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

Magnetic transitions in Cu2xSe 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


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 Cu2xSe 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 Cu2xSe
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

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

Cu2xSe compounds, which are, to our knowl-
Previous extensive structural, transport and edge, the first measurements of these physical
microscopic measurements of the nonstoichio- properties below 77 K. This work was partially
metric Cu2xSe have been performed mostly for motivated by the discovery of a very large
the high temperature (T>400 K) region in order to magnetoresistivity in silver selenides and tellurides
understand its high temperature phase, which is [2–4], since Cu2xSe belongs to the same group of
interesting predominantly because of its superionic compounds.
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- 2. Experimental details
tions. We present here the results for the magnetic
susceptibility, electrical resistivity, magnetoresis- The Cu2xSe samples were prepared by direct
synthesis of the precisely weighed copper and
*Corresponding author. Tel.: +385-1-460-55-44; fax: +385-
selenium, both of nominal purity 99.999%. The
1-468-03-36. nominal sample compositions were 2x=1.905,
E-mail address: hamzic@phy.hr (A. Hamzi!c). 1.82 and 1.77. The synthesis was carried out in an
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
182 A. Hamzic! et al. / Journal of Magnetism and Magnetic Materials 233 (2001) 181–186

evacuated silica tube, which was slowly heated to the susceptibility was measured during heating.
about 11001C (the melting point of Cu2Se). These results are shown in Fig. 1. In spite of some
Samples were then cooled to room temperature differences, it is evident that all the susceptibility
over about 3 days. The magnetic susceptibility was data can be divided into three temperature regions,
measured with a SQUID (in magnetic fields up to separated by a rather well-defined peak at B50 K
5 T). The magnetization curves were linear with and an increase above 170 K.
applied field. The magnetotransport properties Let us look first at the susceptibility data in the
were measured with a standard AC and DC set- intermediate temperature region, i.e. for
up, and in magnetic fields up to 9 T. 50 KoTo170 K. In accordance with the previous
discussion concerning the phase diagram, the
measured susceptibility was treated as a sum of
3. Experimental results and discussion two independent contributions (Wiederman’s law)
coming from the magnetically different phases:
Before presenting our experimental results we C
shall briefly recall that the phase diagram of the wmeas ¼ kwdia þ ð1  kÞ ; ð1Þ
T þY
Cu–Se system [5] shows the eutectic isotherm to be
at Ta C170 K: Accordingly, when a sample is where k ¼ m1 =ðm1 þ m2 Þ; and m1 and m2 are the
cooled from room temperature, a mixture of two masses of the diamagnetic Cu1.995Se and para-
aggregates form: one is the low temperature (non- magnetic Cu3Se2 phases, respectively. Such an
cubic) Cu1.995Se phase and the other one is the approach has already been used for this system
eutectoid mixture of Cu1.995Se and Cu3Se2 phases. and for temperatures above 77 K [6]; however, the
Generally, under non-equilibrium conditions, the analysis of the mixed state did not fully take into
relative ratio of the weight factors for these phases account the phase diagram.
is not only temperature, but also time dependent. Previous magnetic susceptibility measurements
However, if the sample (with a given composition of the pure Cu3Se2 compound (down to 100 K)
2x) is kept for a sufficiently long time at (or suggested [7] the existence of an antiferromagnetic
below) Ta, this ratio remains unchanged, and there ordering at To100 K, with the corresponding
are no further phase transitions as long as ToTa : Weiss temperature Y=122 K. We have assumed
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 Fig. 1. Temperature dependence of measured magnetic sus-
cooled from room temperature down to 5 K in ceptibility wmeas(T) of Cu2xSe. Numbers denote the sample
several hours, left at 5 K for at least 48 h, and then composition 2x.
A. Hamzic! et al. / Journal of Magnetism and Magnetic Materials 233 (2001) 181–186 183

that for our samples Y value is the same. Then for rise to a stronger diamagnetic contribution and
each sample first the diamagnetic contribution manifest itself as an increase of the Dw1, but this is
(wextr) was extrapolated from the wmeas vs. not observed experimentally. The second possibi-
(T+122)1 plot, and then Dw1=(wmeaswextr)1 lity could be that the Cu3Se2 phase is frozen in up
calculated. Its temperature dependence is shown in to 270 K. In this case, however, the slope of the
Fig. 2. It can be seen that the extrapolated Y Dw1 term should remain unchanged, which again
values obtained from these data agree well with is not the case. Finally, there is also the third
our initial assumption (and previous measure- option, that for temperatures between 170 and
ments [7]). Also, in accordance with Wiederman’s 270 K, the conditions for the fast crystallization of
law, the slopes of the linear Dw1 term (between 50 Cu3Se2 are particularly favourable. The cubic
and 170 K) should be inversely proportional to the Cu2xSe phase would then appear as a dominant
mass contribution of the Cu3Se2 and such depen- phase only above 270 K. Our susceptibility data
dence is indeed observed. Moreover, there is also a (cf. Fig. 2) strongly support this assumption: for
good qualitative agreement between the relative 170 KoTo270 K the slope of the Dw1 term is
ratio of the Cu3Se2 phase determined in this way reduced (which means that the quantity of Cu3Se2
and its estimation from the phase diagram. increases), whereas the Y value remains practically
When the temperature increases above 170 K, unchanged. Finally, the increase of the Dw1 above
one could, in principle, envisage several possible 270 K should be associated with the presence of
processes. The first one would be the equilibrium the Cu2xSe phase.
transition of Cu3Se2 into a new diamagnetic, but The low temperature susceptibility data of all
cubic, Cu2xSe phase. Such a process should give 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 2x=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
Fig. 2. Temperature dependence of inverse magnetic suscept- could just be the consequence of the several
ibility Dw1 ¼ ðwmeas  wextr Þ1 of Cu2xSe. 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 decreases at higher temperatures and becomes
dependence above B50 K (cf. lower part of negligible for T>100 K. All the samples obey
Fig. 3), is in line with the results found for the Kohler’s rule, with DrðBÞ=rð0ÞBB2 for Bo5 T,
resistivity of some antiferromagnetic metals above and a deviation towards aBB dependence at
TN [8]. Between 170 and 300 K there is a clear higher fields (cf. Fig. 6, where the Kohler plot is
difference between the curves obtained in cooling shown for the 2x=1.82 sample at 4.2 K).
and heating, which is the consequence of the phase The temperature dependence of the magneto-
transition above 170 K. As expected, the width of resistivity DrðBÞ=rð0Þ (for B=9 and 5 T) is shown
this hysteresis depends on the cooling (or heating) for the samples with 2x=1.905 and 1.77 in the
rate. inset of Fig. 4. Two different temperature regimes
(below and above B45 K) can be clearly distin-
3.3. Magnetoresistivity guished. At low temperatures there is no signifi-
cant difference between the two compositions, and
Further evidence for the magnetic transition the magnetoresistivity is only weakly temperature
comes from the magnetoresistivity data. The dependent. At higher temperatures the overall
magnetoresistivity curves for the 2x=1.905 DrðBÞ=rð0Þ values for the 2x=1.77 sample are
sample are shown in Fig. 4. Again, these are smaller, but, what is more important, one observes
typical curves, which do not vary much with the a faster (and the same, BT  2) decrease of the
sample composition. For all the ‘slowly cooled’ magnetoresistivity with increasing temperature. In
samples, the value of DrðB ¼ 9 TÞ=rð0Þ below any case, regardless of the different temperature
B10 K is about 3.5%. Such a small value is in variations of DrðBÞ=rð0Þ; we emphasize that the
contrast to that found for Ag–Se and Ag–Te value of the temperature separating the two
compounds [2–4], albeit belonging to the same regions agrees rather well with the susceptibility
group of compounds. The magnetoresistivity results.

Fig. 4. Temperature and magnetic field dependence of magne-

toresisitivity DrðBÞ=rð0Þ ¼ ðrðBÞ  rð0ÞÞ=rð0Þ of Cu1.905Se. In-
Fig. 3. Temperature dependence of electrical resistivity of set: temperature dependence of magnetoresistivity for Cu1.905Se
Cu1.82Se. (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) 181–186 185

3.4. The Hall effect of the susceptibility for such samples is very
difficult to analyse. On the other hand, the effects
The Hall effect was measured in the same of the thermal treatment on the transport proper-
temperature interval as the magnetoresistivity. ties are less ambiguous. The main effect of
The Hall resistivity is always linear with magnetic ‘quenching’ is that it reduces the absolute
field (up to 9 T), and the Hall constant RH is values, but it does not affect the temperature- or
positive. The corresponding number of carriers is the magnetic field variation. Consequently, the
between 2.2  1021 and 3.9  1021 cm3, i.e. its ‘quenched’ samples had smaller values of the
variation with the sample composition is rather residual resistivity and the Hall constant. For
small. The Hall constant (Fig. 5) shows a weak instance, the value of the Hall constant for the
decrease as the temperature is increased up to ‘quenched’ sample with 2x=1.82 is the same as
B50 K, and it remains temperature independent at that of the ‘slowly cooled’ sample with 2x=1.77
higher temperatures (measured for 2x=1.82 (cf. Fig. 5). However, the reduction of the r(4.2 K)
sample even up to 200 K). Such temperature and RH(4.2 K) values for the ‘quenched’ sample is
dependence strongly resembles that observed for such that the Hall mobility (defined as RH/r)
antiferromagnetic metals [9]. It should also be remains the same as for the ‘slowly cooled’ sample.
noted that a temperature independent Hall con- Similarly, the ‘quenching’ resulted in a smaller
stant (for 100 KoTo300 K) has been previously magnetoresistivity value DrðB ¼ 9 TÞ=rð0ÞC1:5%
reported as well [10], but for the samples with at 4.2 K, but both ‘quenched’ and ‘slowly cooled’
compositions closer to the stoichiometric one. sample still follow the same Kohler’s dependence
Those samples had smaller RH values, and their (cf. Fig. 6). As for the difference between the two
hole concentrations were not determined from the sets of data in Fig. 6 this is within the error in the
Hall effect data. determination of the r(0) values in two indepen-
dent measurements.

3.5. The effects of different cooling rates

4. Conclusion
Our final remark refers to the effects observed if
the samples are not cooled slowly enough. We In conclusion, we have presented magnetic and
have already stated that the temperature variation transport data for several Cu2xSe samples for
4 KoTo300 K. The observed temperature and

Fig. 5. Temperature dependence of the Hall constant of Fig. 6. The Kohler plot for Cu1.82Se sample at 4.2 K. Open
Cu2xSe. Closed symbols: ‘slowly cooled’ samples. Open symbols: ‘quenched’ sample. Closed symbols: ‘slowly cooled’
symbols: ‘quenched’ Cu1.82Se sample. sample.
186 A. Hamzic! et al. / Journal of Magnetism and Magnetic Materials 233 (2001) 181–186

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