ARTICLE IN PRESS

Journal of Magnetism and Magnetic Materials 321 (2009) 295–299

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Journal of Magnetism and Magnetic Materials

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

Magnetic properties for the Mn2GeTe4 compound

M. Quintero a,, E. Quintero a, D. Caldera a, E. Moreno a, M. Morocoima a, P. Grima a, D. Ferrer a,
N. Marchan a, P. Bocaranda a, G.E. Delgado b, J.A. Henao c, M.A. Macı́as c, J.L. Pinto c, C.A. Ponce d
a
Departamento de Fı́sica, Facultad de Ciencias, Centro de Estudios de Semiconductores, Universidad de los Andes, Mérida 5101, Venezuela
b
Laboratorio de Cristalografı́a, Departamento de Quı́mica, Facultad de Ciencias, Universidad de Los Andes, Mérida 5101, Venezuela
c
Grupo de Investigación en Quı́mica Estructural (GIQUE), Centro de Investigación en Biomoléculas (CIBIMOL), Facultad de Ciencias, Escuela de Quı́mica,
Universidad Industrial de Santander, Apartado aéreo 678, Bucaramanga, Colombia
d
Facultad de Ciencias Exactas y Naturales y Agrimensura, Universidad Nacional del Nordeste, Corrientes 3400, Argentina

a r t i c l e in fo abstract

Article history: Measurements of magnetic susceptibility w, in the temperature range from 2 to 300 K, and of
Received 26 May 2008 magnetization M vs. applied magnetic field B, up to 5 T, at various temperatures were made on
Received in revised form polycrystalline samples of the Mn2GeTe4 compound. It was found that Mn2GeTe4 has a Néel
22 August 2008
temperature TN of about 135 K, shows mainly antiferromagnetic behavior with a very weak
Available online 7 September 2008
superimposed ferromagnetic component that is attributed to spin canting. Also, the magnetic results
Keywords: suggest that a possible spin-glass transition takes place at TfE45 K. The spin-glass order parameter q(T),
Magnetic material determined from the susceptibility data, was found to be in agreement with the prediction of
Magnetic susceptibility conventional spin-glass theory. The M vs. B results indicated that bound magnetic polarons (BMPs)
Antiferromagnetism
occur in the compound, and that the effects from BMPs disappear at approximately 80 K. The M vs. B
curves were well fitted by a Langevin type of equation, and the variation of the fitting parameters
determined as a function of temperature. Using a simple spherical model, the radius of the BMP in the
material was found to be about 27 Å; this value is similar to the effective Bohr radius for an acceptor in
the II–IV–V2 and I–III–VI2 ternary semiconductor compounds.
& 2008 Elsevier B.V. All rights reserved.

1. Introduction the magnetic properties of the material such as the magnetization

and susceptibility curves at low temperature, etc.
Magnetic semiconducting materials (MSMs) are of interest The materials that have been most studied are the semimagnetic
because of the manner in which the magnetic behavior associated semiconductor alloys obtained from the tetrahedrally coordinated
with the concerned magnetic ion can modify and complement the II–VI semiconductor compounds by replacing a fraction of the group
semiconductor properties [1]. These MSMs have received atten- II cations with manganese, giving alloys such as Cd1zMnzTe [1].
tion because of their potential application in optoelectronic and These studies have been extended to the investigation of the
magnetic devices. It has been found that the particular magnetic tetrahedrally coordinated I–III–VI2, II–III2–VI4 and I2–II–IV–VI4
behavior occurring in any given case depends to a large extent on compounds and alloys [4–6]. Another group of semiconducting
the distribution of the magnetic atoms in the lattice. Thus, for materials, which would show similar tetrahedrally bounded form,
MSMs in which these atoms are at random in the cation lattice, are the II2–IV–VI4 compounds. These materials can also be regarded
the material mainly shows spin-glass form [1]. For MSMs, where as derived from the II–VI binaries, in which the cation has been
the arrangement of magnetic atoms on the cation lattice is substituted by two types of cations and an array of vacancies is
regular, a variety of magnetic states can occur, viz. antiferromag- introduced. The crystal structure of various II2–IV–VI4 compounds
netism, ferromagnetism, canted ferromagnetism, magnetic com- has been investigated by several workers [7], and it has been
petition between magnetic neighbors leading to magnetic indicated that three structure types exit: a distorted spinel structure
frustration, etc. [2,3]. Also, the presence of charge carries localized [8], an olivine-type structure (Mg2SiO4, space group Pnma, No. 62,
at the impurities can induce sizable magnetization in their Z ¼ 4) and a structure type with the orthorhombic space group
vicinity or within the sphere of its effective Bohr orbit, i.e. Cmmm reported for Mn2SnS4 [9].
formation of bound magnetic polarons (BMPs) [1], which affects Regarding the olivine structure of II2–IV–VI4, the anions are in
almost regular hcp disposition, the IV cations are in tetrahedral
coordination and the II cations are in distorted octahedral
 Corresponding author. Tel.: +58 274 2716979. coordinations. In the case of the magnetic olivines (II ¼ Mn, Fe
E-mail address: mquinter@ula.ve (M. Quintero). and/or Co) there are four magnetic ions per cell on 4a sites with

0304-8853/$ - see front matter & 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2008.09.003
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296 M. Quintero et al. / Journal of Magnetism and Magnetic Materials 321 (2009) 295–299

inversion symmetry and four on 4c sites with mirror symmetry,

giving various magnetic configurations at low temperature. The
magnetic properties of the Mn2SiS4 and Fe2GeS4 have been
studied by magnetization and neutron diffraction measurements,
and it was found that several different magnetic configurations in
succession going from helium to room temperature occur in these
compounds [10,11]. Neutron diffraction experiments, carried out
on olivine samples of Fe2xZnxSiO4, have revealed that, in addition
to the above magnetic configurations, short-range magnetic order
exists at low temperature [12]. The magnetic results obtained on
amorphous samples of II2SnTe4 showed that these materials
exhibit spin-glass behavior with an evident weak ferromagnetic
component observed at low temperature [13]. However, as
indicated by Mikus et al. [14], a comprehensive picture for the
magnetic properties of this group of materials is still lacking.
In the present program of work, we are studying the properties
of some II2–IV–VI4 materials with II ¼ Mn, Fe; IV ¼ Si, Ge, Sn and
VI ¼ Se, Te. The initial work on the crystallographic and magnetic
properties of Mn2GeTe4, Fe2GeTe4 and Fe2SnSe4 compounds was
already published in Ref. [15]. It was found that Mn2GeTe4 has an
orthorhombic olivine-type structure with crystallographic para-
meter values of a ¼ 13.600(1) Å, b ¼ 10.745(1) Å, c ¼ 7.775(1) Å
and V ¼ 1136.2(2) Å3. The susceptibility curve for this material
was shown but no detailed magnetic analysis was given. The aim
of the present paper is to show some results on the magnetic
properties of the Mn2GeTe4 compound.

2. Samples and measurements

The polycrystalline samples used were prepared by the usual

melt and anneal technique. The appropriate amounts of the Fig. 1. Variation of magnetic susceptibility w with T for the Mn2GeTe4 compound
component elements were melted together, at 1150 1C for 3 h, and obtained with an applied field B of 100 G. The direction of the ZFC (heating run), or
then cooled to 550 1C. After annealing at this temperature for FC (cooling run), is indicated by the corresponding arrow.
1 month, the ingot was very slowly cooled to room temperature.
An X-ray powder diffraction pattern was recorded at 300 K to check
the equilibrium conditions as well as the presence of secondary
phases and to estimate lattice parameter values. Measurements of
magnetic susceptibility w as a function of temperature T in the range
2–300 K were made with a fixed value of magnetic field B of 100 G,
using a Quantum Design SQUID magnetometer. 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 discussions

The obtained magnetic susceptibility w vs. temperature T curve

for the Mn2GeTe4 is shown in Fig. 1 for 2 KoTo300 K, and the
corresponding inverse of susceptibility 1/w vs. T curve is
illustrated in Fig. 2. The resulting curves of magnetization M vs.
applied magnetic field B obtained at various fixed temperatures
are shown in Fig. 3. It is seen from Fig. 1 that in this range of T a
transition occurs at about 45 K and below this temperature 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
Tf45 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
Fig. 2. Variation of 1/w with T for the Mn2GeTe4 compound. Inset: variation of d(1/
quenched and the interactions between spins are in conflict with w)/dT with T.
each other leading to frustration. It is seen in Fig. 2 that another
possible transition, which is clearly seen in the d(1/w)/dT vs. T
curve shown in the inset of Fig. 2, occurs at about 135 K, and, as paramagnetic state above 135 K. Also, it is found that, for data
will be suggested below, this one would involve a change from above 200 K, the reciprocal susceptibility seems to vary as
antiferromagnetic behavior between the localized Mn’s spins to a 1/wTya, with ya50 K, giving an unexpected value of m7.1 mB,
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M. Quintero et al. / Journal of Magnetism and Magnetic Materials 321 (2009) 295–299 297

involving a change from long-range antiferromagnetic behavior,

between the localized Mn’s spins, to a paramagnetic state occurs
at the Néel temperature TNE135 K, with a possible spin-glass
transition at about 45 K. Similar magnetic frustration has been
reported by Holger et al. [14] in amorphous samples of Co2SnTe4
and by Haushalter et al. [18] in samples of M2SnTe4 with M ¼ Cr,
Mn, Fe, Co. Short-range magnetic order has been observed in
samples of Fe2xZnxSiO4 [12]. To describe the spin-glass state
theoretically, Edwards and Anderson introduced a spin-glass
order parameter q as a function of temperature T [19]. Based on
the appropriate form of the mean-field theory (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 [20,21]. 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 [22]:
T wðTÞ
qðTÞ ¼ 1  (1)
C SG þ ySG wðTÞ
An effective spin-glass Curie constant (CSG ¼ 44.4 emu K/mol
Oe) and an effective spin-glass Curie–Weiss temperature
Fig. 3. Variation of magnetization M as a function of applied field B for a range of
temperatures. Full lines: fits to Eq. (3). For the sake of clarity the curve at 4 K has
(ySG ¼ 45 K) are obtained by fitting the susceptibility with the
been omitted. Curie–Weiss-like law from 55 to about 75 K (Fig. 4). Fig. 5 displays
the temperature dependence of the spin-glass order parameter
q(T). It is seen that the value of q(T) drops to zero at TfE45 K as
which is higher than the expected value for the effective magnetic was mentioned above. In the inset of Fig. 5, the normalized order
moment of Mn2+ (S ¼ 52 and meff ¼ 5.92 mB). It is to be mentioned parameter q(T/Tf) is plotted vs. the normalized temperature
that, with the present results, the reliability and/or an explanation (TfT)/Tf together with the resulting data fitted by the equation:
on this point could not be given here; in order to obtain clearer
qðT=T f Þ ¼ q0 ðT=T f Þ þ aððT  T f Þ=T f Þb (2)
information on the overall form of the 1/w vs. T curve, and hence to
understand more on this behavior, it is necessary to carry out From the fit it was obtained q0 ¼ 0.03370.0001, a ¼ 0.977
experimental work above 300 K, the upper temperature limit of 0.001 and b ¼ 1.0870.003, close to the values predicted by the
the present measurements. Nevertheless, it is to be noted that the MFT [20].
curve in Fig. 2 seems to have a form that is similar to that of a Turning to the M vs. B curves for Mn2GeTe4, it can be seen that
ferrimagnetic material with Néel temperature TN ¼ 135 K. Thus, the data in Fig. 3 showed the general form expected when BMPs
when the Néel theory of ferrimagnetism [16], C/w ¼ Tya(TNya)
(TNy)/(Ty), was used to fit the experimental curve in Fig. 2, it
was found that not good fit to the 1/w vs. T data could be obtained.
This result, together with the M vs. B data to be discussed below,
would suggest that below TN the Mn2GeTe4 is not ferrimagnetic
and, as was indicated above, instead it consists of antiferro-
magnetically couple planes of spins with a possible very weak
superimposed ferromagnetic component that could be attributed
to spin canting, and this mechanism can give similar 1/w vs. T
curve. This magnetic configuration has been observed by Bodenan
et al. [17] in samples of olivine Mn2SiSe4. It is to be mentioned
that no spontaneous magnetic moment, usually shown by
ferrimagnetics, as well as no evident magnetic hysteresis were
observed in the magnetization M vs. applied magnetic field B data
obtained at each temperature investigated; this would indicate
that the canted component is very small and that the transition at
135 K is from an antiferromagnetic to a paramagnetic state. This
transition will be further discussed below. As was indicated by
Mikus et al. [14], the explanation for the very weak ferromagnetic
component that was derived from earlier magnetic susceptibility
measurements [14,17] remains still speculative, and it may result
from local non-zero components that do not show up in the
overall magnetic structure. The M vs. B results will be discussed
further below.
Returning to the w vs. T and 1/w vs. T curves of Figs. 1 and 2,
respectively, the observed temperature hysteresis below Tf ¼ 45 K,
and the change of slope around 135 K, together with the absence
of magnetic hysteresis as well as spontaneous magnetic moment Fig. 4. Variation of 1/w(T) between 20 and 80 K. The solid line is a linear regression
in the M vs. B results would suggest that, again, a transition extrapolated to the temperature axis.
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298 M. Quintero et al. / Journal of Magnetism and Magnetic Materials 321 (2009) 295–299

Fig. 5. 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. (TfT)/Tf ; the line represents the fit to Eq. (2).

are present in the material. In this figure it is seen that the spacing
and shape of the curves are of the same regular form given
previously [23,24] for other materials showing BMP effects. From
the form of the M vs. B curves, it is seen that, within the limits
of experimental errors, the magnitude of the BMPs resultant
moment falls with increasing temperature, becoming practically
zero at about 120 K, where the linear form of the graph
corresponds to antiferromagnetic behavior. These results suggest
that the present magnetization data could be analyzed in terms of
Fig. 6. Mn2GeTe4: (a) total BMP magnetization M0 ( ¼ Nms) vs. T, (b) effective
BMPs. Thus, the M vs. B curves for BMPs can be very well fitted to moment per BMP meff vs. T and (c) susceptibility wm vs. T.
an equation of the form:

M ¼ M 0 LðxÞ þ wm B (3)
of experimental errors, and in the range where N is nearly
independent of T, the variation of ms with T is practically linear,
where the Langevin term L(x) ( ¼ coth x1/x) represents the and extrapolates to a value of about 3400 mB/BMP at T ¼ 0 K.
contribution of BMPs and the term wmB the contribution of Taking the magnetic moment for Mn2+ as 5.9 mB gives the mean
the matrix. Here, M0 ¼ Nms and x ¼ meff B/KBT where N is the number of Mn atoms in each BMP as 566. The assumption that in
number of BMPs involved, ms and meff are, respectively, the true a very simple model all Mn ions inside a spherical BMP are aligned
and effective spontaneous moments per BMP. In the Langevin and that none outside the sphere contribute gives the radius of
function, the effective moment meff determines how quickly the the BMP to be 27 Å. This value is higher than the typical effective
true moment aligns along B. Because of the effects of interaction Bohr radius for an acceptor in the II–VI materials. However, using
between the BMPs, it was proposed that meffEmsT/(T+T0 ), where T0 the standard values of eoE12 for the static dielectric constant and
represents the interaction [23]. With T0 relatively small, at mhE0.25mo for the hole effective mass, a typical value of 25 Å is
the higher temperatures investigated, to a good approximation obtained for the effective Bohr radius for an acceptor in the
meffEms. Thus, for a good approximation, the M vs. B data can be II–IV–V2 and I–III–VI2 semiconductor compounds [25], which is
analyzed in terms of Eq. (1), with M0, meff and wm used as fitting close to the value obtained here.
parameters. The resulting fitted curves are shown in Fig. 3, where
it is seen that in each case, a good fit was obtained. Values of the
fitting parameters were thus determined as a function of 4. Conclusions
temperature, and these are plotted against T in Fig. 6.
At higher temperatures, in the range where meffEms, values for The magnetic results suggest that, at about TNE135 K, the
N can be obtained from the ratio M0/meff. In Fig. 7a, values are Mn2GeTe4 compound consists of antiferromagnetically couple
shown for M0/meff ( ¼ N) as a function of T. It is seen that, within planes of spins with a very weak superimposed canted ferromag-
the limits of experimental errors, in the range 15 KpTp80 K, the netic component; similar magnetic configurations have been
value of N tends to level out and is almost constant with a mean reported earlier for this type of material. The observed tempera-
value of 5.01 104 Am2/Kg mB, this is illustrated in the inset of ture hysteresis in the susceptibility curve together with the M vs. B
Fig. 7a. This mean value of N gives a concentration of non-ionized results suggest that a spin-glass transition occurs at about 45 K.
acceptors of 5.5  1016/cm3. Using this value for N, values for ms The variation of the order parameter q(T) was found to be typical
can be obtained from the M0 values and the resultant variation of of a spin-glass state, giving parameter values in good agreement
ms with T is shown in Fig. 7b. It is seen that, within the limits with the prediction of the MFT.
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M. Quintero et al. / Journal of Magnetism and Magnetic Materials 321 (2009) 295–299 299

Acknowledgements

This work was supported by the CDCHT-ULA (Projects no. C-

1436-06-05-AA, C-1437-06-05-Ed, C-1438-06-05-F, C-1532-07-
05-B and C-1547-08-05-B) (Mérida-Venezuela) and FONACIT
(Project no. LAB-97000821).

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