Journal of Magnetism and Magnetic Materials 242–245 (2002) 201–204

Neutron diffraction and magnetotransport properties in

sulphur spinel
Sam Jin Kim, Woo Chul Kim, Chul Sung Kim*
Department of Physics, Kookmin University, Seoul 136-702, South Korea

Abstract

Magnetic properties and magnetotransport of FeCr2S4, Co0.1Fe0.9Cr2S4 and Cu0.5Fe0.5Cr2S4 have been studied using
.
X-ray and neutron diffraction, Mossbauer spectroscopy, magnetization, and magnetoresistance measurements.
.
Neutron diffraction above 10 K shows that there is no static Jahn–Teller distortion. Mossbauer spectra for
Co0.1Fe0.9Cr2S4 were recorded from 12 K to room temperature. Below the Ne! el temperature the asymmetric line
broadening was observed and considered to be dynamic Jahn–Teller effect. r 2002 Elsevier Science B.V. All rights
reserved.

.
Keywords: Mossbauer spectroscopy; Neutron diffraction; Magnetoresistance; Dynamic Jahn–Teller effect

Recently colossal magnetoresistance (CMR) effects in
sulphur spinel compounds (Fe1
xCuxCr2S4; x ¼ 0; 0.5)
have been reported, and it was suggested that the
conduction mechanism in these materials may not be
caused by the double exchange (DE) of the carriers [1].
Since the crystal and magnetic structures are different
from Mn perovskites, renewed interest has been focused
on the conduction mechanism of sulphur spinel com-
pounds. Yang et al. [2] invoked a magnetic polaron
model in FeCr2S4 on the basis of electron spin resonance
study and Greaves et al. [3] reported an unusual
reduction of the Fe magnetic moment by neutron
diffraction study. Also Min et al. [4] interpreted its
conduction mechanism by half-metallic properties. Very
recently, authors have published on Cu0.5Fe0.5Cr2S4 by
valence band photoemission study and reported mono-
valence of copper and ferric character of iron ions,
respectively [5]. Therefore it is essential to determine the
valence state and magnetic structure of iron ions in
various sulphur spinel compound to understand the
underlying backgrounds properly. Here we present the
.
results of Mossbauer experiments and compare them
with those of X-ray and neutron diffraction, magne-
*Corresponding author. Tel.: +82-2-910-4752; fax: +82-2-
910-4728.
E-mail address: cskim@phys.kookmin.ac.kr (C.S. Kim).
toresistance (MR), and SQUID magnetometry for
sulphur spinel compounds.
FeCr2S4, Co0.1Fe0.9Cr2S4, and Cu0.5Fe0.5Cr2S4 were
prepared by the direct reaction of the high-purity
elements Fe, Cr, Cu, and S in an evacuated quartz tube.
The crystal structures of the samples were examined by
X-ray diffractometer with Cu Ka radiation and neutron
diffractometer at Korea atomic energy research institute
reactor HANARO HRPD (high resolution powder
( The Mossbauer
diffractometer, l ¼ 1:8348 A). . spectra
were recorded using a conventional spectrometer of the
electromechanical type with a 57Co source in a rhodium
matrix.
The X-ray and neutron diffraction patterns for
samples exhibited cubic spinel phase for all our sulphur
spinel samples. In order to examine whether there is
static Jahn–Teller distortion in FeCr2S4, we obtained
neutron diffraction patterns from 10 to 300 K. Crystal
structure is determined to be cubic spinel of Fd3% m by
Rietveld refinement. Figs. 1(a) and (b) show the results
of neutron diffraction refinement for FeCr2S4, at 10 and
175 K, respectively. The determined lattice constants,
oxygen parameter u; Bragg factor Rb ; Rex ; and magnetic
factor Rm ; and magnetic moments of atoms are listed in
Table 1. The determined N!eel temperature TN for
FeCr2S4 from magnetization measurement was 172 K.
Fig. 1(b) shows diffraction pattern of paramagnetic
nuclear peaks. In Fig. 1(a) we could not find any other

0304-8853/02/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 8 8 5 3 ( 0 1 ) 0 1 1 6 7 - 2
202 S.J. Kim et al. / Journal of Magnetism and Magnetic Materials 242–245 (2002) 201–204

10000
(a) 100 0.3
Yobs 45.5

R ( Ω)
10 K Ycal
Intensity (arb. units)

8000

(R(0)-R(1.6 T))/R(0)
80 45.4
Yobs-Ycal
H=0 kOe 0.2
Bragg-position 45.3

R (Ω)
6000
Mag-Position
H=16 kOe
60
0 2 4 6 8 10
4000 H (kOe)
0.1
40
2000

20
0 0.0

150 200 250 300

10000
(a) T (K)
(b) Yobs
8000
175 K
Ycal 1.41
2.00
Intensity (arb. units)

Yobs-Ycal

µB
1.40
Bragg-position
6000 1.60

µB / formula
1.39
4 8 12 16 20
4000 1.20
T (K)

0.80
2000

0.40
0

0.00
20 40 60 80 100 120 140 0 50 100 150 200 250
2θ (degree) (b) T (K)

Fig. 1. Refined neutron diffraction patterns of FeCr2S4: (a)
10 K, and (b) 175 K. Solid circle and continuous lines represent
the observed, calculated and difference (obs–calc) profiles,
respectively. Tick marks show the position nucleus (upper) and
magnetic (lower) reflections.
Fig. 2. Temperature dependence of Co0.1Fe0.9Cr2S4 (a) resis-
tance R and MRH at 16 kOe, where MRH ¼ ðRð0Þ

Rð1:6TÞÞ=Rð0Þ; (b) magnetization under H ¼ 5 kOe; inset (a)
shows field scanning of MR RðHÞ vs. H at 192 K; inset (b)
shows enlarged shape around 12 K.

shown in temperature range between 140 and 178 K,

Table 1 while semiconducting behavior is shown in T > 178 K
Results of refinement parameters of neutron diffraction on and To140 K. The N!eel temperature TN ; which is
FeCr2S4. [Fd3% m; Fe(8a), Cr(16d), S(32e; (u,u, u)] indicated by an arrow on the magnetization curve, was
10 K 175 K 178 K. The MR peak (TM ) was 192 K with its MR ratio
8% at H ¼ 1:6 T. At temperatures above TM ; the
(
a (A) 9.9756(3) 9.9813(3) resistance data for the samples FeCr2S4 and Co0.1-
u (S) 0.3834(3) 0.3843(3) Fe0.9Cr2S4 exhibit an activated behavior which can be
mB (Fe) 3.52
fitted well by the Arrhenius formula RðTÞ ¼
mB (Cr)
2.72
Rexp 3.76% 3.66% R0 expðEr =kB TÞ: The activation energies for the samples
Rb 4.62% 4.45% FeCr2S4 and Co0.1Fe0.9Cr2S4 are 46 and 63 meV,
Rm 4.97% respectively. This result for FeCr2S4 is in good agree-
ment with the value reported previously by Ramirez [1],
while for the Co0.1Fe0.9Cr2S4 sample it is increased by as
much as 17 meV. The inset of Fig. 2(a) shows the field
different positions of magnetic superstructure peaks dependence of resistance of Co0.1Fe0.9Cr2S4 at 192 K. As
other than the nuclear peaks. Namely, all magnetic increasing external magnetic field, resistance decreases
peaks are overlapped on nuclear peaks. Therefore, it is linearly. This means a gradual increase of the magne-
concluded that the intersublattice superexchange inter- tization on application of the magnetic field. But the
action of Fe(A)–Cr(B) is antiferromagnetic, while dominant grain boundary MR effects are not shown.
intrasublattice superexchange interaction of Fe(A)– This is to be compared to GMR multilayer materials
Fe(A) and Cr(B)–Cr(B) is ferromagnetic, respectively. where MR in order of 10% at 100 Oe has been achieved
Figs. 2(a) and (b) show the temperature dependence in Permalloy/Au multilayers [6]. The inset of Fig. 2(b)
of zero-field resistance, resistance measured in the field shows the enlarged shape of magnetization between 4
of 1.6 T, magnetoresistivity defined as MRH ðTÞ ¼ and 20 K. This cusp-like anomaly at 9 K is explained by
½Rð0Þ
Rð1:6TÞ=Rð0Þ; and SQUID magnetization for changing from static to dynamic Jahn–Teller stabiliza-
Co0.1Fe0.9Cr2S4, respectively. Metallic behavior is tion [7].
 S.J. Kim et al. / Journal of Magnetism and Magnetic Materials 242–245 (2002) 201–204 203

0 250 3.0
178 K H hf
10
200 EQ 2.5
20

0 2.0

H hf (kOe)

EQ (mm/s)
150
120 K 1.5
5
ABSORPTION (%)

100
10 1.0
0
50
80 K 0.5
5

0 0.0
10
0 0 40 80 120 160

50 K T (K)
5
Fig. 4. Temperature dependence of magnetic hyperfine fields
10 and quadrupole splittings of Co0.1Fe0.9Cr2S4.
0
5 12 K
10
4.0
-8 -6 -4 -2 0 2 4 6 8
VELOCITY (mm/s) 3.0
µB / formula

TN : 357K
.
Fig. 3. Mossbauer spectra of Co0.1Fe0.9Cr2S4 at various tem-
2.0
peratures.

1.0

In order to study the conduction mechanism and local 0.0

.
properties on Co0.1Fe0.9Cr2S4, Mossbauer spectra of the
sample were measured at various absorber temperatures
from 12 K to room temperature. Some of the represen-
tative spectra for Co0.1Fe0.9Cr2S4 are shown in Fig. 3.
.
We analyzed the Mossbauer spectra using an eight
Lorentzian fitting. The detailed procedures are expressed
in Ref. [8]. Fig. 4 shows the temperature dependence of
magnetic hyperfine fields Hhf and electric quadrupole
splittings DEQ for Co0.1Fe0.9Cr2S4, respectively. The
isomer shift at room temperature is 0.60 mm/s relative to
Fe metal, which means that the charge of Fe ions is
ferrous in character. In this sample the magnetic
structure is ferrimagnetic and there are no iron species
other than Fe2+. We note that quadrupole splitting EQ
rapidly decreases with increasing temperature. In the
tetrahedral site, the ground state of Fe2+ is a degenerate
orbital doublet 5 Eg : This situation is unstable and must
be resolved via a Jahn–Teller distortion, which may
explain the observed appearance of quadrupole splitting
below TN : However, the low temperature neutron
diffraction patterns for FeCr2S4 in Fig. 1 showed that
no static Jahn–Teller distortion appeared below 77 K
[9,10]. Even though no static Jahn–Teller distortion is
observed, dynamic Jahn–Teller distortion can cause a
quadrupole shift if the distortion relaxes between a
number of equivalent crystal axes [11]. This kind of
100 200 300 400
T (K)
Fig. 5. Temperature dependence of magnetization under
H ¼ 5 kOe for Cu0.5Fe0.5Cr2S4.
relaxation consists of the asymmetrical line broadening
apparent in Fig. 3.
We also note that unusual increasing is observed in
Hhf below 80 K as temperature increased. The unusual
increasing of magnetic hyperfine field below 80 K may
be explained in terms of cancellation effect between the
mutually opposite HL and HC [12]. Here HL and HC are
the orbital current field and the Fermi-contact field,
respectively.
On the other hand, we have studied the effects of
substitution of Fe with Cu ions. Fe ions are substituted
with Cu ions up to 50%, and we have studied how the
MR effects occur. Resistivity measurement showed a
very similar behavior as in Ref. [2]. Fig. 5 shows the
temperature dependence of magnetization using VSM
for the sample Cu0.5Fe0.5Cr2S4. The saturation magne-
tization value at 80 K is 3.78 mB/atom in the H ¼ 0:5 T.
This value is greater than that of FeCr2S4 by as much as
2.35 mB/atom. Since the magnetic ions A and B are
coupled antiferromagnetically, and the spin magnetic
204 S.J. Kim et al. / Journal of Magnetism and Magnetic Materials 242–245 (2002) 201–204
moment of the Cu ion is lower than the Fe ions,
substituting Fe ions with Cu ions resulted in increasing
.
the magnetic moment. The Mossbauer data analysis also
leads to the conclusion that the iron ions are ferric. This
agrees with the previous report [13]. It is noticeable that
the iron ions are ferric in Cu0.5Fe0.5Cr2S4 while they are
ferrous in FeCr2S4 and Co0.1Fe0.9Cr2S4.
Acknowledgements
The present studies were supported by the Korea
Science and Engineering Foundation (R01-1977-00109),
and KISTEP.
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