Multiferroic phase stability in non-stoichiometric MnWO4

H. W. Yu, X. Li, L. Li, M. F. Liu, Z. B. Yan, and J.-M. Liu

Citation: Journal of Applied Physics 115, 17D722 (2014); doi: 10.1063/1.4866087
View online: http://dx.doi.org/10.1063/1.4866087
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JOURNAL OF APPLIED PHYSICS 115, 17D722 (2014)

Multiferroic phase stability in non-stoichiometric MnWO4

H. W. Yu, X. Li, L. Li, M. F. Liu, Z. B. Yan, and J.-M. Liua)
Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, China

(Presented 7 November 2013; received 14 September 2013; accepted 14 November 2013; published
online 26 February 2014)
We investigate the multiferroic phase stability of MnWO4 in response to the non-stoichiometry of Mn
and W, given the Mn:W ratio g. It is observed that the non-stoichiometry does not affect remarkably
the ferroelectric transition point (the AF3-AF2 transition point) and the AF2-AF1 transition point, but
the non-polar AF1 phase is partially replaced by the ferroelectric AF2 phase. The measured electric
polarization is slightly enhanced with increasing stoichiometric deviation jg  1j. The possible
C 2014 AIP Publishing LLC.
underlying mechanism for these effects is discussed. V
[http://dx.doi.org/10.1063/1.4866087]
Multiferroic materials have inspired much attention in
recent years. The coexistence of spontaneous polarization
and magnetization in the same phase and the magnetoelectric
coupling between them makes the mutual control of magnetism and ferroelectricity possible.13 These potentially useful
phenomena are observed in a wide class of materials, including orthorhombic rare-earth manganites,46 triangular
cuprates,79 Ni3V2O8,10 Ca3CoMnO6,11 and so on. While
most of them show more than one magnetic phase, the magnetoelectric coupling is available only in certain phases that feature noncollinear spin orders. The Dzyaloshinskii-Moriya
(DM) interaction is believed to induce such couplings based
on a magnetic structure that results in a macroscopic electric
polarization,1214 mainly in 3d magnetic transition metal
oxides of noncollinear spin order.15,16
MnWO4 (MWO) has been well studied in recent years.
MWO undergoes successive magnetic phase transitions upon
decreasing temperature T. The first antiferromagnetic transition occurs at T TAF3 13.5 K, where a sinusoidal incommensurate spin structure is developed (AF3 phase). The AF3
phase is replaced by the AF2 phase with a tilted elliptical
spiral structure at T TAF2 12.6 K. The collinear commensurate AF1 phase with characteristic ""## spin order appears
at T TAF1 7.8 K and below. It is noted that only the helical AF2 phase is ferroelectric with polarization P aligned
along the b-axis. Plenty of works have been done to modulate the stability of these phases, based on the fact that the
spin structure is sensitive to any small perturbations such as
external fields17,18 and chemical substitutions.1922
The purpose of this work is to investigate the multiferroic
phase stability of MWO against the Mn:W non-stoichiometry.
The spin structure is a compromise between multifold
interactions competition and the effective interactions can be
over the 11th-neighbor.23 The spin-lattice interaction is
believed to play a substantial role. It was reported that substitution of Mn2 by Co, Zn, or Mg can seriously suppress the
AF1 phase and slightly destabilize the AF2 phase.20,21,24,25
Since these substitutions all result in chemical disorder and
lattice contraction, it is argued that the spin-lattice interactions
a)

Author to whom correspondence should be addressed. Electronic mail:

liujm@nju.edu.cn.

0021-8979/2014/115(17)/17D722/3/$30.00

in addition to the multifold spin interactions are major ingredients for the magnetic transitions.
Here, for non-stoichiometric MWO, either Mn- or
W-deficiency can be viewed as a kind of chemical disorder
too. In this case, the relative stability of one magnetic phase
over the other will be modulated. By synthesizing a series of
MWO samples with different g, we investigate the stability
of the AF1 and AF2 phases.
We define an atomic ratio g Mn/W and quantity jg  1j
measures the non-stoichiometry. Our experiment is on polycrystalline samples prepared using standard solid-state reactions. The high-purity WO3 and MnO powder was chosen as
reagents and thoroughly mixed for 24 h. The dried mixture was
ground for 1 h each and then annealed in air for 12 h at 600  C.
After another intermediate grindings, the mixture was compressed into pellets and annealed at 950  C for 20 h in air.
The sample crystallinity was checked using X-ray diffraction (XRD) with Cu Ka radiation at room temperature.
The valence states of Mn and W ions and chemical composition were examined by X-ray photoelectron spectroscopy
(XPS; ULVAC-PHI PHI5000 VersaProbe using Al Ka radiation). The magnetization M and dc magnetic susceptibility v
were measured using the Quantum Design Superconducting
Quantum Interference Device (SQUID) in the zero-field
cooled (ZFC) mode and field-cooling (FC) mode, respectively. The cooling and measuring fields were both 1000 Oe.
The electric polarization as a function of T was measured
using the pyroelectric current method by Keithley 6514 electrometer connected to the Physical Properties Measurement
System.26 The samples were first poled in a static electric
field of 10 kV/cm, and then the pyroelectric currents measured through warming the samples were integrated to obtain
polarization P as a function of T.
The high-precision XRD data of several samples are
plotted in Fig. 1. All the spectra fit the standard database satisfactorily. Here, it is critical to exclude any manganese
oxides or tungsten oxides. By focusing on the local (030)
and (022) reflections in Fig. 1(b), one sees gradual shifting
of the two peaks towards the high-angle with increasing
jg  1j, indicating clearly the lattice contraction. For clarifying the details, we perform the Rietveld refining of the XRD
data using the GSAS program. For a reliable refining of the

115, 17D722-1

C 2014 AIP Publishing LLC

V

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J. Appl. Phys. 115, 17D722 (2014)

FIG. 2. Measured v-T curves under the ZFC and FC modes for five samples
g 1.04, 1.02, 1.00, 0.98, and 0.96. The measuring field is 1000 Oe.

FIG. 1. (a) Measured h-2h XRD spectra of several samples, and (b) the
amplified (030) and (022) reflections. The XPS spectra of Mn(2p1/2,3/2) and
W(4f5/2,7/2) core levels for g 1.04, 1.00, and 0.94 are shown in (c) and (d).
The evaluated lattice constants (a, b, c) and lattice unit volume V are plotted
in (e)-(h).

data, one needs to know the variations of lattice occupation

in these non-stoichiometric samples. First, we employ the
XPS to probe the g value and Mn/W valence states. For
examples, the XPS spectra for samples g 1.04, g 1, and
g 0.94 are shown in Fig. 1(d) for W and (e) for Mn. No
identifiable shift of the peaks corresponding to the Mn2p1/2,3/2 and W-4f5/2,7/2 is observed, implying that the valence states of Mn and W ions remain to be Mn2 and W6,
although the existence of tiny Mn and/or W ions with different valences cannot be excluded. Second, generation of ionic
defects in the g 6 1 samples is needed to meet the electric
neutrality condition. It is noted that Mn2 ion is bigger than
W6 ion and there is big valence difference between them.
For g > 1, no possibility for occupation of the W-vacant site
by Mn ion is expected and thus, the W-vacancies are
assumed with oxygen vacancies surrounding the W vacancies. On the other hand, for g < 1, two possible situations
may appear. One is that the excess W6 ions occupy the
Mn2-vacant sites. The electrostatic energy due to the big
valence difference between Mn2 and W6 can be high. The
other is the generation of Mn vacancies and surrounding oxygen vacancies, which are favored from the energy
consideration.
Based on this site occupation model, high precision
Rietveld refining is obtained. The evaluated lattice constants
(a, b, and c) and lattice unit volume V as a function of g are
plotted in Figs. 1(e)1(h). These parameters decrease with
increasing jg  1j. This feature is similar to those cases with
the Co, Zn, or Mg-substituted MWO.20,21,24,25 It is then suggested that the AF1 phase may be destabilized, and the AF2
phase may be or not. The AF1 phase will most likely be partially replaced by the AF2 phase, to be confirmed below.

The v-T data in both the ZFC and FC modes for five
samples are presented in Fig. 2. Rather than any quantitative
discussion, we list several qualitative features. First, the
magnetization over the whole T range is suppressed with
increasing jg  1j. This phenomenon may be understandable
for g < 1 since the magnetic Mn species is deficient.
However, it is true for g > 1 too. A reasonable argument is
that the non-stoichiometry releases the spin frustration and
stabilizes the spin structures. Second, a comparison of the
ZFC and FC data shows that the separation between the two
modes becomes weaker with increasing jg  1j, and the two
modes even merge together at g 0.96. This also evidences
that the spin phase stability against, e.g., thermal activations,
is enhanced with increasing jg  1j. Third, the v-T curves at
the ZFC mode show quite similar shapes, indicating that the
magnetic transition sequence does not change much for different g. Unfortunately, the AF3-AF2 and AF2-AF1 transition points cannot be clearly identified from the v-T data
although several weak anomalies can be roughly seen, which
are marked as TAF1, TAF2, and TAF3 shown in Fig. 2.
Finally, we consult to the ferroelectricity for illustrating
the effect of Mn/W non-stoichiometry. The measured I-T
curves and evaluated P-T curves for several samples are shown
in Figs. 3(a)3(f). The P-T data for the g 1 sample is similar
to earlier results.17 Several clear features are shown. First, if
defining the initiating point of the pyroelectric current I from
the high-T side as TAF2, and the initiating point from the low-T
side as TAF1, one sees that both TAF2 and TAF1 do not shift with
increasing jg  1j, noting that the two points for the g 1 sample coincide well with earlier reports.17,21,22,24,25 This is different from those Co, Mg, or Zn-substituted MWO where TAF1
disappears immediately and TAF2 is slightly down-shifted. For
the Fe-substituted case, however, TAF1 is up-shifted and TAF2 is
down-shifted. Second, for both g > 1 and g < 1, not only the P
within TAF1 < T < TAF2 is gradually enhanced but also nonzero polarization is identified below TAF1. Meanwhile, the
polarization at T 2 K, P(2 K), increases too. The P(max) and
P(2 K) data as functions of g are plotted in Figs. 3(g) and 3(h),
respectively. In those substituted MWO, however, the P of the
AF2 phase is gradually damaged upon the increasing substitution. Third, the above data show the incomplete AF2-AF1
6 1 samples, leadphase transitions initiating at TAF1 in these g
ing to the AF1 and AF2 phase coexistence below TAF1. This is
also different from those substituted MWO.2022,24
From the measured results, we can highlight the multiferroic phase diagram in the (g, T) plane at H 0, as shown

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17D722-3

Yu et al.

J. Appl. Phys. 115, 17D722 (2014)

FIG. 4. Evaluated multiferroic phase diagram in the g  T plane at H 0.

FIG. 3. (a)-(f) Measured pyroelectric current I (red solid curves) and evaluated electric polarization P (blue dashed curves) as a function of T. The
arrows indicate TAF2 and TAF1, respectively. (g) and (h) The evaluated
P(2 K) and P(max) as a function of g.

in Fig. 4. In the low-T range, the phase diagram is divided

into three regions: the AF1 phase close to g 1 and the
AF1 AF2 coexisting regions on the two sides.
Furthermore, from the ferroelectric data, the TAF1 at which
the AF2-AF1 phase transition begins does not change. Here,
we acknowledge that the proposed phase diagram is still
more or less qualitative, and more data on the spin structure
are needed for a quantitative phase diagram.
The obtained structural and ferroelectric data allows us
to have a qualitative discussion on the underlying mechanism for the effects of the Mn/W non-stoichiometry.
First, the similarity between the present materials and
those Co, Zn, and Mg-substituted MWO lies in the fact that
chemical disorder is induced and the lattice contracts. The
chemical disorder is believed to destabilize the magnetic
phases via the spin-lattice interactions.24,25 This effect seems
more significant in suppressing the AF1 phase rather than the
AF2 phase. The induced lattice contraction is equivalent to
the effect of a chemical pressure, believed to destabilize the
non-polar AF1 phase.27 The chemical disorder induced here
seems weak, and the lattice contraction at the maximal value
here is only one-tenth of that for those Co, Zn, and Mgsubstituted MWO. Therefore, it is reasonable to observe an
incomplete taking-over of the AF1 phase by the AF2 phase,
leading to the AF1 AF2 phase coexistence.
Second, the ferroelectric polarization in the AF2 phase
is enhanced in the g 6 1 MWO, while it is suppressed for
those Co, Zn, and Mg-substituted MWO. This P-enhancement may be related to the overall high stability of the magnetic phases (both AF2 and AF1) in the g 6 1 MWO with

respect to the g 1 MWO (Fig. 2). This higher stability and

thus the ferroelectric domains in the AF2 phase against internal fluctuations reasonably allows larger polarization.
Third and surely, both magnetic and non-magnetic
substitutions in the g 6 1 samples and those Co, Zn, and
Mg-substituted MWO definitely impose impact on the spin
interactions. It was claimed that the effects of non-magnetic
substitutions seem independent of the nature of substituting
species, and the three-dimensional nature of magnetic interactions and the spin frustration remain less affected.25 The
Mn-deficient MWO is equivalent to a kind of non-magnetic
substitution, while the W-deficient MWO does not include
additional magnetic species either since the substituted sites
are W-vacancies. Therefore, a reasonable argument is that, similar to the Zn/Mg-substituted cases, the non-stoichiometry here at
low jg  1j imposes less influence on the magnetic interactions,
and the major contributions are from the chemical disorder and
modulated spin-lattice interactions.
This work was supported by the National 973 Projects
of China (Grant No. 2011CB922101), the Natural Science
Foundation of China (Grant Nos. 11234005 and 51332006),
and the Priority Academic Program Development of Jiangsu
Higher Education Institutions, China.
1

Y. Tokura, Science 312, 1481 (2006).

S. W. Cheong and M. Mostovoy, Nat. Mater 6, 13 (2007).
K. F. Wang, J.-M. Liu, and Z. F. Ren, Adv. Phys. 58, 321 (2009).
4
T. Kimura et al., Nature (London) 426, 55 (2003).
5
T. Goto et al., Phys. Rev. Lett. 92, 257201 (2004).
6
N. Hur et al., Nature (London) 429, 392 (2004).
7
S. Park et al., Phys. Rev. Lett. 98, 057601 (2007).
8
T. Kimura et al., Phys. Rev. B 73, 220401(R) (2006).
9
K. Kimura et al., Phys. Rev. Lett. 103, 107201 (2009).
10
G. Lawes et al., Phys. Rev. Lett. 95, 087205 (2005).
11
L. Lin et al., J. Appl. Phys. 111, 07D901 (2012).
12
H. Katsura et al., Phys. Rev. Lett. 95, 057205 (2005).
13
M. Mostovoy, Phys. Rev. Lett. 96, 067601 (2006).
14
I. A. Sergienko and E. D. Dagotto, Phys. Rev. B 73, 094434 (2006).
15
M. Kenzelmann et al., Phys. Rev. Lett. 95, 087206 (2005).
16
S. G. Condran et al., J. Phys.: Condens. Matter 22, 162201 (2010).
17
K. Taniguchi et al., Phys. Rev. Lett. 97, 097203 (2006).
18
K. Taniguchi et al., Phys. Rev. Lett. 101, 207205 (2008).
19
F. Ye et al., Phys. Rev. B 78, 193101 (2008).
20
Y. S. Song et al., Phys. Rev. B 79, 224415 (2009).
21
R. P. Chaudhury et al., Phys. Rev. B 83, 014401 (2011).
22
H. W. Yu et al., Phys. Rev. B 87, 104404 (2013).
23
H. Ehrenberg et al., J. Phys.: Condens. Matter 11, 2649 (1999).
24
F. Ye et al., Phys. Rev. B 86, 094429 (2012).
25
L. Meddar et al., Chem. Mater. 21, 5203 (2009).
26
G. Q. Zhang et al., Phys. Rev. B 84, 174413 (2011).
27
R. P. Chaudhury et al., Physica B 403, 1428 (2008).
2
3

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