peaks were found
Vol. 30, No. 12 COPPER CHALCOGEtNIDES 1497

-2.0T

-2.1

-2.2

02.3

-2.4

-2.5

100 200
Temperature(K)
FIG. 2
Electrical resistivity p of tetragonal Cy_$ (2-x = 1.95 and l.%)

cW.96s
3
‘2
a

28 (degrees)

FIG.3
XRD patterns of Cut.g& after aging of the tetragonal phase at room
temperature for 6 months (a), and after 30 min of MA of the aged sample (b).

20 (degrees)

FIG.4
XRD pattern of Cut.g$ after 10 months of aging at room temperature.
1498 T. OHTANI et al. Vol. 30, No. 12

to be djurleite. As shown in Fig. 3 (b), the aged sample almost entirely recovered to the
original tetragonal phase after milling for 30 min. Similar effects were observed in many
samples of the tetragonal phase. The transformation rate during aging, however, varied greatly
from sample to sample, e.g., Cut.93S changed to djurleite almost entirely by aging for 6
months (Fig. 4 shows the pattern of 10 months of aging), whereas another sample with the
same composition only partially transformed to djurleite by aging for 1 year. Further, a
sample of Cu1.95.Y showed no change even after 1 year. This may be due to differences in the
microstructures in the initial products. The samples also showed the transformation when
annealed at temperatures between 40 and 1OO’C in evacuated silica tubes. The rate of the
change was accelerated as the annealing temperature increased. These observations clearly
show that the obtained tetragonal phase is surely in the metastable state. Skinner reported that
the tetragonal phase is stable under high pressure and is capable of being quenched to room
temperature (12), i.e., the pressure-temperature diagram of Cu2S has an invariant point at
107°C and 0.8 kbars and the tetragonal phase expands from this point towards the higher
pressure region. It is most likely, thus, that the tetragonal phase was formed by MA under
high pressure and high temperature. The fact that the reactions go to completion in relatively
short time would show that the conditions generated by the high-energy milling are more than
sufficient for the formation of the tetragonal phase. This seems to be supported by the earlier
reports that the tetragonal phase often occurs in the course of the grinding used to prepare
samples for X-ray diffraction analysis (11,12). As far as we know, only a little has been
reported on the formation of me&stable high-pressure phase by MA, e.g., Han et al. obtained a
high-pressure polymorph y-Y 2S3 by milling a stable phase of 6-Y2S3 (13).

I
B
CUl.SOS

.z
5
~exagooal.
a= s-w A. c = 49.mA)
(RhOnlbohchral)
I- 60 min

10 20 30 40 50 60 70 80

213 (degrees)

FIG.5
XPD pattern of metastable rhombohedral phase of Cut.& after 60 min of MA.

Figure 5 shows the XRD pattern of Cut,-& obtained by 60 min of MA. The pattern was able
to be indexed hexagonal (rhombohedral) according to the published data (14). The calculated
lattice parameters for the hexagonal lattice were a = 3.9341 8, and c = 49.151 A. The X-ray
analysis showed that the homogeneity range extends from Cut.7fS to Cul.&L With regard to
the stability range as well as the diffraction pattern, the phase is considered to correspond to the
metastable hexagonal-tetragonal phase (Cu1,75S-CuI.mS) designated by Potter (11). and most
likely to the Cut&S II phase (Cu1,73S-Cut.&) reported by Djurle (10). Here, we refer to this
phase as rhombohedral Cu2_.$3. Aging effects were also observed in these samples. Figure
6 (a) shows the X-ray pattern of Cut.& after aging at room temperature for 2 months. The
extra peaks are djurleite. Similar patterns were found in the samples of cU1.fgs-cU1.89s.
Vol. 30, No. 12 COPPER CHALCOGENIDES 1499

Interestingly, Cut.8uS showed little change even after 6 months of aging. The pattern of the
aged sample entirely recovered to the original metastable one after 30 min of MA, as shown for
Cut.83S in Fig.6 (b). In the range of Cut.71S-Cut.79S many unknown extra X-ray peaks
appeared after aging. At the composition of Cu~75S, anilite exists as a stable phase, but the
extra peaks do not belong to anilite. The extra peaks also disappeared after 30 min of milling.
Several authors have pointed out that this metastable phase can only be synthesized in the
presence of oxygen, and hence belongs to the system Cu-O-S (11). If the phase contains
oxygen atoms, however, one can hardly explain the reversible changes between the stable and
the metastable phases, especially as observed in Cut.@-Cut.-&. Now we are planning to
perform MA under conditions without oxygen.

- CUL83S l djurleite
s.

FIG.6
XRD patterns of Cut.& after aging of the rhombohedral phase at room temperature
for 2 months under a vacuum (a), and after 30 min of MA of the aged sample (b).

CuS (covellite) was synthesized by 60 min of MA. MA for the starting compositions
between CuS and CuS2 resulted in the formation of two-phase mixtures of CuS and S. The
metastable high-pressure phase of CUR reported in the literatures was not obtained by MA for
periods longer than 180 min.

CODDN selenides

Several copper selenides were successfully prepared by MA. Figure 7 shows the XRD
pattern of 6 Cut.75Se obtained by 60 min of MA. Contrary to the sulfides, the pattern shows
rather good crystallinity. The peak intensity is comparable to that of the samples prepared by
normal high temperature synthesis. X-ray analysis revealed that the phase is homogeneous
from Cu t.+e to Cut.&e. According to Heyding (IS), Cq_$e (1.75 5 2-x 5 2.0) has two
polymorphs of a and p; the fi phase is stable above ca. 13O’C at CuZSe and the a-p transition
temperature decreases with departure from the stoichiometry; at room temperature. the fl phase
is stable only in a very narrow composition range centered at ca.Cut&e. The rather wide
homogeneity range of the fl phase obtained in the present studies would show that the reactions
occurred at relatively high temperatures, and thus the p phase was quenched to room
temperature probably due to the slow a-p transition as previously reported (16).
1500 T. OHTANI et al. Vol. 30, No. 12

Figure 8 gives temperature variations of resistivity p of p Cu2_,_Se prepared by 60 min of

MA, where the samples of 2 - x = 1.70 and 1.73 are mixed phases. The samples show metallic
behaviors. Although as-pressed pellets were used for the measurements, the values of p are
comparable to those of sintered pellets of p Cy_$e which were separately prepared by heating
the elements in silica tubes. It is notable that Cu1,75Se shows a drop of p below ca. 8 K,
indicative of a superconductivity. In addition, a small drop of pis found in Cur&Se below 4
K. However, the reproducibility of superconductivity was poor. The appearance ,of
superconductivity seems to originate from strongly stressed surface states generated during
MA, which would produce high pressure locally or the second phase, sensitively depending on
the preparation conditions. Similar behaviors were observed in bundled filamentary single
crystals of NbSe3, where the superconductivity of educed metals occurs along the crystal chain
direction (17). Figure 8 shows an anomaly at ca.160 K in every sample, suggesting the
presence of a phase transition. We observed that the anomaly is associated with the first order

r : 3 P Cu75Se
(Cubic,a = 5.7~7 A)

60 min

50 $0 70 80

20 (degrees)

FIG.7
XRD pattern of b Cu 1.-&e prepared by 60 min af MA.

-3.6

E -3.8
e
Q -4.0

g -4.2

100 200
Temperature(K)

FIG.8
Temperature variations of resistivity p of fI Cu&Se prepared by 60 min of MA.
Vol. 30, No. 12 COPPER CHALCOGENIDES 1501

structural change by electron microscopic study. The details of the transition will be reported
elsewhere.

Figure 9 shows the XRD pattern of CusSe;! prepared by 60 min of MA. The pattern shows
well crystallized state of the compound, and is consistent with the tetragonal structure reported
by Morimoto and Koto (18) and Heyding and Murray (19). Based on reference data (20),
lattice parameters were calculated to be a = 6.4161 A and c = 4.2834 A. The crystallinity was
observed to be getting better during aging at room temperature. The XRD pattern of CuSe
prepared by !vlA is shown in Fig. 10. CuSe has three polymorphs of a, p (> 51”C), and y (>
120°C) (21). The X-ray pattern belongs mainly to the y phase, suggesting that the reaction
occurs at temperatures above ca. 100°C. However, possibility of coexistence of the f3 phase
can not be excluded because the XRD patterns of p and y phases are close to each other.

I 1
10 20 30 40 M 60 70 a0

28 (degrees)

FIG. 9
XRD pattern of Cu3Se2 prepared by 60 min of MA.

28 (degrees)

FIG. 10
XRD pattern of y CuSe prepared by 60 min of MA.

CuSq has two polymorphs: a low-pressure modification with marcasite structure and a high-
pressure modification with pyrite structure (19). The 60 min of MA for CuSq formed the
two-phase mixture of y CuSe and Se, and the high-pressure phase began to appear after 90 min
1502 T. OHTANI et al. Vol. 30, No. 12

of MA. The XRD pattern of CuSe2 obtained by 120 min of MA is shown in Fig. 11. The
main peaks are consistent with those of the high-pressure polymotph; the extra peaks belong to
the low-pressure form with marcasite structure. The low-pressure marcasite phase was not
diminished by further MA, and was not increased by aging at room temperature. Bither et al.
prepared the high-pressure polymorph at 60-65 kbars (22). Based on the present results, it

CuSez K . marcasite type

s cpyritclypc. a = 6.1213 A)
5 120 min
d
I.
a
.z .
z
2

FIG. 11
XRD pattern of CuSe3 prepared by 120 min of MA.

Cui.gsTe (4

60 min

CusTe;! Z (b)
(0 ,tm,rt,mbic. a = 4.~6 A.
b:: 3.977 A. and c D 6.nS A) 60 min

FIG. 12
XRD patterns of Cut.BTe (a), and Cu3Te3 (b). which were obtained by 60 min of MA.
Vol. 30, No. 12 COPPER CHALCOGENIDES 1503

is considered that the high-pressure phase can form at the lower pressure, because the present
experimental conditions can not produce pressure as high as 60-65 kbars. According to Bither
et al., the pyrite-type CuSe2 showed superconductivity at 2.30-2.43 K (22). We could not
observe superconductivity above 2 K in the present samples, while a small drop of p was
observed below 3 K.

CoDDer tellurides

We were able to prepare Cu2_xTe and Cu3Te2 by 60 min of MA. The patterns of Cut.mTe
and Cu3Te2 are respectively shown in Fig. 12 (a) and (b). The pattern of Cut.BTe is similar
to reported one of CuZSrTe with hexagonal lattice (23, 24). But, the exact identification was
difficult because of the rather complex phase diagram around Cu2-XTe (24). It is notable that
the grinding effects were observed in Cu2_xTe (24). The pattern of Cu3Te2 is consistent with
reported one of CU~_~TQwith orthorhombic structure (space group, Pmmn) (25,26). Lattice
parameters were obtained to be a = 4.006 A, b = 3.977 A, and c = 6.126 A. Cu7Teg also
showed the XRD pattern identical with Cu3Te2. The compounds are supposed to contain
variable superstructures. However, we could not carry out the more detailed structural
analysis because of relatively poor crystahinity of obtained compounds. Copper monotelhuide
CuTe was prepared, but the XRD pattern was not found in the literature. Pyrite-type CuTe2,
which was prepared at high-pressure by Bither et al. (22), could not be obtained by MA.

Conclusions

Many copper chalcogenides (sulfides, selenides, and tellurides) were successfully synthesized
by 60-120 min of MA (high-energy ball milling process). These results are characterized by the
formation of two metastable high-pressure phases by MA: tetragonal Cut.g+-Cut.ggS and
pyrite-type CuSe2. The present results suggest that MA may provide an easy and useful
means to prepare many other metastable high-pressure phases. Further, aging effects may
provide an interesting subject for thermodyamical studies. Oxygen atoms seem to play an
important role in some products. We plan to perform MA under oxygen-free conditions. We
have been also succeeded in the preparation of many silver chalcogenides, which will be
reported elsewhere.

Acknowledgment

Thanks are expressed to Dr. Y. Yamada for helpful discussion and advices on MA. This
work was supported in part by a Grant-in-Aid for Scientific Research from the Ministry of
Education.

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