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Physica B 404 (2009) 1819–1825

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Physica B
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T(z) diagram and magnetic behavior of the Zn1zMnzIn2Te4 alloy system

M. Morocoima a, F. Pineda a, M. Quintero a,, E. Quintero a, E. Moreno a, P. Grima a, R. Tovar a,
P. Bocaranda a, J.A. Henao 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: Measurements of X-ray diffraction, differential thermal analysis (DTA) and of magnetic susceptibility w,
Received 20 September 2008 in the temperature range from 2 to 300 K, were carried out on polycrystalline samples of the
Received in revised form Zn1zMnzIn2Te4 alloy system. The X-ray diffraction patterns were used to check the equilibrium
7 February 2009
conditions and to estimate crystalline parameter values. The DTA transition temperature values were
Accepted 24 February 2009
plotted as a function of alloy composition z. The 1/w vs T curves indicated that samples in the a1 I4̄ range
(0ozo0.4) were antiferromagnetic showing ideal Curie–Weiss behavior, but for all samples in the g
Keywords: I4̄2m range (0.4ozo1) the behavior was spin-glass. The values of the Curie–Weiss temperature y
Magnetic semiconductor alloys determined from all of the 1/w vs T curves were used to give the type ordering and the degree of order of
X-ray diffraction
the Mn atoms in the several solid fields which occur in the present T(z) diagram.
Phase diagram
& 2009 Elsevier B.V. All rights reserved.
Magnetic susceptibility

1. Introduction different magnetic behavior from those showing an ordered Mn

During recent years a great deal of attention has been given to
semimagnetic semiconductor alloys whose lattice is made up in
part of substitution of magnetic ions. The understanding of
magnetic properties of these materials is important not only
because of its inherent interest as a problem in magnetism, but
also because of its impact on electrical and optical behavior of
these materials. Exchange causes novel spin-dependent phenom-
ena in such materials including giant spin-splitting of the bands,
large Faraday rotations, magnetic polarons, etc. [1]. The materials
that have been most studied are the semimagnetic semiconductor
alloys obtained from the tetrahedrally coordinated II–VI semi-
conductor compounds by replacing a fraction of the group II
cations by manganese, e.g. Cd1zMnzTe, etc. [1]. Similar alloys can
be obtained by introducing manganese into the equivalent ternary
compounds, the tetrahedrally coordinated I–III–VI2 chalcopyrites,
e.g. CuInTe2. One way of introducing Mn into these chalcopyrites
is to form alloys with MnTe, e.g. (CuIn)1zMn2zTe2. These alloys
have been investigated in some detail [2–4]. Another group of
compounds that shows the tetrahedrally bonded form and
contains Mn are the Mn–III2–VI4 compounds, e.g. MnIn2Te4,
which have a defect I4̄2m tetragonal structure closely related to
the I4̄2d [5,6]. It has been shown, for the Mn–III2–VI4 compounds,
that those in which the Mn atoms are disordered have very
 Corresponding author. Tel.: +58 274 2716979.
E-mail address: mquinter@ula.ve (M. Quintero).
arrangement. In recent work [7,8], the crystallographic and
magnetic behaviors were studied for some II–III2–VI4 compounds
and their alloys, and it was found that when the Mn and III atoms
are ordered on the cation sublattice, as in the case of MnGa2Se4,
the compound shows almost ideal antiferromagnetic behavior.
However, when the Mn and III atoms are randomly mixed in the
sublattice, as in the case of MnIn2Te4, the compound shows spin-
glass behavior. It was found that these conditions apply also in the
various alloy systems and it was shown [7,8] that values of the
Curie–Weiss constant y, determined from magnetic susceptibility
measurements, gave a very good indication of the ordered
arrangement of the Mn atoms in the various materials.
In the present work, the alloy system Zn1zMnzIn2Te4 is
investigated. Earlier crystallographic studies made on the term-
inal compounds have shown that the crystal structure of ZnIn2Te4
is a defect tetragonal chalcopyrite, space group I4̄ with crystal
parameter values a ¼ 6.119 Å and c ¼ 12.257 Å [9], while for
MnIn2Te4, the structure is defect tetragonal stannite, with space
group I4̄2m and lattice parameter values a ¼ 6.191 Å and
c ¼ 12.382 Å [5]. For the case of ZnIn2Te4, the lattice vacancies
and the In and Zn atoms are ordered on the cation sublattice, but
for MnIn2Te4, the Mn and In atoms are randomly distributed on
these sites. Here, measurements of X-ray diffraction, differential
thermal analysis (DTA) and magnetic susceptibility w as a function
of temperature T, in the range 2–300 K, were made for a wide
range of z values. From the resulting data, the type of ordering of
the Mn atoms on the cation sublattice and the T(z) phase diagram
have been obtained.

0921-4526/$ - see front matter & 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2009.02.027
 ARTICLE IN PRESS

1820 M. Morocoima et al. / Physica B 404 (2009) 1819–1825

2. Sample preparation and experimental measurements Te

Alloy samples of Zn1zMnzIn2Te4 with various values of z were

prepared by the melt and anneal technique. In each case, the
components of 1 g sample were made from appropriate amounts
of high-purity elements (Zn 99.99 wt%; Mn 99.99 wt%; In
ZnTe
99.99 wt%; Te 99.99 wt%) by sealing the elements under vacuum MnTe
(E105 Torr) in small quartz ampoules, which have previously
been carbonized to prevent interaction of the alloy with the ZnIn2Te4 MnIn2Te4
In2Te3
quartz, and melting together at 1150 1C for about 1 h in a vertical
furnace with a flat temperature profile. The furnace temperature Zn Mn
was brought slowly (4 1C/h) down to 500 1C, and the samples were
annealed at this temperature for 50 days in order to homogenize
the material. Then, the samples were slowly cooled to room
temperature (RT) using a rate of about 2 1C/h. Preliminary
scanning electron microscopy and energy dispersive (EM-EDS)
experiments carried out on the present Zn1zMnzIn2Te4 alloys In
showed that the composition of the samples were in good
agreement with the nominal stoichiometry. Similar results were Fig. 1. General composition diagram showing the Zn1zMnzIn2Te4 section
found in earlier work made on the MnIn2(1z)Ga2zSe4 system [10], investigated in this work.

using the same experimental arrangement. Details of the EM-EDS

results obtained for the present alloys will be given in a further
work.
X-ray powder photographs, taken at RT, on a KODAK DEF-392
film with a calibrated Guinier de Wolf camera (Enraf Nonious FR
552) using Cu (l ¼ 1.5406 Å) radiation, were used to check the
equilibrium conditions of each resulting sample. It was found that
the annealing period indicated above (50 days) produces speci-
mens with good equilibrium conditions. After the equilibrium
condition of the prepared sample was checked, the angular, 2y,
peak positions were measured visually with an Enraf Nonious
FR508V52 optical system. The X-ray diffraction patterns were
analyzed with the computer program DICVOL91 [11] using an
absolute error of 0.031 (2y) in the calculations, and hkl indices as
well as lattice parameter values for each sample were obtained,
silicon being used as an internal standard. The final lattice
parameter values were determined with a least square computer
program using the corrected values of 2y together with the
Fig. 2. Variation of lattice parameter a with z for Zn1zMnzIn2Te4 alloy system.
corresponding hkl indices as known parameters. It was found that
the lattice parameter values given by DICVOL91 were very similar
to those obtained from the least square fit. space groups I4̄ and I4̄2m reported previously for the terminal
Transition temperatures were determined from DTA measure- compounds [5,9]. As was indicated above, it was found that the
ments made with a Perkin-Elmer DTA 7 equipment, with gold intensities of these ordering lines did not vary with z; this result is
used as the reference material. The charge was of powdered alloys to be expected since the scattering factor of Mn is similar to that
of typical weight 50–100 mg. For each peak in the difference of Zn and the In2Te3 compound is, in the triangular composition
signal between the sample and the reference, a phase transition diagram, a common ending point for both compounds, Fig. 1. For
temperature was determined from the baseline intercept of the each sample, values of lattice parameters were determined as
tangent to the leading edge of the peak. Both heating and cooling indicated above, and the resulting variation of ‘‘a’’ with z is shown
runs were made, the average rates of heating and cooling being in Fig. 2. It is seen from Fig. 2 that, within the limits of
approximately 10 K/min. The error in determining these tempera- experimental errors, the form of a vs z is nonlinear in the
tures is of about 78 K. composition range 0ozo0.4, while that from about zE0.4 to
For each sample, magnetic susceptibility measurements as a z ¼ 1 the behavior appears to be linear. This result indicates that
function of the temperature T from 2 to 300 K were made using a the expected change from I4̄ to I4̄2m would occur around z ¼ 0.4.
Quantum Design MPMS-5 SQUID magnetometer with an external This transition will be discussed further below together with the
magnetic field of 1 102 T. Resulting 1/w versus T curves were phase diagram and magnetic data. Values of the volume V and
analyzed to give various magnetic parameters, as discussed below. the X-ray density Dx were determined and the resulting data are
shown plotted as a function of z in Fig. 3. It is observed from this
figure that the decrease of the values of Dx is consistent with the
3. X-ray and DTA results increase of V with z.
DTA measurements were made on each sample as indicated
In all cases, the X-ray photographs for the samples prepared as above and typical heating and cooling thermograms for z ¼ 0
described above showed single phase behavior. Each photograph (ZnIn2Te4) and 1 (MnIn2Te4) are shown, respectively, in Figs. 4 and 5.
showed pseudo-cubic (zinc blende) form, but with faint ordering The results of the DTA measurements are shown by the points
lines for which the intensities did not vary with z. Analysis in Fig. 6 where heating and cooling are indicated separately. The
indicated tetragonal symmetry with lattice parameter ratio c/a proposed boundaries determined from these points together with
very close to 2, and the ordering lines were consistent with the those given by X-ray and/or magnetic results, to be discussed
 ARTICLE IN PRESS
M. Morocoima et al. / Physica B 404 (2009) 1819–1825
Fig. 3. Variation of volume V (full squares) and X-ray density Dx (full circles) vs z
for Zn1zMnzIn2Te4 alloy system.
Fig. 4. Zn1zMnzIn2Te4: DTA thermograms for z ¼ 0.0. The direction of the heating
run, or cooling run, is indicated by the corresponding arrow.
Fig. 5. Zn1zMnzIn2Te4: DTA thermograms for z ¼ 1.0. The direction of the heating
run, or cooling run, is indicated by the corresponding arrow.
1821
Fig. 6. T(z) phase diagram for Zn1zMnzIn2Te4 alloy system. Open circles: DTA
heating data; full circles: DTA cooling data.
below, are shown as full lines. In the case of the MnIn2Te4
compound, in earlier DTA work [8], made on rapidly cooled
samples to RT, only two transitions were observed in the heating
run. In the present work, an additional transition is observed at
about 594 1C in the heating curve in Fig. 5; this transition will be
discussed further below. At high temperatures, above 700 1C, the
structure b is of the disordered zinc-blende type with cations and
vacancies at random on the cation sublattice, and having F4̄3m
symmetry. It is probable that the b1 phase has also a zinc-blende
structure but of different composition than b. It is to be
mentioned that small pieces of sample, with z ¼ 0.9 and 1
(MnIn2Te4), were annealed at 720 1C, and no traces of liquid
phase or melting were observed on the annealed samples. These
results would indicate that samples in the range from z ¼ 0
(ZnIn2Te4) to about zE0.9 melt incongruently, while that alloys
with z40.9 melt congruently.
4. Magnetic results
For each sample, magnetic susceptibility w measurements as a
function of temperature T were made as indicated above. It was
found that samples with zX0.7 showed a cusp at a temperature TN
which increased with increasing z, Fig. 7. As has been seen for
other similar materials [7,12], extrapolation of TN to zero gives a
value of z of about 0.2, corresponding well with the nearest
neighbor percolation limit predicted for the phase centered cubic
structure [13]. For samples with zo0.7, no cusp was observed and
the material behaved like a paramagnetic down to 2.0 K, the
lowest temperature which could be reached in the present
measurements. In Figs. 8–10, typical 1/w vs T curves obtained for
samples with z ¼ 0.4, 0.5 and 0.9 are, respectively, shown. It is
seen from Fig. 8 that in the range 0ozo0.4 the samples showed
ideal antiferromagnetic behavior, giving a linear 1/w vs T form
down to the transition temperature TN, which in this figure is
below the lower limit of temperature used. However, in the range
0.4ozo1.0, Figs. 9 and 10, the 1/w vs T curves showed deviations
from the Curie–Weiss behavior at low temperature, indicating
spin-glass behavior. In all cases, the linear regions of the 1/w vs T
graphs were extrapolated to obtain values of the Curie–Weiss
 ARTICLE IN PRESS
1822 M. Morocoima et al. / Physica B 404 (2009) 1819–1825
Fig. 7. Variation of Neél temperature TN with z for Zn1zMnzIn2Te4 alloy system.
Fig. 8. Zn1zMnzIn2Te4: variation of 1/w with temperature T for z ¼ 0.4.
Fig. 9. Zn1zMnzIn2Te4: variation of 1/w with temperature T for z ¼ 0.5.
temperature y and Curie constant C. In each case, the fitted value
of C(z) was similar to the one expected for Mn2+ (meff ¼ 5.92mB,
S ¼ 5/2). It is to be mentioned that another indication of
Fig. 10. Zn1zMnzIn2Te4: variation of 1/w with temperature T for z ¼ 0.9. 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.
spin-glass form is illustrated in the inset in Fig. 10. It can be seen
from this figure that the susceptibility 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 TN 3.4 K. The difference in the two experiments
is a common characteristic of magnetic disorder and frustration
and is the hall mark 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 [14].
As mentioned above, the curve in Fig. 8, for a sample with
z ¼ 0.4, shows a linear 1/w variation with T over the complete
range investigated, with a Curie–Weiss y value of –18 K. The
curves in Figs. 9 and 10, for the z ¼ 0.5 and 0.9 samples, are linear
down to approximately 75 K, but then deviates appreciably from
the Curie–Weiss behavior. In this case extrapolation of the linear
region of the curves gave values for y of about 45 K for z ¼ 0.5
and 90 K for z ¼ 0.9. As was shown previously [7,8], the
antiferromagnetic behavior occurs when the Mn atoms are
ordered on the cation sublattice, while disordered, random
distribution of the Mn results in the spin-glass behavior. Thus
the value of y obtained from the magnetic susceptibility
measurements gives a very good indication of the degree of order
of the Mn on the cation sublattice. The resulting variation of these
y values as a function of z is shown in Fig. 11, also shown in this
figure are the values of y obtained, in earlier work [8], for
quenched or rapidly cooled samples from 500 1C.
5. Analysis and discussion
As indicated above, the a vs z results suggested that below
400 1C, there are two single phase fields labeled a1 and g1, which
are shown in Fig. 6, both having body-centered tetragonal lattice
based on some cation ordering in the zinc-blende sublattice, but
with different arrangement of the Mn in each lattice. As will be
seen below, the values of the Curie–Weiss constant y determined
from magnetic measurements give a good indication of the
ordering of the Mn atoms in the lattice. Thus, in the present work,
the values of y shown in Fig. 11 can be used to give information on
the form of the a1 and g1 phases.
For ordered structures which have a body-centered tetragonal
structure with c/a2, based on a cubic zinc blende type subcell,
 ARTICLE IN PRESS
M. Morocoima et al. / Physica B 404 (2009) 1819–1825
Fig. 11. Variation of Curie–Weiss temperature y with z for Zn1zMnzIn2Te4 alloy
system. Full circles: slowly-cooled samples, the solid lines are to guide the eyes.
Dashed line: quenched samples (from Ref. [8]). Dash dotted line: slowly-cooled
samples of Zn1zMnzGa2Se4 (from Ref. [8]). Vertical dotted line: boundary between
a and g phases.
the anions form a cubic close-packed lattice. The cations sites
form four different pairs, the sites in each pair being identical
because of the body-centered symmetry, and these can be
conveniently labeled:
ðiÞ 0; 0; 0 and 1=2; 1=2; 1=2 ðiiÞ 1=2; 1=2; 0 and 0; 0; 1=2
ðiiiÞ 0; 1=2; 1=4 and 1=2; 0; 3=4 ðivÞ1=2; 0; 1=4 and 0; 1=2; 3=4
These positions can also be labeled according to the standard
crystallographic nomenclature, viz.
I4̄ : ðiÞ  2a ðiiÞ  2b ðiiiÞ  2c and ðivÞ  2d;
I4̄2m : ðiÞ  2a ðiiÞ  2b ðiiiÞ and ðivÞ  4d;
i.e. (iii) and (iv) must be identical.
It can be seen that when the Mn atoms are present over (a) on
only one of the four different sites (resulting in I4̄ or I4̄2m
symmetry), with antiferromagnetic exchange between the Mn
atoms, no frustration occurs, the material shows the ideal
Curie–Weiss behavior described above, and it shows antiferro-
magnetic behavior at low temperatures. For the cases when the
Mn atoms are randomly distributed over (b) three different sites
or (c) over all available sites, with antiferromagnetic interaction
between the Mn atoms, frustration will always occur, the
geometry of the occupied sites being identical with that for
face-centered cubic case.
Returning to the magnetic data, the variation of y vs z obtained
for the present slow cooled samples (solid lines) together with the
y values obtained, in earlier work [8], for quenched samples from
500 1C (dashed line) is shown in Fig. 11. It is seen from this figure
that the y values fall into two different groups showing a
discontinuity at zE0.4. This discontinuity would correspond to
the transition from the a1 phase to g1 phase shown in Fig. 6. As
was indicated above, this result is in agreement with the different
forms shown by the a vs z graph in Fig. 2, so that the a1 phase is I4̄,
while that g1 is I4̄2m. For all of the samples in the a1 phase field
(z o0.4), the 1/ w versus T curves are of type shown in Fig. 8, and
values of y are relatively low. These results indicate that, in this
field a1, the Mn atoms are ordered on the cation sublattice in such
1823
a way that magnetic frustration does not occur below the
magnetic ordering temperature TN. Thus the Mn atoms are
situated on one type of site, e.g. on site (i), or on two sites, e.g.
on (i) and (iii) sites, but not on three or four types of site since this
would result in frustration. For the space group I4̄, the occupation
of two sites, e.g. (i) and (iii), is ruled out in this case, since it
results in I4̄2d symmetry. Thus, for this I4̄ symmetry sites are
occupied as (i) 2a Zn and/or Mn, (ii) 2b In, (iii) 2c In and (iv)
2d vacancy, and frustration will not occur in agreement with the
magnetic data and the X-ray data for the ZnIn2Te4 compound [9].
The higher temperature a2 phase should show a little more
disorder. One possibility is that in this a2 phase the vacancies are
again fixed on the (iv) 2d sites, but the Zn, Mn and In on the (i)
2a, (ii) 2b and (iii) 2c sites, thus, conserving the tetragonal I4̄
symmetry. This structure model has been observed by Gastaldi
et al. in single crystal samples of ZnIn2Se4 [15].
In the case of the tetragonal I4̄2m (g) fields, for all samples in
the g1 field, the 1/w versus T curves is of the type shown in Fig. 9
and/or 10, and give values of y which are relatively high,
compared with the ones obtained for slowly cooled samples of
Zn1zMnzGa2Se4, having similar a1 full ordered I4̄ symmetry (dash
dotted line in Fig. 11) [8], but lower than those values obtained for
brine-quenched samples of Zn1zMnzIn2Te4 (dashed line in Fig. 11)
[8]. These magnetic results indicate that in both g1 and g2 the Mn
atoms are at random on the cation sublattice, resulting in spin-
glass behavior. Hence, for g1 the vacancies are ordered on the (ii)
2b, and the Mn, Zn and In atoms are at random on the (i) 2a
and (iii) 4d and (iv) 4d sites. For the g2, the site (ii) 2b can be
occupied by vacancies and Mn atoms, while, once again, the Mn,
Zn and In atoms are at random on the (i) 2a and (iii) 4d and (iv)
4d sites, i.e. in this case the Mn atoms are at random on all
cation sites, including the vacancy (ii) 2b sites. Thus, the values
of y given by the dashed line in Fig. 11 correspond to g2. It is of
interest to note that the dash dotted line in Fig. 11 also represents
the values of y that the Zn1zMnzIn2Te4 would have if the Mn
atoms are fixed on the (i) 2a sites of the common defect stannite
I4̄2m structure.
Another point of interest here is to discuss the magnetic
interactions in the present alloys. The magnetic data in Fig. 11
indicate that, for ordered body-centered tetragonal structures, the
magnetic exchange interactions should increase as the crystal-
lographic ordering of the magnetic ion is decreased. This is
consistent with the mean field theory (MFT) [16], which gives
P
y mi J i ðri Þ, mi being the number of equidistant, ri, magnetic
neighbors coupled to a chosen Mn ion by the exchange constant
Ji(ri). In the case of disordered zinc-blende magnetic alloys,
superexchange of the type Mn–VI–Mn has been found to be the
dominant mechanism responsible for the magnetic interaction
between nearest magnetic ions [1,17]. Also, it has been observed
that the contribution from magnetic nearest neighbors is higher
than the one due to farther magnetic neighbors [18,19]. Assuming
that the lattice parameter a varies very little with temperature, so
that the nearest neighbor exchange constant J1(a/O2) is the same
for both g1 and g2, the main reason for the lower values of y for g1
(solid line in Fig. 11) compared with the ones for the g2 (dashed
line) is that, in the former one, there are fewer magnetic nearest
neighbors, since, as was discussed above, for the g1 phase the Mn
atoms cannot occupy the (ii) 2b sites, resulting in a reduction of
the number of nearest neighbors from m1 ¼ 12 for g2 to m1 ¼ 8
for g1. Regarding the much lower y values observed for the
Zn1zMnzGa2Se4-a1 (I4̄) samples (dash dotted line in Fig. 11), as
mentioned above, in this ordered I4̄ structure of the a1 phase, the
Mn atoms are fixed at (i) 2a sites, so that in this structure each
Te anion is surrounded by two In, one Mn and one vacancy, and in
this case the magnetic superexchange pathways are of the type
Mn–TeyTe–Mn, and in contrast to the g1 and g2 no magnetic
 ARTICLE IN PRESS
1824 M. Morocoima et al. / Physica B 404 (2009) 1819–1825
Fig. 12. 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) versus (TfT)/Tf, the line represents the fit to Eq. (2).
contact of the type Mn–Te–Mn occurs in the a1 structure. Hence,
the smaller values of y would be due to the lack of superexchange
of the type Mn–Te–Mn, and that the closest magnetic neighbors
are separated by a distance (r2 ¼ a) which corresponds to the
second neighbors in the structure of the g1 and/or g2, i.e. J1 is
absent in a1. Furthermore, there are fewer neighbors connected
by J2, J3 and J4 (m2 ¼ 4, m3 ¼ 8 and m4 ¼ 4 for a1 compared
to m2 ¼ 6, m3 ¼ 24 and m4 ¼ 12 for the present g I4̄2m or for
zinc-blende F4̄3m).
We come back to the MnIn2Te4 and the additional transition
observed at about 594 1C in the DTA heating curve in Fig. 5. It is
seen from Fig. 6 that this transition was also observed for samples
in both a and g phase fields, i.e. it extends across the whole
composition range, with temperature decreasing, in each field, as
z is decreased. One possibility for the structure above this
transition is that the g2 as well as the a2 would disorder totally
and hence become zinc-blende. However, this transformation is
ruled out since, as indicated above, the disordered zinc-blende
b phase is present above 700 1C. This result would suggest that
these transitions involve the transformations of the g2 and a2 into,
respectively, (b+g2) for z40.4 and (a2+b) for zo0.4, so that there
exists, at about700 1C, a horizontal phase boundary where both
(b+g2) and (a2+b) transform into zinc-blende b, as illustrated in
Fig. 6.
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 introduced a
spin-glass order parameter q as a function of temperature T [20].
Based on the appropriate form of the MFT, Sherrington and
Kirkpatrick predicted that the spin-glass order parameter q(T)
vanishes at the freezing temperature Tf and it is proportional to
(1T/ Tf) below Tf [21,22]. 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 [23]:
T wðTÞ
qðTÞ ¼ 1 
C SG þ ySG wðTÞ
Thus, in the present work, it was of interest to estimate, when
possible, the order parameter q(T) and Tf. Fig. 12 shows a typical
q(T) curve obtained using the data, for z ¼ 0.9, shown in the inset
of Fig. 10, with CSG ¼ 1.42  103 emu K/g and ySG ¼ 7.5 K. It is
seen that the value of q(T) drops to zero at Tf E3.45 K, which is
very similar to the one given by the maximum in the cusp of the
ZFC curve. In the inset of Fig. 12, the normalized order parameter
q(T/Tf) is plotted versus the normalized temperature (TfT)/Tf
together with the resulting data fitted by the equation:
qðT=T f Þ ¼ q0 ðT=T f Þ þ aððT  T f Þ=T f Þb (2)
From the fit it was obtained q0 ¼ 0.04170.004, a ¼ 0.96070.006
and b ¼ 1.1870.01, close to the values predicted by the MFT [22].
6. Conclusions
The results show that, at the higher temperatures, there is one
single solid phase field with the zinc-blende b structure. At lower
temperatures, several tetragonal ordered structures occur, i.e., a
defect chalcopyrite (thiogallate) a (I4̄) and a defect stannite g
(I4̄2m) types of structures. This is due to that the ordering of the
Mn atoms appears to occur at different temperatures from that for
the other cations. The magnetic results show that samples in the
a1, the Zn and Mn are arranged at random on the site (i) 2a
positions, and no magnetic frustration occurs, resulting in normal
antiferromagnetic behavior. For samples in the g1 and/or g2, the
Mn atoms are found to be disordered through, respectively, three
or all four of the different possible cation site positions, resulting
in spin-glass behavior. The variation of the order parameter q(T)
was found to be typical of a spin-glass state, giving parameter
values in good agreement with the prediction of the MFT.
Acknowledgments
This work was partially supported by the CDCHT-ULA (Project
nos. C-1547-08-05-B, C-1436-06-05-AA, C-1437-06-05-Ed, C-
1438-06-05-F and C-1532-07-05-B). Thanks are due to the Plan
de Desarrollo de Talento Humano de Alto Nivel of FONACIT,
through contract no. 2008002062, Venezuela. Also, the authors
would like to thank Dr. A.E. Mora, Dr. J.M. Briceño and Mr. J.L.
Fernandez for their assistance in the chemical analysis work.
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