Journal of Magnetism and Magnetic Materials 233 (2001) 181–186

Magnetic transitions in Cu2
xSe below room temperature

A. Hamzi!c*, Z. Ogorelec, K. Zadro, M. Basleti!c
Department of Physics, Faculty of Science, P.O. Box 331, 10002 Zagreb, Croatia

Received 26 September 2000

Abstract

We have measured the magnetic susceptibility, resistivity, magnetoresistivity and Hall effect of nonstoichiometric
cuprous selenide between 5 and 350 K. Our results show that below 170 K Cu2
xSe is a mixture of diamagnetic
Cu1.995Se and paramagnetic Cu3Se2. The phase diagram of the Cu–Se system, in which 170 K represents the eutectic
isotherm, governs the relative content of the two phases. For the Cu3Se2 phase a transition to an antiferromagnetic state
is observed at about 50 K, with the corresponding Weiss temperature Y=120 K. On heating above 170 K Cu2
xSe
becomes completely diamagnetic, but the transformation is slow and strongly time dependent. The complicated
magnetic behaviour is ascribed to a broad temperature hysteresis of the process. r 2001 Elsevier Science B.V. All rights
reserved.

PACS: 72.80.Jc; 75.20.
g; 75.40.Cx; 72.20.My

Keywords: Crystalline inorganic semiconductors; Magnetic susceptibility; Galvanomagnetic and other magnetotransport effects

1. Introduction tivity and Hall effect of several nonstoichiometric

Previous extensive structural, transport and
microscopic measurements of the nonstoichio-
metric Cu2
xSe have been performed mostly for
the high temperature (T>400 K) region in order to
understand its high temperature phase, which is
interesting predominantly because of its superionic
properties [1]. On the other hand, data below room
temperatures (where the superionic character is
not present) are less numerous, and they all reflect
the complexity of the structural and phase rela-
tions. We present here the results for the magnetic
susceptibility, electrical resistivity, magnetoresis-
*Corresponding author. Tel.: +385-1-460-55-44; fax: +385-
1-468-03-36.
E-mail address: hamzic@phy.hr (A. Hamzi!c).
0304-8853/01/$ - see front matter r 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 8 8 5 3 ( 0 1 ) 0 0 1 3 8 - X
Cu2
xSe compounds, which are, to our knowl-
edge, the first measurements of these physical
properties below 77 K. This work was partially
motivated by the discovery of a very large
magnetoresistivity in silver selenides and tellurides
[2–4], since Cu2
xSe belongs to the same group of
compounds.
2. Experimental details
The Cu2
xSe samples were prepared by direct
synthesis of the precisely weighed copper and
selenium, both of nominal purity 99.999%. The
nominal sample compositions were 2
x=1.905,
1.82 and 1.77. The synthesis was carried out in an
182 A. Hamzic! et al. / Journal of Magnetism and Magnetic Materials 233 (2001) 181–186
evacuated silica tube, which was slowly heated to
about 11001C (the melting point of Cu2Se).
Samples were then cooled to room temperature
over about 3 days. The magnetic susceptibility was
measured with a SQUID (in magnetic fields up to
5 T). The magnetization curves were linear with
applied field. The magnetotransport properties
were measured with a standard AC and DC set-
up, and in magnetic fields up to 9 T.
3. Experimental results and discussion
Before presenting our experimental results we
shall briefly recall that the phase diagram of the
Cu–Se system [5] shows the eutectic isotherm to be
at Ta C170 K: Accordingly, when a sample is
cooled from room temperature, a mixture of two
aggregates form: one is the low temperature (non-
cubic) Cu1.995Se phase and the other one is the
eutectoid mixture of Cu1.995Se and Cu3Se2 phases.
Generally, under non-equilibrium conditions, the
relative ratio of the weight factors for these phases
is not only temperature, but also time dependent.
However, if the sample (with a given composition
2
x) is kept for a sufficiently long time at (or
below) Ta, this ratio remains unchanged, and there
are no further phase transitions as long as ToTa :
On the other hand, when the sample is cooled
rapidly below Ta, one ends up with a mixture of
phases whose relative amounts are practically
impossible to identify and the measured magnetic
properties are difficult to interpret. In what follows
we shall present principally the data for the
samples which, we believe, are in thermal equili-
brium (the so-called ‘slowly cooled’ samples). At
the end we shall comment also on some of the
observed features when this was not the case (the
so-called ‘quenched’ samples).
3.1. Magnetic susceptibility
As the magnetic properties proved to be
particularly sensitive to the thermal treatment,
we have adopted the following procedure to ensure
equilibrium conditions. Each sample was first
cooled from room temperature down to 5 K in
several hours, left at 5 K for at least 48 h, and then
the susceptibility was measured during heating.
These results are shown in Fig. 1. In spite of some
differences, it is evident that all the susceptibility
data can be divided into three temperature regions,
separated by a rather well-defined peak at B50 K
and an increase above 170 K.
Let us look first at the susceptibility data in the
intermediate temperature region, i.e. for
50 KoTo170 K. In accordance with the previous
discussion concerning the phase diagram, the
measured susceptibility was treated as a sum of
two independent contributions (Wiederman’s law)
coming from the magnetically different phases:
C
wmeas ¼ kwdia þ ð1
kÞ ; ð1Þ
T þY
where k ¼ m1 =ðm1 þ m2 Þ; and m1 and m2 are the
masses of the diamagnetic Cu1.995Se and para-
magnetic Cu3Se2 phases, respectively. Such an
approach has already been used for this system
and for temperatures above 77 K [6]; however, the
analysis of the mixed state did not fully take into
account the phase diagram.
Previous magnetic susceptibility measurements
of the pure Cu3Se2 compound (down to 100 K)
suggested [7] the existence of an antiferromagnetic
ordering at To100 K, with the corresponding
Weiss temperature Y=122 K. We have assumed
Fig. 1. Temperature dependence of measured magnetic sus-
ceptibility wmeas(T) of Cu2
xSe. Numbers denote the sample
composition 2
x.
 A. Hamzic! et al. / Journal of Magnetism and Magnetic Materials 233 (2001) 181–186
that for our samples Y value is the same. Then for
each sample first the diamagnetic contribution
(wextr) was extrapolated from the wmeas vs.
(T+122)
1 plot, and then Dw
1=(wmeas
wextr)
1
calculated. Its temperature dependence is shown in
Fig. 2. It can be seen that the extrapolated Y
values obtained from these data agree well with
our initial assumption (and previous measure-
ments [7]). Also, in accordance with Wiederman’s
law, the slopes of the linear Dw
1 term (between 50
and 170 K) should be inversely proportional to the
mass contribution of the Cu3Se2 and such depen-
dence is indeed observed. Moreover, there is also a
good qualitative agreement between the relative
ratio of the Cu3Se2 phase determined in this way
and its estimation from the phase diagram.
When the temperature increases above 170 K,
one could, in principle, envisage several possible
processes. The first one would be the equilibrium
transition of Cu3Se2 into a new diamagnetic, but
cubic, Cu2
xSe phase. Such a process should give
Fig. 2. Temperature dependence of inverse magnetic suscept-
ibility Dw
1 ¼ ðwmeas
wextr Þ
1 of Cu2
xSe.
183
rise to a stronger diamagnetic contribution and
manifest itself as an increase of the Dw
1, but this is
not observed experimentally. The second possibi-
lity could be that the Cu3Se2 phase is frozen in up
to 270 K. In this case, however, the slope of the
Dw
1 term should remain unchanged, which again
is not the case. Finally, there is also the third
option, that for temperatures between 170 and
270 K, the conditions for the fast crystallization of
Cu3Se2 are particularly favourable. The cubic
Cu2
xSe phase would then appear as a dominant
phase only above 270 K. Our susceptibility data
(cf. Fig. 2) strongly support this assumption: for
170 KoTo270 K the slope of the Dw
1 term is
reduced (which means that the quantity of Cu3Se2
increases), whereas the Y value remains practically
unchanged. Finally, the increase of the Dw
1 above
270 K should be associated with the presence of
the Cu2
xSe phase.
The low temperature susceptibility data of all
our samples show a peak at TNB50 K, which can
be associated with the predicted [7] antiferromag-
netic N!eel temperature of Cu3Se2. However,
Cu3Se2 is only one of the phases present in the
whole sample (which quantity could be determined
only qualitatively), and the dynamics of its
transition is not known. We feel therefore that at
this point it would be too presumptuous to
elaborate further on the nature of the antiferro-
magnetic phase and its evolution above TN.
Nevertheless, additional indications for this transi-
tion could be recognized from the magnetotran-
sport measurements.
3.2. Resistivity
We first consider the electrical resistivity, shown
in Fig. 3 for the 2
x=1.82 sample (the same type
of temperature variation was found for other
compositions as well). At lowest temperatures the
resistivity is constant (the residual resistivity was,
depending on the composition, between 40 and
80 mO cm). Above 5 K the resistivity starts increas-
ing as Tn, where the value of the exponent n varies
between nX3 (at the lowest temperatures) and
np2 (as the temperature approaches TN). This
could just be the consequence of the several
scattering mechanisms operating simultaneously.
184 A. Hamzic! et al. / Journal of Magnetism and Magnetic Materials 233 (2001) 181–186
On the other hand, the observed change to a linear
dependence above B50 K (cf. lower part of
Fig. 3), is in line with the results found for the
resistivity of some antiferromagnetic metals above
TN [8]. Between 170 and 300 K there is a clear
difference between the curves obtained in cooling
and heating, which is the consequence of the phase
transition above 170 K. As expected, the width of
this hysteresis depends on the cooling (or heating)
rate.
3.3. Magnetoresistivity
Further evidence for the magnetic transition
comes from the magnetoresistivity data. The
magnetoresistivity curves for the 2
x=1.905
sample are shown in Fig. 4. Again, these are
typical curves, which do not vary much with the
sample composition. For all the ‘slowly cooled’
samples, the value of DrðB ¼ 9 TÞ=rð0Þ below
B10 K is about 3.5%. Such a small value is in
contrast to that found for Ag–Se and Ag–Te
compounds [2–4], albeit belonging to the same
group of compounds. The magnetoresistivity
Fig. 3. Temperature dependence of electrical resistivity of
Cu1.82Se.
decreases at higher temperatures and becomes
negligible for T>100 K. All the samples obey
Kohler’s rule, with DrðBÞ=rð0ÞBB2 for Bo5 T,
and a deviation towards aBB dependence at
higher fields (cf. Fig. 6, where the Kohler plot is
shown for the 2
x=1.82 sample at 4.2 K).
The temperature dependence of the magneto-
resistivity DrðBÞ=rð0Þ (for B=9 and 5 T) is shown
for the samples with 2
x=1.905 and 1.77 in the
inset of Fig. 4. Two different temperature regimes
(below and above B45 K) can be clearly distin-
guished. At low temperatures there is no signifi-
cant difference between the two compositions, and
the magnetoresistivity is only weakly temperature
dependent. At higher temperatures the overall
DrðBÞ=rð0Þ values for the 2
x=1.77 sample are
smaller, but, what is more important, one observes
a faster (and the same, BT
2) decrease of the
magnetoresistivity with increasing temperature. In
any case, regardless of the different temperature
variations of DrðBÞ=rð0Þ; we emphasize that the
value of the temperature separating the two
regions agrees rather well with the susceptibility
results.
Fig. 4. Temperature and magnetic field dependence of magne-
toresisitivity DrðBÞ=rð0Þ ¼ ðrðBÞ
rð0ÞÞ=rð0Þ of Cu1.905Se. In-
set: temperature dependence of magnetoresistivity for Cu1.905Se
(open symbols) and Cu1.77Se (closed symbols) for B=9 and 5 T.
 A. Hamzic! et al. / Journal of Magnetism and Magnetic Materials 233 (2001) 181–186
3.4. The Hall effect
The Hall effect was measured in the same
temperature interval as the magnetoresistivity.
The Hall resistivity is always linear with magnetic
field (up to 9 T), and the Hall constant RH is
positive. The corresponding number of carriers is
between 2.2  1021 and 3.9  1021 cm
3, i.e. its
variation with the sample composition is rather
small. The Hall constant (Fig. 5) shows a weak
decrease as the temperature is increased up to
B50 K, and it remains temperature independent at
higher temperatures (measured for 2
x=1.82
sample even up to 200 K). Such temperature
dependence strongly resembles that observed for
antiferromagnetic metals [9]. It should also be
noted that a temperature independent Hall con-
stant (for 100 KoTo300 K) has been previously
reported as well [10], but for the samples with
compositions closer to the stoichiometric one.
Those samples had smaller RH values, and their
hole concentrations were not determined from the
Hall effect data.
3.5. The effects of different cooling rates
Our final remark refers to the effects observed if
the samples are not cooled slowly enough. We
have already stated that the temperature variation
Fig. 5. Temperature dependence of the Hall constant of
Cu2
xSe. Closed symbols: ‘slowly cooled’ samples. Open
symbols: ‘quenched’ Cu1.82Se sample.
185
of the susceptibility for such samples is very
difficult to analyse. On the other hand, the effects
of the thermal treatment on the transport proper-
ties are less ambiguous. The main effect of
‘quenching’ is that it reduces the absolute
values, but it does not affect the temperature- or
the magnetic field variation. Consequently, the
‘quenched’ samples had smaller values of the
residual resistivity and the Hall constant. For
instance, the value of the Hall constant for the
‘quenched’ sample with 2
x=1.82 is the same as
that of the ‘slowly cooled’ sample with 2
x=1.77
(cf. Fig. 5). However, the reduction of the r(4.2 K)
and RH(4.2 K) values for the ‘quenched’ sample is
such that the Hall mobility (defined as RH/r)
remains the same as for the ‘slowly cooled’ sample.
Similarly, the ‘quenching’ resulted in a smaller
magnetoresistivity value DrðB ¼ 9 TÞ=rð0ÞC1:5%
at 4.2 K, but both ‘quenched’ and ‘slowly cooled’
sample still follow the same Kohler’s dependence
(cf. Fig. 6). As for the difference between the two
sets of data in Fig. 6 this is within the error in the
determination of the r(0) values in two indepen-
dent measurements.
4. Conclusion
In conclusion, we have presented magnetic and
transport data for several Cu2
xSe samples for
4 KoTo300 K. The observed temperature and
Fig. 6. The Kohler plot for Cu1.82Se sample at 4.2 K. Open
symbols: ‘quenched’ sample. Closed symbols: ‘slowly cooled’
sample.
186 A. Hamzic! et al. / Journal of Magnetism and Magnetic Materials 233 (2001) 181–186
field dependencies of the measured properties have
been associated with the presence of magnetically
different phases, in accordance with the phase
diagram of this system. The dynamics of their
transformation is strongly temperature- and time-
dependent.
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