Research Article

Received: 3 April 2009

Accepted: 23 September 2009

Published online in Wiley Online Library: 20 November 2009

(wileyonlinelibrary.com) DOI 10.1002/jrs.2542

Temperature-dependent Raman scattering

study of multiferroic MnWO4
Luc Huy Hoang,a,b Nguyen T. M. Hien,a W. S. Choi,c Y. S. Lee,d K. Taniguchi,e
T. Arima,e S. Yoon,a X. B. Chena and In-Sang Yanga
We have measured polarized Raman spectra of MnWO4 single crystals at low temperatures, and studied the temperature
dependence of the various phonon modes. From our Raman studies of the MnWO4 , a new transition temperature, 180 K, was
found. We have completely assigned the symmetries of the 18 observed Raman modes of the MnWO4 , as expected from a group
theoretical analysis. These Raman modes have been classified into three groups according to weak, intermediate and strong
temperature dependence of the modes in each group. Six internal modes have been identified by their weak temperature
dependence of the Raman wavenumbers. The temperature dependence of the wavenumbers of the Bg modes in MgO bonds,
modes of intermediate temperature dependence group, shows an anomalous behavior under 50 K. The phonon modes of
strong temperature dependence show an anomalous change at 180 K in the linewidths. This is believed to be a new transition
c 2009 John Wiley & Sons, Ltd.
temperature which involves the changes in the inter-WO6 octahedra structure. Copyright

Keywords: multiferroics; MnWO4 single crystals; Raman scattering; transition temperature

Introduction

J. Raman Spectrosc. 2010, 41, 10051010

Experimental
Single crystals of MnWO4 were grown by the floating zone
method.[8] The resulting crystal was cut and polished into a
rectangular block of 2.5 2 1 mm3 with edges parallel (within
1 ) to the crystallographic axes. The Raman spectra were excited
with the 647.1 nm line of a krypton ion laser in a back-scattering
geometry. Micro-Raman measurements were performed using

Correspondence to: In-Sang Yang, Department of Physics and Division of NanoSciences, Ewha Womans University, Seoul, 120-750, Korea.
E-mail: yang@ewha.ac.kr

a Department of Physics and Division of Nano-Sciences, Ewha Womans

University, Seoul, 120-750, Korea
b Faculty of Physics, Hanoi National University of Education, 136 Xuanthuy,
Hanoi, Vietnam
c ReCOE & FPRD, Department of Physics and Astronomy, Seoul National
University, Seoul 151-747, Korea
d Department of Physics, Soongsil University, Seoul 156-743, Korea
e Institute of Multidisciplinary Research for Advanced Materials, Tohoku
University, Sendai 980-8577, Japan

c 2009 John Wiley & Sons, Ltd.

Copyright

1005

Recently, multiferroic materials that show simultaneous ordering

of charge and spin degrees of freedom have been attracting considerable attention.[1,2] Especially, studies have been focused on
magnetoelectric coupling in these materials, where the electric
polarization or magnetization could be controlled by external
magnetic field or electric field, respectively. While several mechanisms of the magnetoelectric coupling have been suggested, the
realization of ferroelectricity induced by the non-collinear spin
structure is rather fascinating. Theoretical predictions and experimental evidences have pointed out that cycloidalspiral spin
structure without centrosymmetry[3] could induce macroscopic
spontaneous polarization through the inverse of the DzyaloshinskiMoriya interaction in this class of materials.[4,5]
MnWO4 is one of the representative materials that exhibit
ferroelectricity induced by spiral spin structure together with the
perovskite RMnO3 (R = Tb and Dy) compounds.[6 8] Compared to
RMnO3 where the rare earth ion can complicate the magnetic
structure, MnWO4 has only one kind of magnetic ion (Mn2+ ) in its
crystal structure. MnWO4 has wolframite crystal structure and is
isomorphic to those of a group of tungstates (MWO4 , M = Zn, Fe,
Hg, . . .) that contain octahedral WO6 group.[1,9,10] Its CurieWeiss
constant is 75 K, but the frustrated antiferromagnetic phase
appears only below TN3 13.5 K. Below TN3 , there are two
more magnetic transitions at TN2 12.5 K and TN1 6.58 K.
So, there are three different antiferromagnetic ordered phases:
AF1 (T TN1 ), AF2 (TN1 T TN2 ) and AF3 (TN2 T TN3 )
phases.[6 8,11,12] The spontaneous ferroelectricity appears at AF2
phase only where the direction of the polarization could be
controlled by external magnetic field.[6 8]
In multiferroic materials, the close interplay between the electric
polarization and magnetic ordering is mediated by the strong
spinlattice coupling. Moreover, the spinorbit coupling should
play a role in the formation of the ferroelectricity by the spiral
spin structure. In this sense, it is essential to clarify the structural

properties for understanding the multiferroic behavior in depth. In

this paper, we investigated the lattice dynamics of MnWO4 by using
Raman spectroscopy. We assigned complete 18 Raman modes that
are expected from group theoretical analysis. The temperature
dependence of Raman wavenumbers and linewidths of MnWO4
Raman modes were analyzed. Some of the Raman phonon spectra
showed anomalous temperature-dependent behavior at 50 and
180 K, indicating a new transition temperature concerning the
structure.

L. H. Hoang et al.

Figure 1. Raman spectra of MnWO4 in two scattering geometries corresponding to Ag and Bg symmetries.

a Jobin-Yvon T64000 spectrometer with a LN2 -cooled chargecoupled device (CCD) detector. Full range spectra were obtained
in the single mode of the spectrometer with 80 m entrance slit.
The triple subtractive configuration with 50 m slit was utilized
to obtain the low wavenumber modes. A closed cycle helium
cryostat was used to vary the sample temperature from 15 to
300 K. For each measurement, the temperature was stabilized for
20 min before acquiring a spectrum. In all cases, the laser power at
the sample surface was kept low in order to minimize the heating
effect.

Results and Discussion

MnWO4 is crystallized in a wolframite structure, which belongs
to monoclinic space group P2/c and C2h point-group with two
formula units per primitive cell. By making the correlation between
site group and factor group for each site, and then eliminating
the acoustic mode, we obtain the vibrational modes of MnWO4 :
 (k=0) = 8Ag + 10Bg + 7Au + 9Bu . Among them, all of the even
(g) vibrations (8Ag and 10Bg ) are Raman active and the odd (u)
vibrations (7Au + 9Bu ) are IR active. The Raman tensors for each of
these modes are given by:


Ag =

a
0
d

0 d
b 0
0 c

, Bg =

0 e 0
e 0 f
0 f 0

Wavenumber (cm1 )
Normalized peak shift
Mode
 = (15 K 300 K )/15 K symmetry

Mode 15 K

300 K

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18

88.7
128.6
159.8
165.3

7.83E-03
1.69E-02
8.07E-03
9.59E-03

205.3
258.3
272.6
293.6
325.9
356.5
397.3
511.4
544.7
673.3
697.7
773.7
884.4

1.63E-02
6.54E-03
7.28E-03
5.42E-03
7.31E-03
7.24E-03
1.26E-03
3.90E-03
6.57E-03
7.43E-04
4.30E-04
1.55E-03
4.52E-04

89.4
130.4
161.1
166.9
179.1
208.7
260
274.6
295.3
328.3
359.1
397.8
513.4
548.3
672.8
697.4
774.9
884

Bg
Ag
Bg
Bg
Bg
Ag
Ag
Bg
Bg
Ag
Bg
Ag
Bg
Ag
Bg
Ag
Bg
Ag

(1)

1006

As derived from the Raman tensors of the respective modes, Ag

and Bg modes can be distinguished by using measurements
performed in Z(XX)Z and Z(XY)Z configurations, respectively,
where X, Y, Z denote (100), (010) and (001) crystal axes. Figure 1
shows polarized Raman spectra of MnWO4 obtained at 15 K in the
two configurations.
Although all Raman modes are strongly polarized, some of
the Ag modes are shown weakly in the spectra where they are
forbidden, and vice versa. The wavenumbers of all the Raman

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Table 1. Wavenumber of 18 Raman modes of MnWO4 at 15 and 300 K

active modes of MnWO4 at 300 and 15 K are listed in Table 1, with

their mode symmetries. It should be noted that the Bg mode at
179 cm1 (mode 5) can be observed at temperature lower than
180 K only.
First of all, we separate the internal vibration modes associated
with WO bonds of the WO6 octahedra from those associated
with MnO bond in between the octahedra. This is reasonable
since the strong electronegativity of hexavalent tungsten would
result in highly covalent WO bond than the more ionic MnO
bond.[13]

c 2009 John Wiley & Sons, Ltd.

Copyright

J. Raman Spectrosc. 2010, 41, 10051010

Temperature-dependent Raman scattering study of multiferroic MnWO4

Figure 2. Temperature dependence of the wavenumbers of the Raman modes of MnWO4 .

Table 2. Correlation diagram for the internal modes of WO6

octahedra in MnWO4
Molecular symmetry Oh
A1g
Eg
T 2g

Site symmetry C2

Space group symmetry

P2/c

A
A+B
2A + B

Ag
Ag + Bg
2Ag + Bg

J. Raman Spectrosc. 2010, 41, 10051010

Figure 3. View of the structure of the WO6 in the wolframite structure of

MnWO4 .[12] .

WO2 group of the short WOI bond from those of the longer
WOII bond that give rise to ribbons with [W2 O4 ]n composition.
The internal modes of the WO6 octahedra are listed in Table 3.
The mode 18 (Ag ) at 884 cm1 is typically assigned for symmetry
stretching of short terminal WOI bond, which correlates with
symmetry stretching A1g mode of the WO6 regular octahedron.[14]
The modes 17 (Bg ) and 16 (Ag ) are identified as asymmetric
stretching of short terminal WOI bond. They are expected to split
from the asymmetric Eg modes of the WO6 regular octahedron
by the crystalline fields. The modes 15 (Bg ), 14 (Ag ) and 12 (Ag )
can be assigned to stretching modes of the longer WOII bond of

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1007

The internal vibrations of the tightly bound ions are expected,

in general, at higher wavenumber than the external vibration.
Moreover, the internal modes should have weak temperature
dependence. The temperature dependence of the wavenumbers
of the 18 vibration modes of MnWO4 are shown in Fig. 2. The
wavenumber change () between 15 and 300 K is divided by
the wavenumber () at 15 K for each mode, which then would be
proportional to ( ln /dT).
It is clearly seen from Fig. 2 that the wavenumbers of the modes
12(Ag ), 15(Bg ), 16(Ag ), 17(Bg ) and 18(Ag ) are weakly dependent on
temperature. Therefore, we can assign these modes to the internal
modes. Based on the data of neutron diffraction of MnWO4 ,[1] we
may assume that primitive cell of MnWO4 is composed of four
WO6 octahedra. This assumption has been successfully applied to
assign the internal modes of ZnWO4 .[14] The correlation diagram
between the Oh symmetry of the WO6 octahedra, C2 site symmetry
and the P2/c space group is shown in Table 2.
Thus, group theoretical analysis shows that there are four Ag and
two Bg internal modes. From the weak temperature dependence
in Fig. 2, three Ag and two Bg modes have been assigned as
the internal modes of WO6 in MnWO4 . Therefore, one more Ag
mode needs to be assigned as the internal mode. Among the
remaining Ag modes, mode 14 (548 cm1 ) has least wavenumber
temperature dependence; we may therefore assign this mode as
the remaining internal mode.
Based on the XRD study of the CdWO4 system, the wolframite
structure can be taken as a slightly distorted octahedral structure,
where the octahedra are occupied alternatively by two different
cations OI and OII . Figure 3 shows that WO6 is separated by the

L. H. Hoang et al.

Table 3. Wavenumber of internal modes in MnWO4 and WO6 regular octahedral

WO6 [8]

Internal modes in MnWO6

Mode

Symmetry

Wavenumber (cm1 )

Wavenumber (cm1 )

Symmetry

Symmetric stretching of WOI bond

18

Ag

884.4

817

A1g

Asymmetric stretching of WOI bond

17
16

Bg
Ag

773.7
697.7

680

Eg

Stretching of WOII bond in (W2 O4 )n

15
14
12

Bg
Ag
Ag

673.5
544.7
397.3

444

T2g

Vibration

Figure 4. Temperature dependence of the wavenumber of internal modes

15, 16 and 18.

1008

the W2 O2 involved in the W2 O4 chain. These 2Ag and Bg modes

consequently arise from the splitting of the T2g bending mode of
the WO6 regular octahedron.
The wavenumbers of the internal modes are weakly dependent
on temperature. The modes 12, 14 and 17 (say, group A) are
slightly shifted to higher wavenumber as the temperature is
lowered. On the other hand, those of modes 15, 16 and 18
(group B) are anomalous in the temperature dependence (Fig. 4).
As the temperature is lowered from 180 K, these modes shift
to lower wavenumbers unlike the conventional phonons. This
anomalous behavior could be related to a phase transition at the
magnetic or electronic transition temperature,[15,16] a structural
phase transition,[17] contraction of the lattice.[18] However, in
MnWO4 , the magnetic and electronic transition temperatures are
well below 180 K. In addition to the phonon softening, we have
observed that one phonon mode (mode 5) disappeared above
180 K. Therefore, the phonon softening in our sample could be
related with microscopic structured change.
The linewidths of each internal mode at different temperatures
were obtained by assuming a convolution of two Lorentzian
curves.[14] In second-order perturbation, the temperature dependence of the linewidth arises only through cubic anharmonic interactions corresponding to decay and combination
process. The best fit to the data of six internal modes is obtained by assuming only the combination of the observed
phonon with another phonon of wavenumber  to create
a third excitation wavenumber  , where  = +  . The

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Figure 5. Temperature dependence of the linewidths of internal modes of

MnWO4 .

linewidths of six internal modes are fitted with functions of the

form:[8]


 =  0 + B n( ) n( +  )
(2)
where  0 is the linewidth at 0 K, B is a temperature independent
factor that reflects the strength of the cubic anhamornic interaction
and n() is the BoseEinstein occupation number given as
n() =

1
hc
e kB T 1

(3)

where h is Plancks constant, c is the speed of light, kB is Boltzmanns

constant and T is absolute temperature. The best fit in the case of
the internal modes (modes 12, 14, 15, 16, 17 and 18) are shown
by solid lines in Fig. 5. The resulting parameters for the internal
modes are listed in Table 4.
It is interesting to see that the fitted values for  are close
(within 10%) to some external vibrations of WO6 octahedra in
the WMnO4 structure and those for  are close to internal
vibrations of group B (modes 15, 16 and 18). The only exception
is for the mode 18, which is not restricted to the wave vectors
near the center of Brillouin zone.[14] We therefore prove that
the temperature dependence of the linewidths of the internal
modes of MnWO4 can be expressed in terms of anharmonic
interactions.
The modes in the region 260300 cm1 , which show moderate
wavenumber shift with temperature (Fig. 2), can be assigned to

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J. Raman Spectrosc. 2010, 41, 10051010

Temperature-dependent Raman scattering study of multiferroic MnWO4

Table 4. Best values of the parameters  and  obtained from

fitting Eqn (2) for the linewidths of the internal modes
Mode
18
17
16
15
14
12

(cm1 )at 15 K

 (cm1 )
(observed peak)

 = +  (cm1 )
(observed peak)

884
775
697
673
548
398

210 (209)
112 (130)
263 (260)
296 (295)
168 (167)
245 (260)

1094 ( )
887 (884)
960 (884)
969 (884)
716 (697)
643 (673)

The values in parentheses are observed Raman wavenumbers close to

the fitted values.

stretching modes of MnO bonds. The temperature dependence

of Ag and Bg modes in this region are plotted again in Fig. 6 for
detailed analysis.
It can be seen from Fig. 6 that the Raman wavenumbers of
mode 7 (Ag ) fit well by the normal wavenumbertemperature
dependence expected for anharmonic decay (solid line). The
Raman wavenumbers of modes 8 and 9 (Bg ), however, deviate
from the expected dependence below 50 K. It should be noted
that these modes involve the vibration of MnO bonds and
can be observed in cross polarization configuration only (Bg
character). Among the remaining modes of MnWO4 , modes 2
and 6 have a strong wavenumber shift with temperature. These
modes are located in the low wavenumber region and the thermal
expansions of a and c axes of MnWO4 crystalline are greater than
that of the b axis,[19] therefore, it is reasonable to assign the
modes 2 and 6 to inter-molecular vibrations along the a and c
axes.
The temperature dependence of the linewidths of modes 2
and 6 cannot be fit using Eqn (2), as shown in the Fig. 7. We can
observe anomalous changes at 180 K for both modes 2 and 6.
This may be due to the contribution from factors other than two

simple anharmonic interactions. As these modes are external to

the WO6 octahedra, such anomaly at 180 K seems to be related
to changes in the inter-WO6 octahedra structure.

Conclusions
The phonons in MnWO4 single crystals are studied by means
of Raman scattering spectroscopy. The 18 zone-center vibration
modes are assigned based on their symmetry and temperature
dependence of the Raman wavenumbers and the linewidths of the
modes. The temperature dependence of the Raman wavenumbers of these modes shows that the modes can be grouped
into three categories namely: (1) weak temperature dependence,
(2) intermediate temperature dependence and (3) strong temperature dependence. The six internal modes are identified to
be in category (1) by their weak temperature dependence of
the Raman wavenumbers. The broadening of all the internal
modes are well explained in terms of anharmonic interactions.
The modes in the category (2) can be assigned to stretching Ag
and Bg modes of MnO bonds. However, the temperature dependence of the Ag mode is normal in terms of anharmonic decay
model, whereas that of the Bg mode is anomalous below 50 K.
The temperature dependence of the linewidths of modes in category (3) shows anomalous change at 180 K. As these modes
are external to the WO6 octahedra, such anomaly at 180 K
seems to be related with changes in the inter-WO6 octahedra
structure.
Acknowledgements
I. S. Y. acknowledges the National Research Foundation of Korea
Grant funded by the Korean Government (2009-0063320) and
L.H.H thanks NAFOSTED grant 103.06.14.09 and Vietnam Ministry
of Education and Training Basic Research under Project B2009
17-188.

J. Raman Spectrosc. 2010, 41, 10051010

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1009

Figure 6. Temperature dependence of the wavenumber of mode 7, 8 and 9. Squares, triangles, and circles are the experimental points and the solid line
is normal wavenumbertemperature dependence expected for anharmonic decay.

L. H. Hoang et al.

Figure 7. Temperature dependence of the linewidths of modes 2 and 6.

References
[1] W. Eerenstein, N. D. Mathur, J. F. Scott, Nature (London) 2006, 442,
759.
[2] S.-W. Cheong, M. Mostovoy, Nat. Mater. 2007, 6, 13.
[3] T. Arima, A. Tokunaga, T. Goto, H. Kimura, Y. Noda, Y. Tokura, Phys.
Rev. Lett. 2006, 96, 097202.
[4] H. Katsura, N. Nagaosa, A. V. Balatsky, Phys. Rev. Lett. 2005, 95,
057205.
[5] M. Mostovoy, Phys. Rev. Lett. 2006, 96, 067601.
[6] O. Heyer, N. Hollmann, I. Klassen, S. Jodlauk, L. Bohaty, P. Becker,
J. A. Mydosh, T. Lorenz, D. Khomskii, Condens. Matter. 2006, 18,
L471.
[7] A. H. Arkenbout, T. T. M. Palstra, T. Siegrist, T. Kimura, Phys. Rev. B
2006, 74, 184431.
[8] K. Taniguchi, N. Abe, T. Takenobu, Y. Iwasa, T. Arima, Phys. Rev. Lett.
2006, 97, 097203.
[9] G. Blasse, J. Inorg. Nucl. Chem. 1975, 37, 97.

[10] M. Daturi, G. Busca, M. Borel, A. Leclaire, P. Piaggio, J. Phys. Chem. B

1997, 101, 4358.

[11] G. Lautenschlager, H. Weitzel, T. Vogt, R. Hock, A. Bohm,

M. Bonnet,
H. Fuess, Phys. Rev. B 1993, 48, 6087.
[12] H. Ehrenberg, H. Weitzel, C. Heid, H. Fuess, G. Wltschek, T. Kroener,
J. van Tol, M. Bonnet, J. Phys. Condens. Matter. 1997, 9, 3189.
[13] T. Moeller, Inorganic Chemistry, A Modern Introduction, John Wiley &
Sons, Inc.: New York, 1982.
[14] H. Wang, F. D. Medina, Y. D. Zhou, Q. N. Zhang, Phys. Rev. B 1992,
45, 10356.
[15] M. N. Iliev, H. Guo, A. Gupta, Appl. Phys. Lett. 2007, 90, 151914.
[16] M. Takesada, M. Itoh, T. Yagi, Phys. Rev. Lett. 2006, 96, 227602.
[17] L. V. Gasparov, K. G. Brown, A. C. Wint, D. B. Tanner, H. Berger,
G. Margaritondo, R. Gaal, L. Forro, Phys. Rev. B 2002, 66, 094301.
[18] J. Lockwood, R. S. Katiyar, V. C. Y. So, Phys. Rev. B 1983, 28, 1983.
[19] R. P. Chaudhury, F. Yen, C. R. Cruz, B. Lorenz, Y. Q. Wang, Y. Y. Sun,
C. W. Chu, Physica B 2008, 403, 1428.

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