ARTICLE IN PRESS

Journal of Physics and Chemistry of Solids 71 (2010) 993–998

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Journal of Physics and Chemistry of Solids

journal homepage: www.elsevier.com/locate/jpcs

Magnetic properties for the Cu2MnSnSe4 and Cu2FeSnSe4 compounds

E. Quintero a, M. Quintero a,n, E. Moreno a, L. Lara a, M. Morocoima a, F. Pineda a, P. Grima a,
R. Tovar a, P. Bocaranda a, J.A. Henao b, M.A. Macı́as b
a
Centro de Estudios de Semiconductores, Departamento de Fı́sica, Facultad de Ciencias, Universidad de Los Andes, Mérida 5101, Venezuela
b
Grupo de Investigación en Quı́mica Estructural (GIQUE), Facultad de Ciencias, Escuela de Quı́mica, Universidad Industrial de Santander,
Apartado aéreo 678, Bucaramanga, Colombia

a r t i c l e in fo abstract

Article history: Magnetic susceptibility w measurements in the range from 2 to 300 K were carried out on samples of
Received 21 October 2009 the Cu2FeSnSe4 and Cu2MnSnSe4 compounds. It was found that Cu2FeSnSe4 was antiferromagnetic
Received in revised form showing ideal Curie–Weiss behavior with a Néel temperature TN of about 19 K and Curie–Weiss
1 April 2010
temperature y ¼  200 K, while for Cu2MnSnSe4 the behavior was spin-glass with a freezing
Accepted 11 April 2010
temperature Tf of about 22 K and Curie–Weiss temperature y ¼  25 K. The spin-glass order parameter
q(T), determined from the susceptibility data, was found to be in agreement with the prediction of
Keywords: conventional spin-glass theory.
A. Inorganic compounds & 2010 Elsevier Ltd. All rights reserved.
A. Semiconductors
D. Magnetic properties

1. Introduction compounds by replacing the II cations with Mn, Fe, Co and/or

Magnetic semiconducting materials (MSM) are of interest
because of the manner in which the magnetic behavior associated
with the concerned magnetic ion can modify and complement the
semiconductor properties [1,2]. These MSM have received atten-
tion because of their potential application in optoelectronic and
magnetic devices. It has been found that the particular magnetic
behavior occurring in any given case depends to a large extent on
the distribution of the magnetic atoms in the lattice. Thus for
MSMs in which these atoms are at random in the cation lattice the
material mainly shows spin-glass form [1]. For MSMs, where the
arrangement of magnetic atoms on the cation lattice is regular, a
variety of magnetic states can occur, viz antiferromagnetism,
ferromagnetism, canted ferromagnetism, magnetic competition
between magnetic neighbors leading to magnetic frustration, etc.
[2,3]. The materials that have been most studied are the
semimagnetic semiconductor alloys obtained from the tetrahed-
rally coordinated II–VI semiconductor compounds by replacing a
fraction of the group II cations with a paramagnetic ion as Mn + 2,
Fe + 2, etc., giving alloys such as Cd1  zMnzTe, which show spin-
glass behavior, very large magneto-optical effects, bound mag-
netic polarons (BMPs), etc. [1,2]. It was recently suggested [3,4]
that another set of magnetic compounds and alloys, which could
show larger magneto-optical effect than the II–VI derived alloys,
can be obtained from the tetrahedral bonded I2–II–IV–VI4
n
Corresponding author. Tel.: + 58 274 2716979; fax: + 58 274 2401286.
E-mail address: mquinter10@intercable.net.ve (M. Quintero).
Ni ions. These compounds can be found in the section
(I2–IV)1  xII3xVI3 at x¼0.25 with I¼ Cu, Ag, II ¼Mn or Fe,
IV¼Ge, Sn, Pb and VI¼S, Se, Te. The crystal structure of various
I2–II–IV–VI4 compounds has been investigated by several authors
[3,4,5], and it has been found that in almost all cases, the
compounds showed either the tetrahedral tetragonal stannite
(I42m) structure based on zinc-blende, or an orthorhombic
superstructure derived from wurtzite (known as wurtz-stannite,
Pmn21).
With regard to the work done on the I2–II–IV–VI4 materials,
the crystallographic and magnetic properties of the Cu2FeGeSe4
and Cu2FeGeTe4 compounds have been given in earlier work [6],
and it was found that Cu2FeGeSe4 was antiferromagnetic with
bound magnetic polarons (BMPs) observed at low temperature,
while that the obtained results for Cu2FeGeTe4 could be analyzed
using the Néel theory of ferrimagnetism [6]. Guen and Glaun-
singer [7] measured the magnetic susceptibility, using the
Faraday method, on crystal and powder samples of Cu2MnSiS4,
Cu2MnGeS4, Cu2FeGeS4, Cu2MnSnS4, Cu2MnGeSe4 and
Cu2MnSnSe4. Their results showed that the first four compounds
were antiferromagnetic, while that the last two ones, i.e.
Cu2MnGeSe4 and Cu2MnSnSe4, were ferromagnetic. However,
according to the magnetic measurements of Chen et al. [8], which
were made using a SQUID magnetometer on 19 polycrystalline
samples of I2–Mn–IV–VI4 with I ¼Cu, Ag, IV¼Si, Ge; Sn, Pb and
VI¼Se,Te, these two compounds were found to be antiferromag-
netic. More recently, in the work made on the magnetic properties
of the Cu2Cd1  zMnzGeSe4 system [9], it was found that the
Cu2MnGeSe4 compound is antiferromagnetic. This result is in

0022-3697/$ - see front matter & 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jpcs.2010.04.010
 ARTICLE IN PRESS
994 E. Quintero et al. / Journal of Physics and Chemistry of Solids 71 (2010) 993–998
agreement with the data of Chen et al. [8], but it is in conflict with
the result of Guen and Glaunsinger [7] for this compound. The
above results suggest that the type of magnetic interaction in
some of these materials is still not clear. Hence, in the present
work the properties of the Cu2MnSnSe4 and Cu2FeSnSe4 com-
pounds are investigated. The X-ray powder diffraction studies
made on these compounds have been reported in previous works
[10,11], and it was found that, at room temperature, these
compounds have the tetragonal stannite structure (I42m), with
lattice parameter values a ¼5.7362(5) Å, c¼11.401(5) Å for
Cu2MnSnSe4 and a ¼5.7086 (2) Å, c¼11.2786 (2) Å for Cu2-
FeSnSe4. The phase transition temperatures for the Cu2MnSnSe4
and Cu2FeSnSe4 compounds have been obtained in earlier work
[11], using differential thermal analysis (DTA) measurements.
From these DTA experiments, it was concluded that both
compounds melt incongruently, with a value of the liquid
temperature TL of about 800 1C for Cu2MnSnSe4 and 675 1C for
Cu2FeSnSe4. Regarding the available magnetic data for these
compounds, as was indicated above, in the case of Cu2MnSnSe4
there are some discrepancies on the type of magnetic behavior of
this compound. Information on the magnetic parameter values for
the Cu2FeSnSe4 compound has not yet been given. Here, results of
magnetic susceptibility w measurements as a function of tem-
perature T are presented for the Cu2MnSnSe4 and Cu2FeSnSe4
compounds. In addition, magnetization measurements made on
Cu2FeSnSe4 at various temperatures are given.
2. Sample preparation and experimental techniques
The samples were produced by the melt and anneal technique. In
each case, the components of 1 g sample were sealed under vacuum
(E10  5 Torr) in a small quartz ampoule, and then the components
were heated up to 200 1C and kept for about 1–2 h, then the
temperature was raised to 500 1C using a rate of 40 K/h, and held at
this temperature for 14 h. After the samples were heated from 500 to
800 1C at a rate of 30 K/h and kept at this temperature for another
14 h, the temperature was raised to 1150 1C at 60 K/h, and the
components were melted together at this temperature, initially, for
about 1 h. The furnace temperature was brought slowly (4 K/h) down
to 600 1C, and the samples were annealed at this temperature for 1
month. Then, the samples were slowly cooled to room temperature
using a rate of about 2 K/h. Hence, the resulting as-grown samples
were investigated by X-ray powder diffraction, with a Rigaku D/MAX
IIIB diffractometer equipped with an X-ray tube (CuKa radiation:
l ¼1.5406 Å; 40 kV, 30 mA) using a diffracted beam graphite
monochromator. The X-ray diffraction patterns, obtained for each
sample, were indexed with the computer program DICVOL04 [12]
using an absolute error of 0.031 (2y) in the calculations, lattice
parameter values were estimated. The space group was established
using CHECKCELL program [13]. It was found that, for each as-grown
compound, few extra lines were observed in the diffraction pattern
and these were found to be due to the presence of small amounts of a
secondary phase [11]. Each sample, showing to be two phase, was
carefully crushed and the final powder was compressed in a new
quartz ampoule. Then, the compressed sample was re-melted at
1150 1C for about 3 or more hours, and the annealing procedure
indicated above was repeated. It was found that, for the compressed
samples, the intensities of the extra lines were considerably reduced,
and no sensible variation of lattice parameter values of the main
phase was observed for the as grown and compressed samples, both
giving similar parameter values [11]. Also, in each case, the stannite
structure I42m was observed.
Measurements of magnetic susceptibility w as a function of
temperature T in the range 2–300 K were made, on the as grown
and compressed samples, with a fixed value of magnetic field B of
100 G, using a quantum design SQUID magnetometer. The
magnetic measurements showed that, in each case, the amount
of secondary phase for the compressed samples was considerably
smaller than for the as-grown sample. For the magnetic
parameter values could be estimated for the compressed samples,
these magnetic results will be further discussed below. In the
case of Cu2FeSnSe4, measurements of magnetization M as a
function of applied field B up to 5 T were made at various fixed
temperatures.
3. Results, analysis and discussion
It was indicated above that the traces of secondary phase were
observed for each of the as grown compound, and that the
magnetic measurements showed that the amounts of any extra
phase for the compressed samples were considerably smaller than
for the as grown samples. Thus, for the as grown samples, while it
was possible to determine separate values of the magnetic
transition temperature for each phase, no values for the magnetic
parameter y or C, to be discussed below, could be estimated in
these cases. This is illustrated in Figs. 1 and 2, where the
variations of the inverse of the magnetic susceptibility 1/w with
temperature T, for as grown and compressed samples, are,
respectively, shown for Cu2MnSnSe4 and Cu2FeSnSe4. It can be
seen from Fig. 1 that, for temperatures above 50 K, the 1/w vs T
curve obtained for the as grown sample presents the typical form
shown by the secondary MnSe phase [14], while that the amount
of this extra phase is significantly reduced for the compressed
sample. Furthermore, the 1/w vs T curve obtained for the
compressed sample is linear at higher temperatures and the
extrapolation of this line to 1/w ¼0 gives a negative value of the
Curie–Weiss y   25 K indicating that this compound is
antiferromagnetic. It is also seen in the inset of Fig. 1 that the
susceptibility w measurements carried out under zero-field
cooling ZFC (heating run) and field cooling FC (cooling run) gave
different results, i.e. temperature hysteresis is observed below
Tf  22 K. The difference in the two experiments is a common
characteristic of magnetic disorder and frustration and could be a
hallmark of a spin-glass state, in which the magnetic disorder is
quenched and the interaction between spins are in conflict with
each other leading to frustration, this state will be discussed
below. For antiferromagnetic behavior, the variation of 1/w with T
above the Néel temperature TN is given by the relation [15]
1=w ¼ ðTyÞ=C ð1Þ
where y is the Curie–Weiss temperature and C the Curie constant.
The theoretical value of C is given by [15]
C ¼ NA g 2 mB 2 JðJ þ 1Þ=3KB W ð2Þ
where NA is the Avogadro number, mB the Bohr magneton and W
the molecular weight of the compound. Thus, the experimental
data for T4100 K in Fig. 1, for Cu2MnSnSe4, were fitted to the
above equation and the results were C ¼6.6  10  3 emu K/g
(which gives an experimental effective magnetic moment
mexp  5.7 mB) and y ¼  25 K. The experimental value of C is,
within the limits of the experimental errors, close to the
theoretical value C ¼7.0  10  3 emu K/g (meff ¼5.9 mB), obtained
from Eq. (2) using J¼ S¼5/2, L¼0 and g ¼2 for the Mn2 + ion, this
result indicates that the effect from MnSe is practically negligible
for the compressed sample. It is to be mentioned that the
magnetic results obtained here for the Cu2MnSnSe4, as well as
those obtained earlier for Cu2MnGeSe4 [9], are in agreement with
the ones given by Chen et al. [8], but are in conflict with those
reported by Guen and Glaunsinger [7]. From their magnetic
susceptibility results on Cu2MnSnSe4, they concluded that this
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E. Quintero et al. / Journal of Physics and Chemistry of Solids 71 (2010) 993–998 995

60000
0.030 FC Cu2MnSnSe4
Compressed sample
0.025
50000
0.020

χ (emu/g)
0.015

40000 0.010

ZFC
1/χ (g/emu) 0.005

30000 0.000
10 15 20 25 30 35
T (K)

20000

As grown sample
10000
Compressed sample

0
-50 0 50 100 150 200 250 300
T (K)

Fig. 1. Variation of the inverse of the susceptibility 1/w with temperature T for Cu2MnSnSe4. Squares: as grown sample. Circles: compressed and melted for 3 h. Inset:
variation of magnetic susceptibility w with T. The direction of the ZFC (heating run), or FC (cooling run), is indicated by the corresponding arrow.

50000 4.9 mB. This is consistent with the fact that Fe2+ often exhibits an
As-grown
orbital contribution to the magnetic moment. The main factor that
Compressed and melted for 3 h can affect the value of the magnetic parameter C, so as to give a higher
Melted for more than 3 h value than the theoretical C obtained with J¼ 4, L¼S¼2 and g¼1.5, is
40000
the mass m of the material measured, since the value determined for
Cu2FeSnSe4 w depends upon this mass m. Thus, if an amount of a secondary phase
1/χ (g/emu)

or an impurity is present, the weighed value of the sample would not

30000
20000
10000
0 ruled out here. This result together with the negative value of y
-200 -100 0 100
T (K)
Fig. 2. Variation of the inverse of the susceptibility 1/w with temperature T for
Cu2FeSnSe4. Circles: as grown sample. Squares: compressed and melted for 3 h.
Triangles: melted for more than 3 h.
compound was ferromagnetic with an experimental effective
magnetic moment mexp 4.67 mB and a positive value of y of
19.8 K. The large reduction of m from the value of spin-only
meff ¼5.9 mB for Mn + 2 was explained as possibly due to the strong
covalence of the Mn–Se bond.
It can be seen from Fig. 2 that a similar behavior occurs for as
grown and compressed samples of the Cu2FeSnSe4 compound.
However, in this case, it was found that the compressed sample
melted for 3 h gives an experimental value of C of about 1.9  10  2
emu K/g (mexp  9.6 mB), while that the sample melted for more than
3 h gave a value of 1.0  10  2 emu K/g (mexp  7 mB), which is closer
to the theoretical value C¼0.91  10  2 emu K/g (meff ¼6.7 mB)
determined from Eq. (2) using L¼S¼2, J¼4 and a
g-factor of 1.5 for the Fe + 2 ion. The measured magnetic moment of
Fe + 2 is found to be greater than the theoretical spin-only value of
be accurate for m. In this case, the mass of the main phase contained
in m will be lower than the real one resulting in a high value of C, and
hence in an apparent high value of mexp. This fact is the main reason
for the greater experimental mexp values obtained here, compared to
the full theoretical meff ¼6.7 mB obtained using J¼4 and g¼ 1.5 for
Fe2 + . In contrast to the Cu2MnSnSe4 case, it was observed that for the
Cu2FeSnSe4 compound the ZFC and FC susceptibility measurements
gave similar results showing a peak at about 19 K, i.e. no temperature
hysteresis was detected, so that spin-glass form at low temperature is
200 300 (¼  200 K) suggest that the Cu2FeSnSe4 compound is antiferromag-
netic with a Néel temperature TN of about 19 K.
Coming back to the w vs T results shown in the inset of Fig. 1
for Cu2MnSnSe4, it has been indicated above that the difference in
the ZFC and FC experiments is a common characteristic of
magnetic disorder and frustration typical of a spin-glass state, in
which the magnetic disorder is quenched and the interaction
between spins are in conflict with each other leading to
frustration. To describe the spin-glass state theoretically, Edwards
and Anderson [16] introduced a spin-glass order parameter q as a
function of temperature T. Based on the appropriate form of the
mean-field theory MFT, Sherrington and Kirkpatrick [17,18]
predicted that the spin-glass order parameter q(T) vanishes at
the freezing temperature Tf and it is proportional to (1  T/Tf)
below Tf. The value of q(T) can be extracted from the magnetic
susceptibility, but treating C and y as effective spin-glass
parameters rather than the true constants, i.e. the effective spin-
glass Curie constant CSG, and the effective spin-glass Curie–Weiss
temperature ySG, as follows [19]:
T wðTÞ
qðTÞ ¼ 1 ð3Þ
CSG þ ySG wðTÞ
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996 E. Quintero et al. / Journal of Physics and Chemistry of Solids 71 (2010) 993–998

1.2
1.0

0.8
1.0
0.6

q (T)
0.8 0.4

0.2
q (T)

0.6 0.0
0.0 0.2 0.4 0.6 0.8 1.0
(Tf-T)/Tf
0.4
Tf = 22.9 K

0.2

0.0
0 5 10 15 20 25
T (K)

Fig. 3. Variation of the order parameter q as a function of temperature T, the solid line indicates the mean field theory prediction. Inset: variation of the normalized order
parameter q(T/Tf) vs (Tf  T)/Tf , the line represents the fit to Eq. (4).

Thus, in the present work, it was of interest to estimate the 3

order parameter q(T) and Tf. Fig. 3 shows the q(T) curve obtained
2K Cu2FeSnSe4
using the w vs T data shown in the inset of Fig. 1, with
4K
CSG ¼2.45 emu K/mol Oe and ySG ¼22.3 K. It is seen that the
10 K
value of q(T) drops to zero at about Tf E22.9 K, which, as
20 K
expected, is higher than the temperature given by the maximum
2 40 K
in the cusp of the ZFC curve. In the inset of Fig. 3, the normalized
M (Am2/Kg)

order parameter q(T/Tf) is plotted vs the normalized temperature 50 K

(Tf  T)/Tf together with the resulting data fitted by the equation:
 
TTf b
qðT=Tf Þ ¼ q0 ðT=Tf Þ þa ð4Þ
Tf 1
From the fit we obtained q0 ¼0.006 70.002, a ¼1.01270.002
and b¼1.050 70.008, close to the values predicted by the mean-
field theory (MFT) [17].
Measurements of the magnetization M as a function of the
applied magnetic field B, at various fixed temperatures, were 0
made on the Cu2FeSnSe4 compound. The resulting M vs B curves
for values of B up to 5 T are shown in Fig. 4. It is seen from this 0 1 2 3 4 5
figure, that, for each temperature, the form of the M vs B curve is B (T)
linear and magnetic hysteresis was not observed. The curves
Fig. 4. Variation of magnetization M as a function of applied field B for a range of
obtained below 20 K are in the antiferromagnetic region, and temperatures.
neither spin-flop behavior and/or the saturation field could be
observed in the range of the present measurements. It is to be
crystal structure and values of y and TN are known for a given
noted that the M(B) curves do not have the typical form given by a
antiferromagnetic material, it is possible to determine values of
material showing bound magnetic polarons BMPs, and that the
the exchange interaction parameters between the various
values of M are smaller than those obtained when BMPs are
magnetic ions. The mean field theory gives the following
present in the material. This is illustrated in Fig. 5, where results
equations for y and TN [15]:
obtained at 4 K for the present Cu2FeSnSe4 together with those
reported previously for Cu2FeGeSe4 [20], Cu2Cd0.25Fe0.75GeSe4 2SðS þ 1Þ X
y¼ mi Ji ð5Þ
[21] and Cu2FeGeTe4 [21] are shown, no BMPs were observed for 3k
the Te compound. Moreover, when the data in Fig. 4 was analyzed
using the Langevin relation [20,21], it was found that good fits 2SðS þ 1Þ X
TN ¼ Zi mi Ji ð6Þ
could be obtained. However, in contrast to Cu2FeGeSe4 a 3k
temperature range where meff ¼ms could not be observed for the where the summation is over sets of equidistant magnetic neighbors
compound. Again, these results indicated that BMPs are not from a chosen magnetic atom, mi and Ji being the number and
present in the Cu2FeSnSe4 compound. exchange interaction for the ith set, S being the total spin of each
Another point of interest here is to discuss the exchange magnetic ion and Zi being +1 for antiparallel and 1 for parallel spin.
interaction parameters Ji in the present compounds. When the Values of Ji can now be obtained from Eqs. (5) and (6), but only two
 ARTICLE IN PRESS
E. Quintero et al. / Journal of Physics and Chemistry of Solids 71 (2010) 993–998
6 significant value can be given to Z. However, in analogy with the
Cu2FeGeSe4 T = 5 K
Cu2Cd0.25Fe0.75GeSe4 T = 5 K
Cu2FeGeTe4 T = 5 K
Cu2FeSnSe4 T = 4 K
4
M (Am2/Kg)
2 Mn compound.
0
0 1 2 3 4 5
B (T)
Fig. 5. Variation of magnetization M as a function of applied field B at 4–5 K. Full
squares: Cu2FeSnSe4. Open circles: Cu2FeGeSe4 (from Ref. [20]). Open triangles:
Cu2Cd0.25Fe0.75GeSe4 (from Ref. [21]). Open squares: Cu2FeGeTe4 (from Ref. [21]).
independent parameter values can be obtained. Thus, if various values
of Ji are treated as independent, as is frequently done, only two values
of Ji can be found. As it was indicated above, the present compounds
have the tetragonal stannite structure I42m. Generally, in these I2–II–
IV–VI4 materials the cation positions are I—4d, II—2a, IV—2b, so that
the Mn2 + and/or Fe2 + are on 2a. Thus, assuming that the total spin
system can be treated as two interpenetrating sub-lattices, which
have no resultant interaction between them, then the magnetic unit
cell with this spin arrangement has dimensions 2a, 2a, 2c. Values of Ji
can now be determined from Eqs. (5) and (6), but only two
independent exchange parameter values can be obtained. As it was
discussed previously [9], for a fully ordered stannite structure, such as
for the present Cu2FeSnSe4, with only J2 and J3, Eqs. (5) and (6) reduce
to y ¼A(4J2 +8J3) and TN ¼  A(4J2), where J2 and J3 are, respectively,
the nearest magnetic neighbor and next nearest magnetic neighbor
exchange interaction terms, and A¼2S(S+1)/3k. These are clearly too
approximate to give any realistic value of Ji. If another term is added,
i.e. y ¼A (4J2 +8J3 +4J4) and TN ¼ A (4J2  4J4), then, in this case, it can
be assumed that J3  J4 since r3 and r4 are close. With the values of
TN ¼20 K and y ¼ 200 K given above for Cu2FeSnSe4, and taking
S¼2 for Fe2+ , this gives J2/k¼ 4.06 K and J3/k¼ 2.81 K. The
resulting value of J2/k is about two orders of magnitude smaller than
J1/k for the II1 zMnzVI random alloys, typically J1/k 10 K [22]. This
result is possible since the value of y is of the same order of
magnitude than for II1 zMnzVI, but the number of nearest magnetic
neighbors connected by J2 for the ordered stannite is m2 ¼4
(separated by a distance d¼a) compared to m1 ¼12 (separated by
d¼a/O2) for random alloys.
Turning to the Cu2MnSnSe4, from the magnetic results it can
be concluded that this compound shows spin-glass behavior
similar to the II1  zMnzVI alloys [1,22]. The main property giving
spin-glass form is the random distribution of the corresponding
magnetic ion on the cation sub-lattice. Thus, the difference in
magnetic behavior between Cu2FeSnSe4 and Cu2MnSnSe4 can be
attributed to the fact that in the former the Fe atoms are ordered
on the cation sub-lattice while in the latter the Mn is disordered.
A similar behavior was reported for the MnIn2Te4 compound,
which also is I42m with the Mn and In atoms arranged at random
on the cation sites [23,24]. With the spin-glass behavior of this
Cu2MnSnSe4 compound, the spin orientation of the Mn ions below
Tf will be random so that Eq. (6) cannot be used, since no
997
MnIn2Te4 compound, if some fractions of Cu and/or Mn atoms are
distributed at random on the 2a and 4d sites and with the Sn
atoms fixed on the 2b position, then there will be 8 nearest
magnetic neighbors. Also, considering that the Cu2MnSnSe4 is
equivalent to a sample with z¼0.25 of the II1  zMnzVI alloys and
taking y ¼ 25 K and S ¼5/2 for Mn + 2, Eq. (5) gives J1/k¼  2.14 K
for this compound. It is seen that in this case the value of J1/k is
five times smaller than the typical one for the II1  zMnzVI alloys.
Then a possible reason for this smaller value would be that y for a
random alloy is about seven times higher than that for the present
With regard to the disorder of the Mn atoms, it is worth to
point out that two well known independent techniques are used
to investigate the local structure of a crystal: the X-ray absorption
fine structure (EXAFS) analysis and the fourier transform infra red
(FTIR) spectroscopy. Particularly, from experimental EXAFS
observations it is possible to obtain data on configuration
quantified probability deviation with respect to random conse-
quent to site occupation preferences, i.e. information on the
random distribution of the corresponding magnetic ion on the
cation sub-lattice. This knowledge is important because, as was
indicated above, site occupation preferences may affect crystal
behavior, characteristics and properties of the material.
4. Conclusions
The magnetic results suggest that Cu2MnSnSe4 is spin-glass
while Cu2FeSnSe4 shows ideal antiferromagnetic Curie–Weiss
behavior. In the case of Cu2MnSnSe4, the variation of the order
parameter q(T) was found to be typical of a spin-glass material,
giving parameter values in good agreement with the prediction of
the MFT. In the case of Cu2FeSnSe4, the saturation field and spin-
flop transitions as well as presence of BMPs were not observed in
the present M vs B measurements. The exchange integral values
estimated for the present compounds are found to be smaller than
those obtained for the II1  zMnzVI alloys. It was found that the
amounts of secondary phase present in the as grown samples
were considerably reduced for the compressed compounds.
Acknowledgements
This work was partially supported by the Consejo de
Desarrollo Cientı́fico, Humanistico y Tecnológico CDCHT-ULA
(Projects C-1436-06-05-AA, C-1437-06-05-Ed, C-1547-08-05-B,
C-1532-07-05-B and C-1630-09-05-B). Thanks are due to the Plan
de Desarrollo de Talentos Humanos de Alto Nivel of Fondo
Nacional de Ciencia, Tecnologı́a e Investigación FONACIT, through
Grant ULA-proyecto no. 2008002062 (Contract no. 200900476),
Venezuela.
References
[1] J.K. Furdyna., J. Kossut., Diluted Magnetic Semiconductors, in: R.K. Willardson,
A.C. Beer (Eds.), Semiconductors and Semimetals, vol. 25, Academic Press,
New York, 1988.
[2] Y. Shapira, E.J. McNiff. Jr., N.F. Oliveira. Jr., E.D. Honig., K. Dwight., A. Wold.,
Phys. Rev. B 37 (1988) 411.
[3] G.H. McCabe., T. Fries., M.T. Liu., Y. Shapira., L.R. Ram-Mohan., R. Kershaw., A.
Wold., C. Fau., M. Averous., E.J. McNiff. Jr, Phys. Rev. B 56 (1997) 6673.
[4] W. Shafer, R. Nitsche, Mater. Res. Bull. 9 (1974) 645.
[5] M. Quintero, A. Barreto, P. Grima, R. Tovar, E. Quintero E., G. Sanchez Porras, J.
Ruiz, J.C. Woolley, G. Lamarche, A.-M. Lamarche, Mater. Res. Bull. 34 (1999) 2263.
[6] M. Quintero, R. Tovar, A. Barreto, E. Quintero, J. González, G. Sánchez Porras, J.
Ruiz, P. Bocaranda, J.M. Broto, H. Rakoto, R. Barbaste, Phys. Status. solidi (b)
209 (1998) 135.
[7] L. Guen, W.S. Glaunsinger, J. Solid State Chem. 35 (1980) 10.
 ARTICLE IN PRESS
998 E. Quintero et al. / Journal of Physics and Chemistry of Solids 71 (2010) 993–998
[8] X.L. Chen, A.-M. Lamarche, G. Lamarche, J.C. Woolley, J. Magn. Magn. Mater.
118 (1993) 119–128.
[9] E. Quintero, M. Quintero, E. Moreno, M. Morocoima, P. Grima, J. Henao, J.
Pinilla, J. Alloys Compd. 471 (1–2) (2009) 16–20.
[10] V.P. Sachanyuk, I.D. Olekseyuk, O.V. Parasyuk, Phys. Status Solidi (a) 203
(2006) 459.
[11] E. Moreno, M. Quintero, M. Morocoima, E. Quintero, P. Grimaa, R. Tovar, P.
Bocaranda, G.E. Delgado, J.E. Contreras, A.E. Mora, J.M. Briceño, R. Avila
Godoy, J.L. Fernandez, J.A. Henao, M.A. Macı́as, J. Alloys Compd. , doi:10.1016/
j.jallcom.2009.07.066.
[12] D. Loüer, A. Boultif, J. Appl. Crystallogr. 24 (1991) 987.
[13] Jean Laugier and B. Bochu, CHEKCELL: LMGP-Suite Suite of Programs for the
interpretation of X-ray. Experiments, ENSP/Laboratoire des Matériaux et du
Génie Physique, BP 46. 38042 Saint Martin d’He res, France /http://www.
inpg.fr/LMGPS and /http://www.ccp14.ac.uk/tutorial/lmgp/S, 2002.
[14] J.B.C. Efrem D’Sa, et al., Pramana- J. Phys. 63 (2) (2004).
[15] J.S. Smart, in: Effective Field Theory of Magnetism, Saunders Company,
Philadelphia and London, 1966.
[16] S.F. Edwards, P.W. Anderson, J. Phys. F: Met. Phys. 5 (1975) 965.
[17] D. Sherrington, S. Kirkpatrick, Phys. Rev. Lett. 35 (1975) 1792.
[18] S. Kirkpatrick, D. Sherrington, Phys. Rev. B 17 (1978) 4384.
[19] T. Mizoguchi, T.R. McGuire, S. Kirkpatrick, J.R. Gambino, Phys. Rev. Lett. 38
(1977) 89.
[20] E. Quintero, R. Tovar, M. Quintero, J. González, J. Ruiz, P. Bocaranda, J.M. Broto,
H. Rakoto, R. Barbaste, J. Magn. Magn. Mater. 210 (2000) 208–214.
[21] E. Quintero, M. Quintero, M. Morocoima, P. Bocaranda, J. Appl. Phys. 102 (8)
(2007) 083905.
[22] J. Spalek, A. Lewicki, Z. Tarnawski, J.K. Furdyna, R.R. Galazka, Z. Obuszko, Phys.
Rev. B 33 (1986) 3407.
[23] K.-J. Range, H.-J. Hubner, Z. Naturf. 30b (1975) 145.
[24] M. Morocoima, F. Pineda, M. Quintero, E. Quintero, E. Moreno, P. Grima, R.
Tovar, P. Bocaranda, J.A. Henao, Physica B 404 (2009) 1819–1825.