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A-site and B-site cation ordering induces polar and multiferroic behavior in
the perovskite NaLnNiWO6 (Ln = Y, Dy, Ho, Yb)

Article in Chemistry of Materials · May 2020

DOI: 10.1021/acs.chemmater.0c01149

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A‑Site and B‑Site Cation Ordering Induces Polar and Multiferroic

Behavior in the Perovskite NaLnNiWO6 (Ln = Y, Dy, Ho, and Yb)
Ravi Shankar P N, Fabio Orlandi, Pascal Manuel, Weiguo Zhang, P. Shiv Halasyamani,
and Athinarayanan Sundaresan*
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ABSTRACT: Octahedral distortion in ABO3 perovskite materials is ubiquitous because of

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the ionic size mismatch between A and B cations, leading to various kinds of crystal
symmetry. However, such a distortion always results in centrosymmetric structures except
for the covalent bond formation because of the second-order Jahn−Teller (SOJT) effect
that occurs with d0 or lone-pair cations. Here, we report that an unusual combination of
the layered A-site cation ordering and B-site rock salt ordering in NaYNiWO6 prepared
under high-pressure and high-temperature conditions results not only in a polar (P21)
structure, as revealed by the neutron diffraction analysis, but exhibits multiferroic
properties below the magnetic ordering of Ni2+ ions (TN = 21 K). Analysis of the neutron diffraction data at 20 K reveals an
incommensurate sinusoidal spin ordering with the propagation vector, ki = (0.471(2), 0, 0.491(4)), and a commensurate collinear
spin structure with kc = (0.5, 0, 0.5) below 18 K. X-ray diffraction data confirm the polar structure in Dy, Ho, and Yb compounds. All
four compounds exhibit a switchable change in electric polarization (ΔP) at the magnetic ordering temperatures, demonstrating
coupling between ferroelectricity and magnetism.

1. INTRODUCTION formula A2BB′O6.13−20 Like the simple perovskites, most of

Perovskite (ABO3) oxides cover a large area of materials the double perovskites crystallize in a centrosymmetric
research because of the versatility of their structure and the fact structure except a few polar double perovskites, such as
that they can accommodate a vast majority of elements in the Pb2MnWO6, Bi2NiMnO6, and Bi2Mn4/3Ni2/3O6,21−24 where
periodic table. Owing to their flexibility, these materials exhibit the presence of a stereochemically active cation at the A-site
diverse and interesting physical properties such as ferroelec- drives the system to a polar structure, and the B-site cations
tricity, ferromagnetism, multiferroicity, superconductivity, provide magnetism. Thus, these double perovskites belong to
type-I multiferroics. For the application perspective, a
colossal magnetoresistance, and so forth.1−5 Among the
multiferroic material with a strong coupling between
perovskites, polar oxides such as BaTiO3 and PbZr0.5Ti0.5O3
ferroelectricity and magnetism at room temperature is
exhibit ferroelectricity at room temperature because of the
required. Therefore, it is essential to understand various
second-order Jahn−Teller (SOJT) effect associated with B-site
mechanisms of combining ferroelectricity and magnetism with
cations.6−9 These materials can be applied as sensors,
strong coupling.
capacitors, piezoelectric actuators, and integrated nonvolatile
Recently, an unusual combination of the layered ordering of
memory devices. Other perovskite oxides such as BiFeO3 and
A-site cations and rock-salt ordering of B-site cations in
RMnO3 (R = Tb, Dy) containing partially filled d-orbitals
NaLaMnWO 6 has been shown to exhibit a polar P2 1
exhibit multiferroic properties.10−12 In the former, the
structure.25 Such an unusual ordering of the A-site cations is
stereochemically active lone pair of Bi3+ ions provides
primarily stabilized by highly charged SOJT distortion of the
ferroelectricity, and the magnetism arises from Fe3+ ions.
W6+(d0) cation. Theoretical studies on NaLaMnWO6 revealed
Therefore, the ferroelectric and magnetic transitions occur at
that the stability and amplitudes of the two nonpolar rotation
different temperatures, and thus, the coupling between the two
modes and the induced polar mode cause the spontaneous
order parameters is weak. This kind of material is called a type-
ferroelectric polarization, which is predicted to be as large as
I multiferroic. In the case of centrosymmetric RMnO3,
cycloidal ordering of Mn3+ spins at low temperature breaks
the inversion symmetry and induces ferroelectricity. This oxide Received: March 16, 2020
belongs to type-II multiferroics, where the polarization is Revised: May 27, 2020
relatively small, but the coupling between the two order Published: May 27, 2020
parameters is strong.
Apart from the simple ABO3 perovskites, there are a large
number of B-site ordered double perovskites with the general

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.chemmater.0c01149

A Chem. Mater. XXXX, XXX, XXX−XXX
Chemistry of Materials
16 μC/cm2.26 Further investigation shows that the size of the
A-site cation plays a crucial role in terms of electrical
polarization, with a large increase of the latter with the
difference in the ionic size of the A-site cations.26,27 Several
compounds belonging to this family of oxides have been
reported.25,28−32 However, there is no experimental report on
the existence of ferroelectricity in the paramagnetic state of
these compounds. In this work, we report on the synthesis and
structural characterization of a new series of polar (P21)
compounds, NaLnNiWO6 (Ln = Y, Dy, Ho, and Yb)
containing Ni2+ ions, and show that these compounds exhibit
multiferroic properties below the antiferromagnetic ordering of
Ni2+-ions.
2. EXPERIMENTAL SECTION
2.1. Synthesis. The NaLnNiWO6 compounds with Ln = Y, Dy,
Ho, and Yb were prepared by high-pressure and high-temperature
synthesis using Na2WO4, Ln2O3 (preheated at 950 °C), NiO, and
WO3 as the starting materials. Stoichiometric amounts of the starting
materials were ground and pressed into a cylindrical pellet and
wrapped in a thin gold foil and kept in an enclosure prepared from a
NaCl and ZrO2 mixture, which was covered with a graphite heater. A
molybdenum disc and a stainless-steel ring were placed on both sides
of the heater, and the whole assembly was inserted into the
pyrophyllite cube used as a pressure-transmitting medium. The
pressure was first increased to 4.5 GPa and heated to 1000 °C. After 1
h, the sample was quenched directly to room temperature, and then
the pressure was released slowly.
2.2. Characterization. Powder X-ray diffraction (XRD) was
carried out using a PANalytical Empyrean alpha-1 diffractometer
using monochromatized Cu Kα1 radiation and the data were acquired
in the 2θ range 10−120° for Rietveld refinement, which was
performed using the FullProf suite program.33,34 The neutron powder
diffraction measurements were carried out on the WISH diffrac-
tometer located at the ISIS pulsed neutron and muon facility of the
Rutherford Appleton Laboratory (UK).35 The data were collected in
the temperature range of 1.5−100 K using an Oxford instrument
cryostat. Rietveld refinement of neutron diffraction data was
performed using the JANA2006 program.36 Group theoretical
calculations were performed with the help of the ISOTROPY and
ISODISTORT software.37 Second-harmonic generation (SHG)
measurements were carried out on the NaLnNiWO6 (Ln = Y, Dy,
and Ho) samples at room temperature using a modified Kurtz-
nonlinear optical system with a pulsed Nd:YAG laser (λ = 1064 nm).
The technicalities of the apparatus and procedure have already been
reported in the literature.38,39
dc magnetization measurements were carried out with a Magnetic
Property Measurement System (MPMS3-SQUID), Quantum Design,
USA. Heat capacity data were recorded with a Physical Property
Measurement System (PPMS, Quantum Design). Temperature-
dependent dielectric and pyroelectric measurements were carried
out with an Agilent E4980A LCR and Keithley 6517A electrometer,
respectively. For all electrical measurements, PELCO silver paste was
used to make electrodes. During pyroelectric measurements, the
samples were poled with an electric field (±E), and to remove any
stray charges, the electrodes were shorted for 15 min. The current was
recorded while warming with a rate of 15 K/min because of the small
value of the polarization. These measurements were made with the
PPMS. dc bias current was measured after cooling the sample to
lowest temperature without any poling field and recording the current
during warming the sample at a rate of 10 K/min under an applied
electric field using a Keithley 6517A electrometer.
3. RESULTS AND DISCUSSION
3.1. NaYNiWO6. 3.1.1. Structural Analysis. Room-temper-
ature powder XRD pattern could be best fitted with the polar
P21 space group, which is derived from the undistorted doubly
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ordered structure P4/nmm, and characterized by the
octahedral tilt system a−a−c+ in the Glazer notation,40 as
reported for NaYMnWO6 and NaHoCoWO6.32 The refined
XRD pattern at room temperature and the structural
parameters are given in Figure S1 and Table S1. Because
oxygen positions cannot be determined accurately by XRD, we
have analyzed the neutron data collected at 100 K by Rietveld
refinement using the program JANA2006, and the refined
pattern is given in Figure 1, whereas the corresponding
Figure 1. Rietveld refined neutron data of NaYNiWO6 collected at
100 K from the high-resolution WISH bank with average 2θ = 152.8°.
structural details are given in Table 1. Small amounts of
Y2WO6, NiO, and Na2WO4 were present as impurity phases,
which were included in the refinement. However, we could not
index the peak at 3.3 Å with any known impurity phase. The
crystal structure obtained from the structural data for
NaYNiWO6 is shown in Figure 2, in which each NiO6
octahedron shares all its corners with other WO6 units in an
ordered arrangement typical of rock-salt ordering, while Na
and Y cations are arranged in layers alternatively between the
layers of the B-site octahedra, along the c-axis.
Selected bond lengths and bond angles obtained from the
refinement of the crystal structure are given in Table 2. Careful
inspection of Ni−O and W−O bond lengths suggests that the
WO6 octahedra are highly distorted, with the W−O(6) bond
shorter (1.829(1) Å) than the W−O(5) one (2.074(1) Å)
indicating the displacement of W6+ cations from the center of
the octahedra toward the layer with the monovalent Na+
cations. The displacement of W6+-ions is due to SOJT and it
is usually observed for highly charged d0 cations in the
octahedral coordination as it has been reported for other W
compounds, for example, WO3 and Pb2MnWO6.21,22,41,42
SOJT is favored when the energy gap between the highest
occupied molecular orbital (HOMO; ligand 2p-nonbonding
orbitals) and the lowest unoccupied molecular orbital
(LUMO; metal t2g orbitals) is small, and the mixing of these
orbitals is symmetry forbidden in the undistorted phase. In this
case, a shift of the metal atom from the center of the
octahedron allows the mixing of these orbitals with a
concomitant energy gain. The shift of the metal atom from
the center of octahedra results in a lowering of the filled
HOMO energy while the energy of the empty LUMO
increases, and therefore, it lowers the overall energy of the
structure.43 All the Ni−O bond distances are approximately
equal to 2 Å with almost undistorted octahedra. The calculated
octahedral distortion parameter Δd of both the octahedra (Δd
× 10−3 = 3.733 for the W6+ cation and 0.537 for the Ni2+
cation) indicates that the WO6 octahedra are highly distorted
by the effect of SOJT compared to the NiO6 octahedra. The
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Chemistry of Materials pubs.acs.org/cm Article

Table 1. Structural Parameters of NaYNiWO6 at 100 K from the Refinement of the NPD Dataa
atom Wyckoff position X y z Uiso (Å2) Occ.
Na 2a 0.2545(4) 0.1992(5) 0.0159(3) 0.0286(6) 1.0
Y 2a 0.2682(2) 0.3044(3) 0.5033(1) 0.0423(3) 1.0
Ni 2a 0.7409(2) 0.2672(2) 0.2488(1) 0.0409(1) 1.0
W 2a 0.7461(4) 0.2500 0.7627(2) 0.0311(2) 1.0
O(1) 2a 0.5637(3) 0.5293(3) 0.6840(2) 0.0386(4) 1.0
O(2) 2a 0.5246(2) 0.5545(3) 0.3026(2) 0.0263(4) 1.0
O(3) 2a −0.0578(3) −0.0669(4) 0.2112(2) 0.0440(5) 1.0
O(4) 2a −0.0706(3) −0.0544(3) 0.7901(2) 0.0297(4) 1.0
O(5) 2a 0.8456(3) 0.2165(3) 0.5076(2) 0.0351(4) 1.0
O(6) 2a 0.6617(3) 0.2833(4) −0.0132(2) 0.0383(4) 1.0
a
Space group: P21; a = 5.31362(5) Å, b = 5.48659(5) Å, c = 7.73727(6) Å, and β = 90.202(9)°. Vol.: 225.55 Å3; GOF = 1.52, Rp = 1.37%, and Rwp
= 1.75%.

Figure 2. (a) Crystal structure of NaYNiWO6, where A-site cations (Na and Y) exhibit layered ordering and B-site cations (Ni and W) exhibit rock
salt ordering with distorted NiO6 and WO6 octahedra. (b) Octahedral coordination of Ni2+ and W6+ cations surrounded by oxygen with different
Ni−O and W−O bond lengths.

Table 2. Selected Bond Lengths, Angles, and BVS for NaYNiWO6 at 100 K
bond lengths (Å) bond angles (deg) bond valence sums
Ni O(1) 2.126(1) Ni−O(1)−W 139.85(4) Na 1.26(3)
O(2) 2.059(1) Ni−O(2)−W 143.94(5) Y 2.73(5)
O(3) 2.077(1) Ni−O(3)−W 150.59(5) Ni 2.15(4)
O(4) 2.044(1) Ni−O(4)−W 149.67(5) W 5.8(1)
O(5) 2.063(9) Ni−O(5)−W 147.18(4) O(1) 1.84(6)
O(6) 2.049(8) Ni−O(6)−W 153.00(4) O(2) 1.98(5)
W O(1) 1.970(1) O(3) 1.91(5)
O(2) 1.926(1) O(4) 2.05(7)
O(3) 1.901(1) O(5) 1.86(4)
O(4) 1.870(1) O(6) 2.10(4)
O(5) 2.074(1)
O(6) 1.829(1)

monoclinic structure with space group P21 results from the
antiphase rotation of the octahedra with respect to both a and
b axes and in-phase rotation with respect to the c-axis
according to tilt scheme a−a−c+ in Glazer’s notation, which
results in all Ni−O−W bond angles being smaller than 180°, as
shown in Table 2. The calculated bond valance sums (BVSs)
show expected oxidation states for the cations and anions.44
Also, BVS calculations reveal the underbonding of O(6) ions
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and overbonding of O(5) ions, which is consistent with WO6
octahedral distortion.
3.1.2. SHG Analysis. To further confirm the noncentrosym-
metric nature of these compounds, we have performed SHG
studies at room temperature. All the compounds investigated
in the present study are found to be SHG active under 1064
nm laser. The laser intensity is around 0.53, 0.67, and 0.53
Chem. Mater. XXXX, XXX, XXX−XXX
Chemistry of Materials
times of α-SiO2 for Dy, Ho, and Y compounds, respectively,
confirming the polar nature of these compounds.
3.1.3. Magnetic Properties. Temperature dependence of
the magnetization data M(T) measured under field-cooled
(FC) conditions with an applied magnetic field of 1000 Oe for
NaYNiWO6 is shown in Figure 3a. It may be mentioned here
Figure 3. (a) FC magnetization data of NaYNiWO6 as a function of
temperature measured under a magnetic field of 1000 Oe and heat
capacity divided by temperature on the right axis of the figure at 0 T.
(b) Magnetic field-dependent magnetization M(H) at 3 and 30 K.
that the zero-field cooled and FC curves do not deviate from
each other, and therefore, only the FC curve is shown in figure.
The heat capacity data Cp(T) measured under the zero applied
field is given in the right axis of Figure 3a. Both M(T) and
Cp(T) data indicate a long-range antiferromagnetic transition
of Ni2+ ions at TN = 21.5 K. In addition to the peak at TN in
the Cp(T) data, there is a small shoulder around 18 K. We
show later that these two peaks correspond to incommensurate
and collinear magnetic transitions, respectively. Isothermal
magnetization curves of NaYNiWO6 measured at 3 and 30 K
as a function of the magnetic field are shown in Figure 3b.
These results are consistent with the antiferromagnetic and
paramagnetic nature of the sample, respectively. Temperature-
dependent inverse susceptibility (1/χm) in the high-temper-
ature paramagnetic region follows a Curie−Weiss behavior, as
shown in Figure S2. The obtained effective magnetic moment
(μeff) is 3.36 μB/Ni, slightly higher than the calculated spin
only contribution of Ni2+ ions, which may be due to the small
magnetic impurity present in the compound. The negative
value of Curie−Weiss temperature (−49.76 K) is consistent
with the antiferromagnetic ordering.
3.1.4. Magnetic Structure. The compound NaYNiWO6 was
chosen for the neutron diffraction experiment because it does
not contain any neutron-absorbing element and the only
magnetic element present in the compound is Ni2+. Long scans
were collected at 100 and 30 K to determine the crystal
structure in the paramagnetic state and at 1.5 K to determine
the magnetic ground state. Several short collection scans were
carried out between 4 and 20 K with a step of 2 K. The NPD
data at 100 and 30 K are well fitted with the P21 space group.
On cooling, two small magnetic diffraction peaks appeared just
below TN, around 8.8 Å, which on further cooling became a
single prominent peak at ∼18 K, as shown in Figure S3. This
suggests a change in the magnetic structure at ∼18 K as
indicated by the double peak in the heat capacity data. At 20 K,
the magnetic satellites were indexed by the incommensurate k-
vector (0.471(2), 0, 0.491(4)) and at lower temperatures (1.5
K ≤ T ≤ 18 K), the magnetic peaks can be indexed by the
commensurate k-vector (0.5, 0, 0.5).
ISODISTORT was used to perform group theoretical
calculations to determine the possible magnetic space groups
of the ordered phases. Starting from the magnetic ground state
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at 1.5 K, the collected diffraction data can be well modeled
with the B[a]21 magnetic space group corresponding to the
mA2 irreducible representation. The Rietveld plot is shown in
Figure 4, which shows a good agreement between the observed
Figure 4. Rietveld refinement fit for the WISH neutron powder
diffraction data collected at average 2θ = 58.3° at 1.5 K of the
NaYNiWO6 compound.
and calculated data. The best fit is achieved when refining the
magnetic moments along both a- and c-directions. The
magnitude of the b-component was negligible compared to
the other two and the removal of the latter did not degrade the
refinement. The collinear refined magnetic structure at 1.5 K is
presented in Figure 5a. This magnetic structure has moment
components of Mx = 0.25(2) μB and Mz = 1.88(1) μB with the
total magnetic moment of 1.89(2) μB close to the theoretical
value of 2 μB for Ni2+ ions. At 20 K, the magnetic reflections
can be indexed with the incommensurate propagation vector ki
= (0.471(2), 0, 0.49(4)).
The data can be modeled with the P211′(a0g)0s magnetic
superspace group corresponding to the mF1 irreducible
representation. The obtained magnetic model is a spin density
wave with an amplitude of 0.89(4) μB with the moment
oriented along the c-direction, as shown in Figure 5c. The
evolution of the magnetic moment of Ni2+ as a function of
temperature (Figure 5b) follows a mean-field power-law
behavior, m(T) = m0(1 − T/TN)β with a critical exponent β
= 0.17(1).45
3.1.5. Dielectric, Pyroelectric, and dc-Bias Measurements.
To explore the dielectric properties and the magnetoelectric
coupling near the magnetic ordering temperature, we have
carried out electrical measurements on this compound.
Temperature dependence of dielectric constant, εr(T), under
different magnetic fields at 50 kHz, shows a clear anomaly at
the magnetic ordering temperature (TN = 21 K), as shown in
Figure 6a. Temperature dependence of the dielectric constant
εr(T) with different frequencies is shown for a wide
temperature range in Figure 6b. The dielectric peak at TN
does not shift with an increasing frequency, indicating the
absence of relaxation phenomena. However, it shows broad
maxima around 50 K, corresponding to dipolar relaxation
(DR) as shown in the loss data in the inset of Figure 6b. To
investigate whether the dielectric anomaly at the magnetic
ordering temperature is related to ferroelectric transition, we
have recorded pyroelectric current against temperature with a
poling electric field of E = ±18.9 kV/cm. The observed
pyroelectric current was integrated against time and presented
as temperature-dependent electric polarization, as shown in
Figure 6c. Considering the polar nature of this compound, one
Chem. Mater. XXXX, XXX, XXX−XXX
Chemistry of Materials
Figure 5. (a) Representation of the magnetic structure of NaYNiWO6 with the magnetic moments plotted for the Ni atoms at 1.5 K and (b) the
evolution of the Ni2+ magnetic moment as a function of temperature, showing the power-law fit as discussed in the text and (c) the
incommensurate sinusoidal structure at 20 K.
Figure 6. (a,b) Temperature-dependent dielectric constant εr(T) of
NaYNiWO6 measured at different magnetic fields and various
frequencies, respectively, and the loss data are shown in inset (b).
(c,d) Changes in electric polarization ΔP(T) with the temperature at
different magnetic fields obtained from integration of the pyroelectric
current peak and dc-biased current measured against temperature
with an electric field of Edc = +15.7 kV/cm and magnetic fields of 0
and 8 T.
can expect a nonzero electric polarization above Néel
temperature, but we did not find ferroelectric polarization,
indicating that this doubly ordered perovskite is pyroelectric in
the paramagnetic phase. However, the magnetic ordering
induces a change in polarization (ΔP) that is switchable by
changing the direction of the applied electric field. It should be
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noted that ΔP starts appearing at a temperature slightly higher
than TN because of the higher warming rate (15 K/min)
followed in the pyrocurrent measurement, which is essential
because of the low value of ΔP. It is also worth mentioning
that both commensurate and incommensurate magnetic
structures themselves are nonpolar, but the point group of
the paramagnetic structure is polar. Therefore, the change in
polarization at TN is due to a renormalization of the latter
caused by the magnetic phase transitions. This is usually
related to a magnetoelastic coupling, which is well known in
the literature.46−49 No anomalies were detected in the
evolution of the cell parameters across TN in our data,
probably because of the small value of ΔP. The related
structural changes are likely below the resolution of the present
diffraction experiment. To distinguish between polarization
because of ferroelectric dipoles and thermally stimulated free
charges, the dc-bias current measurement was performed. In
this measurement, the current is recorded around TN with
increasing temperature by applying the dc electric field without
prepoling the sample.50 Temperature-dependent dc-biased
current measured under an applied electric field E = +15.7
kV/cm is shown in Figure 6d. It shows a broad positive peak
associated with the polarization of the dipoles, followed by a
sharp negative current peak, indicating the depolarization of
the polarized diploes, hence confirming the intrinsic polar-
ization of NaYNiWO6. The appearance of electric polarization
at TN and switchability of the polarization direction by
changing the direction of the applied poling electric field
suggests the multiferroic properties of NaYNiWO6.
3.2. NaLnNiWO6 (Ln = Dy, Ho, and Yb). 3.2.1. Structural
Analysis. The structure and macroscopic properties of these
Chem. Mater. XXXX, XXX, XXX−XXX
Chemistry of Materials
three compounds are similar to those of NaYNiWO6. Powder
XRD data of all three compounds at RT are refined with the
P21 space group. Structural parameters for all the compounds
are given in Supporting Information. All the compounds
contain a small amount of Ln2WO6, NiO, and Na2WO4
impurities that are included in the refinement, and weight %
of the main and impurity phases are given in Table S2. The
bond angle Ni−O−W decreases with decreasing size of the
rare earth cation as given in Table S3 because of the higher
degree of Ni/W octahedral tilting. As a consequence,
compounds with smaller rare earth cations exhibit larger
distortions, which should lead to large electric polarization.26,27
3.2.2. Magnetic Properties. Temperature-dependent dc
magnetization measurements, measured under a magnetic
field of 100 Oe, are shown in Figure 7a−c. The absence of
Figure 7. (a−c) Field-cooled magnetization of NaLnNiWO6 (Ln =
Dy, Ho, and Yb) as a function of temperature measured under a
magnetic field of 100 Oe for all three compounds and heat capacity
divided by temperature on the right axis of figures. (d−f) Magnetic
field-dependent magnetization M(H) at different temperatures and
dM/dH for Dy, Ho is shown in the insets of (d,e).
magnetic anomaly in the M(T) data for the ordering of Ni2+
ions in all the three compounds is due to the large
paramagnetic contribution of the Dy3+, Ho3+, and Yb3+ ions
over Ni2+ moments. Therefore, the magnetic ordering
temperature of the Ni2+-ion is determined by heat capacity
measurement, as shown in the right axis of Figure 7a−c. These
compounds exhibit antiferromagnetic transition around 23 K
for Dy, 22 K for Ho, and 20 K for Yb. The small peak in the
heat capacity data of the Ho compound at low temperature ∼
2.3 K indicates the magnetic ordering of Ho3+ ions. There is a
clear double peak in the heat capacity data for the Yb sample
(TN1 ∼ 20 K and TN2 ∼ 18 K) and possibly a shoulder in the
Dy sample data. This double peak structure indicates the
change in the magnetic structure in a similar way to
NaYNiWO6, which has an incommensurate magnetic structure
at 20 K and a collinear magnetic structure below 18 K.
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Magnetic field dependent isothermal magnetization curves are
shown in Figure 7d−f. The nonlinear behavior in M versus H
curves at low temperatures suggests a metamagnetic transition
because of the field-induced effect on the magnetic Ln3+ ion
ordering, as can be seen in the dM/dH curves in the inset of
Figure 7d,e. Temperature-dependent inverse susceptibility (1/
χm) of these compounds follows the Curie−Weiss law, as
shown in Figure S4. The experimental effective paramagnetic
moment (μeff) is in agreement with the calculated moment, as
shown in Figure S4, and the sign of the Curie−Weiss
temperature is negative, confirming the antiferromagnetic
interaction in these compounds.
3.2.3. Electrical Properties. In Figure 8a−c, dielectric
constants (εr) measured in the temperature range of 2−40
K, with 50 kHz under different applied magnetic fields are
shown. An apparent anomaly is observed for all three
compounds at the magnetic ordering temperature. The
frequency-dependent dielectric data εr(T) are shown in Figure
S5. The dielectric constant of NaYbNiWO6 and NaHoNiWO6
increases monotonously with temperature showing a clear
anomaly at TN. Moreover, it exhibits DR around 50 K as
shown in the loss data Figure S5c,f. The Yb sample shows, in
addition to the previous observation, dielectric relaxation at
higher temperatures around 170 K. In the case of
NaHoNiWO6 at low temperature, a broad anomaly corre-
sponding to the short-range ordering of Ho3+ ions is observed.
The anomaly varies slightly with applied fields in the εr(T)
data. Therefore, we have measured magnetocapacitance at
different temperatures between 2 and 30 K and observed a
sizeable magnetocapacitance effect below 10 K, as shown in
Figure S5d. Temperature-dependent polarization and dc-bias
data for NaDyNiWO6 are shown in Figure 8d,g. Temperature-
dependent dc-bias current measurement, measured with an
applied electric field of E = +12.9 kV/cm, shows a small
positive peak, followed by a sharp negative depolarization
current peak, which confirmed the ferroelectric nature of this
compound at magnetic ordering temperature. Also, we have
measured the dc-bias current by applying an electric field of E
= −12.9 kV/cm to get the reverse dc-bias signal. By removing
the small positive polarization peak in the dc-bias signal, we
have integrated the depolarization peak to obtain spontaneous
polarization. The observed dc-bias signal at the magnetic
ordering temperature confirmed the coupling between
ferroelectricity and magnetism in this compound. We could
not measure the pyroelectric current at TN for NaDyNiWO6
likely because the change in the pyrocurrent signal is too low
to be detected.
Temperature-dependent electric polarization, ΔP(T), and dc
bias current measurement for the other two compounds
NaHoNiWO6 and NaYbNiWO6, are shown in Figure 8. The
appearance of the nonzero polarization and dc-bias signal at 0
T below magnetic ordering temperature confirms the multi-
ferroic properties of these doubly ordered perovskites.
Although we have not performed neutron diffraction measure-
ment in the other compounds, the observed heat capacity data
and appearance of ferroelectric polarization at magnetic
ordering temperature of Ni2+ ions suggest that all other
compounds should also have a similar incommensurate and
commensurate magnetic structure of the Ni2+ moments. In all
the compounds, the observed polarization at TN could be due
to possible enhancement of high-temperature polarization
expected from the magnetoelastic coupling.
Chem. Mater. XXXX, XXX, XXX−XXX
Chemistry of Materials pubs.acs.org/cm Article

Figure 8. (a−c) Temperature variation of dielectric constant εr(T) of NaLnNiWO6 (Ln = Dy, Ho, and Yb) compounds. (d) Temperature-
dependent electric polarization ΔP(T) obtained from the integration of the negative depolarization peak in dc-bias current measurement data of
NaDyNiWO6. (e,f) Change in electric polarization ΔP(T) against temperature under different magnetic fields obtained from the integration of the
pyroelectric current peak for Ho, Yb compounds. (g−i) dc-bias current as a function of temperature measured with an electric filed as mentioned in
figure and under magnetic fields 0 and 8 T.

4. CONCLUSIONS
We have synthesized a new family of doubly ordered
■ ASSOCIATED CONTENT
* Supporting Information
sı

perovskites with small rare earth cations NaLnNiWO6 (Ln =
Y, Dy, Ho, and Yb) under high-pressure and high-temperature
conditions. These compounds crystallize in the polar P21
structure with the layered A-site and rock salt B-site cation
ordering. Magnetic measurements show that these compounds
order antiferromagnetically around 20 K. Neutron diffraction
studies revealed that at 20 K, the NaYNiWO6 compound has
an incommensurate sinusoidal magnetic structure and it
changes to a commensurate collinear structure below 18 K.
A double-peak structure in the heat capacity data of
NaLnNiWO6 (Ln = Dy, Ho, and Yb) suggests the presence
of an incommensurate and commensurate magnetic phase
transition in these compounds as well. The switchability of the
polarization change (ΔP(T)) and dc-bias current signal at TN
suggests the multiferroic properties of these compounds. Our
experimental investigation opens up an avenue for further
detailed theoretical studies in doubly ordered perovskites as
well as for the design of new polar materials with interesting
properties.
G https://dx.doi.org/10.1021/acs.chemmater.0c01149
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.chemmater.0c01149.
Rietveld refinement data and experimental character-
ization of NaYNiWO6 (CIF)
Rietveld refinement data and experimental character-
ization of NaDyNiWO6 (CIF)
Rietveld refinement data and experimental character-
ization of NaHoNiWO6 (CIF)
Rietveld refinement data and experimental character-
ization of NaYbNiWO6 (CIF)
Rietveld refined powder XRD data of NaYNiWO6,
NaDYNiWO6, NaHoNiWO6, and NaYbNiWO6 samples
recorded at room temperature; structural parameters of
NaYNiWO6, NaDYNiWO6, NaHoNiWO6,and NaYbNi-
WO6 from the PXRD pattern refinement; linear fit of the
inverse susceptibility (1/χmol) as a function of temper-
ature for NaYNiWO6; neutron powder diffraction
patterns of NaYNiWO6 for selected temperatures;
proportions of main and impurity phases; selected
bond lengths and bond angles from XRD refinement
Chem. Mater. XXXX, XXX, XXX−XXX
Chemistry of Materials
at room temperature; temperature dependence of
dielectric constant εr(T) and loss measured under
different frequencies (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Athinarayanan Sundaresan − School of Advanced Materials
and Chemistry and Physics of Materials Unit, Jawaharlal Nehru
Centre for Advanced Scientific Research, Bangalore 560064,
India; orcid.org/0000-0002-1613-3030;
Email: sundaresan@jncasr.ac.in
Authors
Ravi Shankar P N − School of Advanced Materials and
Chemistry and Physics of Materials Unit, Jawaharlal Nehru
Centre for Advanced Scientific Research, Bangalore 560064,
India; orcid.org/0000-0003-0388-5126
Fabio Orlandi − ISIS Facility, Rutherford Appleton Laboratory,
Didcot OX11 0QX, U.K.; orcid.org/0000-0001-6333-
521X
Pascal Manuel − ISIS Facility, Rutherford Appleton Laboratory,
Didcot OX11 0QX, U.K.
Weiguo Zhang − Department of Chemistry, University of
Houston, Houston, Texas 77204, United States
P. Shiv Halasyamani − Department of Chemistry, University of
Houston, Houston, Texas 77204, United States; orcid.org/
0000-0003-1787-1040
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.chemmater.0c01149
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
A.S. would like to acknowledge the financial support from the
Science and Engineering Board (SERB sanction no. CRG/
2018/000520), Department of Science and Technology
(DST), Government of India. A.S. and R.S. thank the
Nanomission council, Department of Science and Technology,
India (SR/Nm/Z-07/2015(G)) for the financial support to
carryout the experiment, and Jawaharlal Nehru Centre for
Advanced Scientific Research (JNCASR) for managing the
project. We acknowledge the Science and Technology Facility
Council (STFC) for the provision of the neutron beam time at
the WISH beamline. The authors would like to acknowledge
Sheik Saqr Laboratory (SSL) at Jawaharlal Nehru Center for
Advanced Scientific Research (JNCASR) for various exper-
imental facilities. R.S. acknowledges the Council of Scientific
and Industrial Research (CSIR) for providing research
fellowship (JNC/S0581). PSH and WZ thank the Welch
Foundation (Grant E-1457) for support.
■
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