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Na LN Ni WO6 LN YDy Hoand Yb
Na LN Ni WO6 LN YDy Hoand Yb
net/publication/341692834
A-site and B-site cation ordering induces polar and multiferroic behavior in
the perovskite NaLnNiWO6 (Ln = Y, Dy, Ho, Yb)
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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.
16 μC/cm2.26 Further investigation shows that the size of the ordered structure P4/nmm, and characterized by the
A-site cation plays a crucial role in terms of electrical octahedral tilt system a−a−c+ in the Glazer notation,40 as
polarization, with a large increase of the latter with the reported for NaYMnWO6 and NaHoCoWO6.32 The refined
difference in the ionic size of the A-site cations.26,27 Several XRD pattern at room temperature and the structural
compounds belonging to this family of oxides have been parameters are given in Figure S1 and Table S1. Because
reported.25,28−32 However, there is no experimental report on oxygen positions cannot be determined accurately by XRD, we
the existence of ferroelectricity in the paramagnetic state of have analyzed the neutron data collected at 100 K by Rietveld
these compounds. In this work, we report on the synthesis and refinement using the program JANA2006, and the refined
structural characterization of a new series of polar (P21) pattern is given in Figure 1, whereas the corresponding
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
Figure 1. Rietveld refined neutron data of NaYNiWO6 collected at
of the heater, and the whole assembly was inserted into the
pyrophyllite cube used as a pressure-transmitting medium. The 100 K from the high-resolution WISH bank with average 2θ = 152.8°.
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 structural details are given in Table 1. Small amounts of
the pressure was released slowly. Y2WO6, NiO, and Na2WO4 were present as impurity phases,
2.2. Characterization. Powder X-ray diffraction (XRD) was which were included in the refinement. However, we could not
carried out using a PANalytical Empyrean alpha-1 diffractometer index the peak at 3.3 Å with any known impurity phase. The
using monochromatized Cu Kα1 radiation and the data were acquired crystal structure obtained from the structural data for
in the 2θ range 10−120° for Rietveld refinement, which was
performed using the FullProf suite program.33,34 The neutron powder
NaYNiWO6 is shown in Figure 2, in which each NiO6
diffraction measurements were carried out on the WISH diffrac- octahedron shares all its corners with other WO6 units in an
tometer located at the ISIS pulsed neutron and muon facility of the ordered arrangement typical of rock-salt ordering, while Na
Rutherford Appleton Laboratory (UK).35 The data were collected in and Y cations are arranged in layers alternatively between the
the temperature range of 1.5−100 K using an Oxford instrument layers of the B-site octahedra, along the c-axis.
cryostat. Rietveld refinement of neutron diffraction data was Selected bond lengths and bond angles obtained from the
performed using the JANA2006 program.36 Group theoretical refinement of the crystal structure are given in Table 2. Careful
calculations were performed with the help of the ISOTROPY and inspection of Ni−O and W−O bond lengths suggests that the
ISODISTORT software.37 Second-harmonic generation (SHG) WO6 octahedra are highly distorted, with the W−O(6) bond
measurements were carried out on the NaLnNiWO6 (Ln = Y, Dy,
and Ho) samples at room temperature using a modified Kurtz-
shorter (1.829(1) Å) than the W−O(5) one (2.074(1) Å)
nonlinear optical system with a pulsed Nd:YAG laser (λ = 1064 nm). indicating the displacement of W6+ cations from the center of
The technicalities of the apparatus and procedure have already been the octahedra toward the layer with the monovalent Na+
reported in the literature.38,39 cations. The displacement of W6+-ions is due to SOJT and it
dc magnetization measurements were carried out with a Magnetic is usually observed for highly charged d0 cations in the
Property Measurement System (MPMS3-SQUID), Quantum Design, octahedral coordination as it has been reported for other W
USA. Heat capacity data were recorded with a Physical Property compounds, for example, WO3 and Pb2MnWO6.21,22,41,42
Measurement System (PPMS, Quantum Design). Temperature- SOJT is favored when the energy gap between the highest
dependent dielectric and pyroelectric measurements were carried occupied molecular orbital (HOMO; ligand 2p-nonbonding
out with an Agilent E4980A LCR and Keithley 6517A electrometer,
respectively. For all electrical measurements, PELCO silver paste was
orbitals) and the lowest unoccupied molecular orbital
used to make electrodes. During pyroelectric measurements, the (LUMO; metal t2g orbitals) is small, and the mixing of these
samples were poled with an electric field (±E), and to remove any orbitals is symmetry forbidden in the undistorted phase. In this
stray charges, the electrodes were shorted for 15 min. The current was case, a shift of the metal atom from the center of the
recorded while warming with a rate of 15 K/min because of the small octahedron allows the mixing of these orbitals with a
value of the polarization. These measurements were made with the concomitant energy gain. The shift of the metal atom from
PPMS. dc bias current was measured after cooling the sample to the center of octahedra results in a lowering of the filled
lowest temperature without any poling field and recording the current HOMO energy while the energy of the empty LUMO
during warming the sample at a rate of 10 K/min under an applied increases, and therefore, it lowers the overall energy of the
electric field using a Keithley 6517A electrometer.
structure.43 All the Ni−O bond distances are approximately
equal to 2 Å with almost undistorted octahedra. The calculated
3. RESULTS AND DISCUSSION octahedral distortion parameter Δd of both the octahedra (Δd
3.1. NaYNiWO6. 3.1.1. Structural Analysis. Room-temper- × 10−3 = 3.733 for the W6+ cation and 0.537 for the Ni2+
ature powder XRD pattern could be best fitted with the polar cation) indicates that the WO6 octahedra are highly distorted
P21 space group, which is derived from the undistorted doubly by the effect of SOJT compared to the NiO6 octahedra. The
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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 and overbonding of O(5) ions, which is consistent with WO6
antiphase rotation of the octahedra with respect to both a and octahedral distortion.
b axes and in-phase rotation with respect to the c-axis 3.1.2. SHG Analysis. To further confirm the noncentrosym-
according to tilt scheme a−a−c+ in Glazer’s notation, which
metric nature of these compounds, we have performed SHG
results in all Ni−O−W bond angles being smaller than 180°, as
shown in Table 2. The calculated bond valance sums (BVSs) studies at room temperature. All the compounds investigated
show expected oxidation states for the cations and anions.44 in the present study are found to be SHG active under 1064
Also, BVS calculations reveal the underbonding of O(6) ions nm laser. The laser intensity is around 0.53, 0.67, and 0.53
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times of α-SiO2 for Dy, Ho, and Y compounds, respectively, at 1.5 K, the collected diffraction data can be well modeled
confirming the polar nature of these compounds. with the B[a]21 magnetic space group corresponding to the
3.1.3. Magnetic Properties. Temperature dependence of mA2 irreducible representation. The Rietveld plot is shown in
the magnetization data M(T) measured under field-cooled Figure 4, which shows a good agreement between the observed
(FC) conditions with an applied magnetic field of 1000 Oe for
NaYNiWO6 is shown in Figure 3a. It may be mentioned here
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.
three compounds are similar to those of NaYNiWO6. Powder Magnetic field dependent isothermal magnetization curves are
XRD data of all three compounds at RT are refined with the shown in Figure 7d−f. The nonlinear behavior in M versus H
P21 space group. Structural parameters for all the compounds curves at low temperatures suggests a metamagnetic transition
are given in Supporting Information. All the compounds because of the field-induced effect on the magnetic Ln3+ ion
contain a small amount of Ln2WO6, NiO, and Na2WO4 ordering, as can be seen in the dM/dH curves in the inset of
impurities that are included in the refinement, and weight % Figure 7d,e. Temperature-dependent inverse susceptibility (1/
of the main and impurity phases are given in Table S2. The χm) of these compounds follows the Curie−Weiss law, as
bond angle Ni−O−W decreases with decreasing size of the shown in Figure S4. The experimental effective paramagnetic
rare earth cation as given in Table S3 because of the higher moment (μeff) is in agreement with the calculated moment, as
degree of Ni/W octahedral tilting. As a consequence, shown in Figure S4, and the sign of the Curie−Weiss
compounds with smaller rare earth cations exhibit larger temperature is negative, confirming the antiferromagnetic
distortions, which should lead to large electric polarization.26,27 interaction in these compounds.
3.2.2. Magnetic Properties. Temperature-dependent dc 3.2.3. Electrical Properties. In Figure 8a−c, dielectric
magnetization measurements, measured under a magnetic constants (εr) measured in the temperature range of 2−40
field of 100 Oe, are shown in Figure 7a−c. The absence of 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
Figure 7. (a−c) Field-cooled magnetization of NaLnNiWO6 (Ln =
Dy, Ho, and Yb) as a function of temperature measured under a have integrated the depolarization peak to obtain spontaneous
magnetic field of 100 Oe for all three compounds and heat capacity polarization. The observed dc-bias signal at the magnetic
divided by temperature on the right axis of figures. (d−f) Magnetic ordering temperature confirmed the coupling between
field-dependent magnetization M(H) at different temperatures and ferroelectricity and magnetism in this compound. We could
dM/dH for Dy, Ho is shown in the insets of (d,e). not measure the pyroelectric current at TN for NaDyNiWO6
likely because the change in the pyrocurrent signal is too low
magnetic anomaly in the M(T) data for the ordering of Ni2+ to be detected.
ions in all the three compounds is due to the large Temperature-dependent electric polarization, ΔP(T), and dc
paramagnetic contribution of the Dy3+, Ho3+, and Yb3+ ions bias current measurement for the other two compounds
over Ni2+ moments. Therefore, the magnetic ordering NaHoNiWO6 and NaYbNiWO6, are shown in Figure 8. The
temperature of the Ni2+-ion is determined by heat capacity appearance of the nonzero polarization and dc-bias signal at 0
measurement, as shown in the right axis of Figure 7a−c. These T below magnetic ordering temperature confirms the multi-
compounds exhibit antiferromagnetic transition around 23 K ferroic properties of these doubly ordered perovskites.
for Dy, 22 K for Ho, and 20 K for Yb. The small peak in the Although we have not performed neutron diffraction measure-
heat capacity data of the Ho compound at low temperature ∼ ment in the other compounds, the observed heat capacity data
2.3 K indicates the magnetic ordering of Ho3+ ions. There is a and appearance of ferroelectric polarization at magnetic
clear double peak in the heat capacity data for the Yb sample ordering temperature of Ni2+ ions suggest that all other
(TN1 ∼ 20 K and TN2 ∼ 18 K) and possibly a shoulder in the compounds should also have a similar incommensurate and
Dy sample data. This double peak structure indicates the commensurate magnetic structure of the Ni2+ moments. In all
change in the magnetic structure in a similar way to the compounds, the observed polarization at TN could be due
NaYNiWO6, which has an incommensurate magnetic structure to possible enhancement of high-temperature polarization
at 20 K and a collinear magnetic structure below 18 K. expected from the magnetoelastic coupling.
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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 = The Supporting Information is available free of charge at
Y, Dy, Ho, and Yb) under high-pressure and high-temperature https://pubs.acs.org/doi/10.1021/acs.chemmater.0c01149.
conditions. These compounds crystallize in the polar P21 Rietveld refinement data and experimental character-
structure with the layered A-site and rock salt B-site cation ization of NaYNiWO6 (CIF)
ordering. Magnetic measurements show that these compounds Rietveld refinement data and experimental character-
order antiferromagnetically around 20 K. Neutron diffraction ization of NaDyNiWO6 (CIF)
studies revealed that at 20 K, the NaYNiWO6 compound has Rietveld refinement data and experimental character-
an incommensurate sinusoidal magnetic structure and it ization of NaHoNiWO6 (CIF)
changes to a commensurate collinear structure below 18 K. Rietveld refinement data and experimental character-
A double-peak structure in the heat capacity data of ization of NaYbNiWO6 (CIF)
NaLnNiWO6 (Ln = Dy, Ho, and Yb) suggests the presence Rietveld refined powder XRD data of NaYNiWO6,
of an incommensurate and commensurate magnetic phase NaDYNiWO6, NaHoNiWO6, and NaYbNiWO6 samples
recorded at room temperature; structural parameters of
transition in these compounds as well. The switchability of the
NaYNiWO6, NaDYNiWO6, NaHoNiWO6,and NaYbNi-
polarization change (ΔP(T)) and dc-bias current signal at TN WO6 from the PXRD pattern refinement; linear fit of the
suggests the multiferroic properties of these compounds. Our inverse susceptibility (1/χmol) as a function of temper-
experimental investigation opens up an avenue for further ature for NaYNiWO6; neutron powder diffraction
detailed theoretical studies in doubly ordered perovskites as patterns of NaYNiWO6 for selected temperatures;
well as for the design of new polar materials with interesting proportions of main and impurity phases; selected
properties. bond lengths and bond angles from XRD refinement
G https://dx.doi.org/10.1021/acs.chemmater.0c01149
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■ AUTHOR INFORMATION
Corresponding Author
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Electronic and Magnetic Properties of La2NiMnO6 and La2CoMnO6
Complete contact information is available at:
with Cationic Ordering. Appl. Phys. Lett. 2012, 100, 062406.
https://pubs.acs.org/10.1021/acs.chemmater.0c01149 (14) Choudhury, D.; Mandal, P.; Mathieu, R.; Hazarika, A.; Rajan,
S.; Sundaresan, A.; Waghmare, U. V.; Knut, R.; Karis, O.; Nordblad,
Notes P.; et al. Near-Room-Temperature Colossal Magnetodielectricity and
The authors declare no competing financial interest. Multiglass Properties in Partially Disordered La2NiMnO6. Phys. Rev.
■ ACKNOWLEDGMENTS
A.S. would like to acknowledge the financial support from the
Lett. 2012, 108, 127201.
(15) Sobolev, A. V.; Glazkova, I. S.; Akulenko, A. A.; Sergueev, I.;
Chumakov, A. I.; Yi, W.; Belik, A. A.; Presniakov, I. A. 61Ni Nuclear
Forward Scattering Study of Magnetic Hyperfine Interactions in
Science and Engineering Board (SERB sanction no. CRG/ Double Perovskites A2NiMnO6 (A = Sc, In, Tl). J. Phys. Chem. C
2018/000520), Department of Science and Technology 2019, 123, 23628−23634.
(DST), Government of India. A.S. and R.S. thank the (16) Song, W. H.; Dai, J. M.; Ye, S. L.; Wang, K. Y.; Du, J. J.; Sun, Y.
Nanomission council, Department of Science and Technology, P. Preparation and Magnetic Properties of the Double-Perovskite
India (SR/Nm/Z-07/2015(G)) for the financial support to A2FeMoO6 (A=Ca, Sr, Ba) Polycrystals with Nanometer-Scale Par-
carryout the experiment, and Jawaharlal Nehru Centre for ticles. J. Appl. Phys. 2001, 89, 7678−7680.
Advanced Scientific Research (JNCASR) for managing the (17) Yadav, R.; Elizabeth, S. Magnetic Frustration and Dielectric
project. We acknowledge the Science and Technology Facility Relaxation in Insulating Nd2NiMnO6 Double Perovskites. J. Appl.
Council (STFC) for the provision of the neutron beam time at Phys. 2015, 117, 053902.
the WISH beamline. The authors would like to acknowledge (18) Ali, A.; Sharma, G.; Vardhan, A.; Pasrija, K.; Rajput, S.; Maitra,
Sheik Saqr Laboratory (SSL) at Jawaharlal Nehru Center for T.; Kumar, S.; Singh, Y. Magnetocaloric Effects from an Interplay of
Advanced Scientific Research (JNCASR) for various exper- Magnetic Sublattices in Nd2NiMnO6. J. Phys.: Condens. Matter 2019,
imental facilities. R.S. acknowledges the Council of Scientific 31, 305803.
(19) Bull, C. L.; Gleeson, D.; Knight, K. S. Determination of B-Site
and Industrial Research (CSIR) for providing research
Ordering and Structural Transformations in the Mixed Transition
fellowship (JNC/S0581). PSH and WZ thank the Welch Metal Perovskites La2CoMnO6and La2NiMnO6. J. Phys.: Condens.
Foundation (Grant E-1457) for support.
■
Matter 2003, 15, 4927−4936.
(20) Das, H.; Waghmare, U. V.; Saha-Dasgupta, T.; Sarma, D. D.
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