Journal of Alloys and Compounds 656 (2016) 830e834

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Observation of ferroelectricity and magnetoelectric coupling in

Mn-doped orthochromite DyCr0.5Mn0.5O3
B. Yuan a, J. Yang a, *, X.Z. Zuo a, X.C. Kan a, X.B. Zhu a, J.M. Dai a, W.H. Song a, **,
Y.P. Sun a, b, c
a
Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, PR China
b
High Magnetic Field Laboratory, Chinese Academy of Sciences, Hefei 230031, PR China
c
Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, PR China

a r t i c l e i n f o a b s t r a c t

Article history: We investigate the structural, magnetic, and magnetoelectric properties of DyCr0.5Mn0.5O3.
Received 15 May 2015 DyCr0.5Mn0.5O3 exhibits ferroelectricity at the paramagneticeantiferromagnetic transition temperature,
Received in revised form i.e., TN ¼ 74 K, demonstrating the polarization is driven by magnetic order. Furthermore, the ferroelectric
2 October 2015
polarization can be substantially influenced by applied magnetic fields indicating a strong magneto-
Accepted 4 October 2015
Available online 9 October 2015
electric effect in DyCr0.5Mn0.5O3. It is demonstrated that the ferroelectricity in DyCr0.5Mn0.5O3 may stem
from the spin-phonon coupling of Dy and Mn/Cr ions as evidenced by the temperature dependence of
Raman phonon modes. The results manifest that DyCr0.5Mn0.5O3 is a potential candidate for magneto-
Keywords:
Ferroelectricity
electric device applications.
Magnetoelectric effects © 2015 Elsevier B.V. All rights reserved.
Multiferroics

1. Introduction that RCr0.6Mn0.4O3 (R ¼ Y, La, Lu) exhibit ferroelectric polarization

at TN [6]. Compared to YCrO3, previous investigation on DyCrO3
Multiferroic materials which simultaneously exhibit a combi- mostly focused on the structural, magnetic, and magnetocaloric
nation of ferroelectricity (FE), ferromagnetism, and/or ferroelas- properties [11e13]. The magnetic ground state of DyCrO3 is G-type
ticity have attracted much attention because of their potential for antiferromagnetic ordering with TN ¼ 146 K. However, doping Fe at
applications as switches, magnetic field sensors, and memory Cr sites can make DyFe0.5Cr0.5O3 exhibit weak ferromagnetism
storage devices [1,2]. In particular, magnetoelectric (ME) multi- [14,15]. Therefore, doping magnetic ion at the Cr-site is an effective
ferroic materials showing a coupling between the magnetic and way to generate weak ferromagnetism and polarization due to the
electric order parameters have been demonstrated to be useful for nonequivalent disordered spins. Among these substitution ele-
new device applications [1e4]. Recently, the rare-earth ortho- ments, the substitution of Mn3þ for Cr3þ may be interesting
chromites (RCrO3) have attracted much attention because of the because of the identical electronic configuration of Cr3þ with Mn4þ.
potential to exhibit strong ME coupling [5,6]. However, most RCrO3 Therefore, some authors argued that ferromagnetic double ex-
compounds are insensitive to applied magnetic fields due to the change between Cr3þ and Mn3þ ions exists in the Cr-doped man-
antiferromagnetic order, which is an obvious disadvantage in po- ganites [16e19]. We should note that rare-earth manganites show
tential applications [7,8]. One of the members of the rare-earth ferroelectricity and magnetoelectric effect. And also, the ferro-
orthochromite family, YCrO3 does not exhibit dielectric anomaly electric order can be either induced or suppressed by applying a
or ferroelectric polarization at the magnetic transition. By intro- magnetic field in RMnO3 (R ¼ Gd, Tb, and Dy) [20e23]. Although
ducing cation disorder at the Cr-site, Mao found weak ferromag- DyMnO3 exhibits the inherent magnetoelectric coupling, the
netism below the Ne'el temperature (TN) and high temperature saturated ferroelectric polarization is small and ferroelectric as well
multiferroicity in YFe0.5Cr0.5O3 [9,10]. Later, Rajeswaran reported as magnetic transition temperature is very low (TFE < 18 K) [24,25].
As a result, it is natural to combine the advantage of DyMnO3 with
magnetoelectric coupling and DyCrO3 with high magnetic ordering
temperature to obtain a single-phase multiferroic that possess an
* Corresponding author.
** Corresponding author.
enhanced magnetism and magnetoelectric coupling. With this
E-mail addresses: [email protected] (J. Yang), [email protected] (W.H. Song). notion in mind, we have synthesized doped orthochromite

http://dx.doi.org/10.1016/j.jallcom.2015.10.030
0925-8388/© 2015 Elsevier B.V. All rights reserved.
 B. Yuan et al. / Journal of Alloys and Compounds 656 (2016) 830e834 831

DyCr0.5Mn0.5O3 with half of the Cr cations substituted by Mn ions 3. Results and discussion
and investigated the structural, magnetic, and ME properties. The
results showed that DyCr0.5Mn0.5O3 exhibits a strong magneto- Fig. 1(a) shows the XRD pattern of DyCr0.5Mn0.5O3 at room
electric effect at the ferroelectric and magnetic transition temper- temperature. DyCr0.5Mn0.5O3 is of single phase with no detectable
ature of 74 K. secondary phases. During the Rietveld refinement process, we
found that both orthorhombic Pbnm and monoclinic P21/c can be
2. Experimental details utilized to refine the XRD pattern of DyCr0.5Mn0.5O3. However, the
fit result via the orthorhombic structure is slightly better than that
Polycrystalline DyCr0.5Mn0.5O3 was prepared with a conven- via the monoclinic structure. The calculated XRD patterns of
tional solid-state reaction. The stoichiometric amounts of Dy2O3 DyCr0.5Mn0.5O3 are also shown in Fig. 1(a). The fit between the
(99.9%) (Dy2O3 was heated at 1000  C for 12 h before use). Mn2O3 experimental and calculated XRD patterns is relatively good based
(99.9%), Cr2O3 (99.99%), were mixed and grounded, and then on the consideration of the lower RP value of 3.34. Note that the
calcined at 900  C for 10 h. The obtained powders were ground, space group Pbnm corresponds to the random distribution of B-site
pelletized, and sintered at 1300  C for 40 h with two intermediate ions over the octahedral sites, whereas the space group P21/c
grindings, and finally the furnace was cooled slowly to room tem- points to the ordered stacking of B-site ions [26,27]. Moreover, the
perature. The crystal structure was examined by an x-ray diffrac- large difference in the valence state and ionic radius be-tween B-
tometer using Cu Ka radiation at room temperature. A field- site cations for perovskite compounds is suggested to facilitate
emission scanning electron microscope (FESEM, Sirion 200, FEI formation of B-site ordered structure. Taking into account the same
Company) was used to characterize the surface morphology of the valence state between Mn3þ and Cr3þ (as confirmed by the XPS
samples. We determined the chemical composition of results shown below) and slight difference in the ionic radius be-
DyCr0.5Mn0.5O3 with energy-dispersive x-ray spectroscopy (EDX) in tween Mn3þ and Cr3þ, we therefore suggest that DyCr0.5Mn0.5O3
a JEOL JSM-6500 scanning electron microscope. The measurements may exist in the form of B-site disordered state.
of x-ray photoelectron spectroscopy (XPS) were conducted by The typical field emission scanning electron microscopy
VGScientific, ESCALAB250 to obtain information on the valence (FESEM) image of the DyCr0.5Mn0.5O3 sample is shown in inset of
state of the Mn and Cr ions. The magnetic measurement was carried Fig. 1(b). The microstructure of the sample showed average grain
out with a quantum design superconducting quantum interference size of 1e2 mm which are densely packed and homogeneously
device (SQUID) Magnetic Property Measurement System (MPMS) distributed. The well-connected grains and defined grain bound-
system (2  T  400 K, 0  H  4 T). For the electric measurement, aries in DyCr0.5Mn0.5O3 make it possible to measure the pyroelec-
the sample was pelletized to a bulk with a tetragonal shape tric current. The EDX analysis confirms the presence of Dy, Cr, Mn
(2*2*0.52 mm3), then silver-paste (Silver Conductive Epoxy-part A- and O, as shown in Fig. 1(b). The average atomic ratios determined
Resin & B-Hardener) were deposited onto the opposite 2*2 mm2 from EDX spectra are Dy: Cr: Mn ¼ 2.01(2): 1.00(1): 0.98(2) when
pressure surfaces. The pyroelectric currents of the samples were setting the content of Cr as 1. It is consistent with the formula of
determined with an electrometer (Keithley 6517B) with the tem-
perature and magnetic field regulated by the Quantum Design
Physical Property Measurement System (PPMS).

Fig. 1. (a) XRD pattern of DyCr0.5Mn0.5O3 and the crystal structure. Circles indicate the
experimental data and the calculated data are the continuous line overlapping them. Fig. 2. XPS spectra (scattered points),deconvoluted results (solid lines) and back-
The lowest curve shows the difference between the experimental and calculated ground (blue solid lines) of (a) Dy 3d, (b) Mn 2p, and (c) Cr 2p of DyCr0.5Mn0.5O3. (For
patterns. The vertical bars indicated the expected reflection positions. (b) The EDX interpretation of the references to colour in this figure legend, the reader is referred to
spectrum of the sample. The inset of (b) shows SEM image. the web version of this article.)
832 B. Yuan et al. / Journal of Alloys and Compounds 656 (2016) 830e834

DyCr0.5Mn0.5O3. The results of EDX spectrum reveal the presence of both the Mn3þ and Cr3þ ions distribute randomly in
a small amount of DyO, which can be neglected in our study DyCr0.5Mn0.5O3, which lead to a B-site disordered perovskite
ferroelectric properties of DyCr0.5Mn0.5O3, due to that it is not structure. Therefore, several magnetic interactions like MneOeCr,
ferroelectric. CreOeCr, MneOeMn, DyeOeDy, and DyeOe(Mn/Cr) might exist
The XPS measurement was carried out in order to obtain more in DyCr0.5Mn0.5O3. Previous results demonstrated that the
electronic structure information of DyCr0.5Mn0.5O3. Fig. 2(a) illus- CreOeCr and MneOeMn AFM interactions take place at
trates the Dy 3d core-level spectra of DyCr0.5Mn0.5O3. The peak TCrCr ¼ 146 K in DyCrO3 Refs. [9,11] and TMnMn ¼ 57 K in DyMnO3
located at 1296.90 eV can be attributed to Dy 3d5/2 (1297.60 eV) in [24,31], respectively. Moreover, DyeOeDy AFM interactions nor-
Dy2O3 [28]. Fig. 2(b) shows the Mn 2p core-level spectrum of mally take place at temperature below 10 K. Therefore, it is
DyCr0.5Mn0.5O3. The spectrum exhibits the spin-orbit split 2p1/2 reasonable to ascribe the AFM transition to the dominant
and 2p3/2 peaks located at 653.41 eV and 641.8 eV, respectively. MneOeCr interaction. In most cases, the random position of Mn3þ
These values are very close to that of Mn 2p1/2 (653.40 eV) and Mn and Cr3þ ions in materials and the deviation of the bond angle
2p3/2 (641.70 eV) in Mn2O3, implying that the Mn ions in the between Mn3þ and Cr3þ from 180 will give rise to the AFM
DyCr0.5Mn0.5O3 is 3 þ valence state [29]. The core-level spectrum of superexchange interaction between Mn3þeOeCr3þ instead of the
Cr 2p and its deconvoluted curve is shown in Fig. 2(c). It is found 180 FM superexchange interaction proposed by Goodenough-
that the spectrum consists of two peaks located at 586.32 eV and Kanamori rules [32,33]. Moreover, the different ionic radius of
576.61 eV corresponding to the binding energy of Cr 2p1/2 Cr3þ (0.61 Å) and Mn3þ (0.65 Å) will result in lattice distortion.
(586.40 eV) and Cr 2p3/2 (576.60 eV), respectively, in Cr2O3 [30]. Therefore, the weak ferromagnetism may originate from the spin
Fig. 3 shows the temperature dependence of magnetization in canting of AFM coupling of Mn-based and Cr-based sublattices via
the zero-field-cooled (ZFC) and the field-cooled (FC) modes at an the Dzyaloshinskii-Moriya (DM) interaction due to the distorted
applied field of 100 Oe for DyCr0.5Mn0.5O3. It can be seen in Fig. 3 crystal structure with the octahedral tilting between the adjacent
the deviation between two curves begins to occur at about 74 K MneO and CreO octahedra [34,35].
implying the onset of a magnetic ordering. To determine the nature To explore whether the magnetic ordering is accompanied by a
of magnetic transition at 74 K, we plot the temperature dependence ferroelectric order, we measured the pyroelectric below 110 K to
of the reciprocal susceptibility (1/c ¼ H/M) under ZFC modes in probe the possible ferroelectricity in this compound. The sample
right panel of Fig. 3. The result shows that the high-T paramagnetic covered with the top and bottom electrodes (e.g. Ag) was cooled
region obeys the CurieeWeiss law: down to 10 K in an electric field of 1.56 kV/cm, then the poling field
was removed and the sample was short-circuited for sufficient time

  at 10 K. Afterward, we measured the pyroelectric current while
cm ¼ Cm T  qp (1)

where Cm is the molar Curie constant, and qp is the paramagnetic

Curie temperature. The paramagnetic Curie temperature qp is ob-
tained to be 18 K implying the dominant antiferromagnetic in-
teractions in DyCr0.5Mn0.5O3. The MH curve at 5 K (left inset of
Fig. 3(a)) also exhibits a nearly linear behavior with a small coercive
field implying that the magnetic ground state of DyCr0.5Mn0.5O3
may be antiferromagnetic accompanied with weak ferromagnetic
coupled spins. We also carried out the ac susceptibility measure-
ments at the frequencies of 1, 10, and 100 Hz (not shown here).
There is no indication of the existence of long-range magnetic
ordering around 74 K, as is also confirmed by the results of specific
heat. The right inset of Fig. 3 shows specific heat of DyCr0.5Mn0.5O3.
No anomaly at around 74 K was observed.
Based on the refined structural parameters and XPS results, it
should be noted that Mn and Cr ions can occupy only one position,

Fig. 4. (a) Polarization vs T in a poling field of E ¼ ±1.56 kV/cm, (b) the temperature
Fig. 3. (a) Temperature dependence of magnetization for DyCr0.5Mn0.5O3 in the ZFC dependence of polarization for DyCr0.5Mn0.5O3 under various magnetic fields, (c) the
and FC modes measured at H ¼ 100 Oe. The right panel shows the temperature measured pyroelectric current I in a poling field of E ¼ ±1.56 kV/cm (d) the measured
dependence of the inverse susceptibility for DyCr0.5Mn0.5O3, The solid line denotes the pyroelectric current with different warming rate: 1, 2, and 4 K/min, (e) the effect of
best fit to the data based on Eq. (1). The left inset is field dependence of magnetization magnetic field on the ferroelectric transition temperature, (f) the maximum polari-
at 5 K. The right inset is temperature dependence of specific heat for DyCr0.5Mn0.5O3. zation at 15 K for different poling fields.
 B. Yuan et al. / Journal of Alloys and Compounds 656 (2016) 830e834 833

heating the sample at a rate of 4 K/min. The released current Ip ions can be observed due to their interaction with Cr could exist and
exhibits obvious peaks at about 68 K under the application of this induced magnetization cannot lead to ferroelectricity. For
negative and positive poling field (Fig. 4(d)). The spontaneous po- DyCr0.5Mn0.5O3, the spin canting of AFM coupling of Mn-based and
larization calculated via P(T) ¼ !Ip (T, t)dt/A (A is the sample sur- Cr-based sublattices induces the displacement of the oxygen
face) for DyCr0.5Mn0.5O3, as shown in Fig. 4(a). The largest causing local polarization. We should also note that there may exist
polarization of DyCr0.5Mn0.5O3 is 632 mC/m2, which is comparable two possible arrangements of Mn and Cr ions at the B sites. In the
with that of other typical magnetic ferroelectrics and the chromites first case (Fig. 5(a)), the Mn and Cr cations arrange in an orderly
reported previously [1,36]. Furthermore, it is interesting that the manner. All MneOeCr bonds are still equivalent and the local po-
ferroelectric polarization is distinctly enhanced under the appli- larizations would get canceled because of the change in the di-
cation of magnetic field, indicating a possible strong magneto- rection of induced local polarization. In the second case (Fig. 5(b)),
electric coupling in DyCr0.5Mn0.5O3 (Fig. 4(b)). Increasing magnetic both the Mn and Cr ions distribute randomly in DyCr0.5Mn0.5O3. As
field makes the ferroelectric transition slightly shift to higher a result, the net effect is that B-site disorderly arrangement can
temperatures (Fig. 4(e)), which indicates the correlation between induce a net ferroelectric polarization due to the total of oxygen
the spin-phonon coupling and ferroelectricity in DyCr0.5Mn0.5O3 displacements cannot get canceled. The existence of ferroelectric
[37]. In order to check the reliability of electric polarization, we polarization in DyCr0.5Mn0.5O3 manifest again the B-site disorderly
measured the temperature dependence of pyroelectric current (I-T) arrangement between Mn and Cr ions. Note that DyCr0.5Mn0.5O3
with different warming rates: 1, 2, and 4 K/min, as presented in exhibits a spin-canted AFM state below TN. Increasing magnetic
Fig. 4(c). It is observed that the peaks of three I-T curves do not shift field may make the moment of Mn- and Cr-sublattices rotate to-
along the temperature axis and the integral of I(t) for the three ward the direction of magnetic field and thus make a similar
curves are almost identical (not shown), demonstrating that the rotation of ferroelectric polarization [39]. As a result, the pro-
intrinsic pyroelectric current is dominant. Indeed, plotting the jections of P of the Mn- and Cr-sublattices become smaller in the
maximum P of DyCr0.5Mn0.5O3 at the lowest temperature (15 K) as a longitudinal direction. However, the projection of P of oxygen
function of the poling electric field (Fig. 4(f)) reveals that the almost remains the same. In this case, the measured net polariza-
saturation polarization was not achieved in the current experiment. tion in DyCr0.5Mn0.5O3 would increase.
In magnetically induced multiferroic materials, the ferroelectric Now we turn on temperature-dependent Raman spectroscopy
transition would correspond to the magnetic transition. We note measurements, to study the local structure of a material [40] and
that the ferroelectric polarization almost occurs at the magnetic- the spin-phonon coupling. We performed the temperature-
transition temperature for DyCr0.5Mn0.5O3 implying that ferro- dependent Raman spectroscopy measurements. The Raman spec-
electricity and magnetic ordering may exist a coupling. For the end trum recorded at 10 K is shown in Fig. 5(c). Lattice dynamical cal-
compound RCrO3, spontaneous magnetization of R ions at low culations have predicted 24 Raman active modes in the
temperatures can induce ferroelectric polarization in some cases orthorhombic perovskites. The mode assignment corresponding to
[38]. But at higher temperatures only induced magnetization on R various vibrational symmetries for DyCr0.5Mn0.5O3 is performed

Fig. 5. Schematic illustration of induced ferroelectric polarization in canted antiferromagnetic systems with (a) an ordered and (b) a disordered arrangement. (c) Raman spectrum
of DyCr0.5Mn0.5O3 recorded at 10 K. Inset shows the deconvoluted peak centered around 645 cm1 into B3g and B2g modes. (d) T-dependent B3g and B2g modes near TN. The dashed
lines are the fitting results based on Eq. (2). (e) T-dependent linewidth for B3g and B2g modes around TN. The solid lines in (d) and (e) are guides to the eye.
834 B. Yuan et al. / Journal of Alloys and Compounds 656 (2016) 830e834

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Academy of Sciences' Large-Scale Scientific Facility (Grants Nos. [44] M. Balkanski, R. Wallis, E. Haro, Phys. Rev. B 28 (1983) 1928.
U1232138, U1232210 and U1432137). Y. P. Sun acknowledges sup-
port by the National Key Basic Research (Grant No. 2011CBA00111).