Abstract
Double-perovskite multiferroics have been investigated because alternating orders of magnetic ions act as distinct magnetic origins for ferroelectricity. In Yb2CoMnO6, the frustrated antiferromagnetic order emerging at TN = 52 K induces ferroelectric polarization perpendicular to the c axis through cooperative O2− shifts via the symmetric exchange striction. In our detailed measurements of the magnetoelectric properties of single-crystalline Yb2CoMnO6, we observe full ferromagnetic-like hysteresis loops that are strongly coupled to the dielectric constant and ferroelectric polarization at various temperatures below TN. Unlike Lu2CoMnO6 with non-magnetic Lu3+ ions, we suggest the emergence of additional ferroelectric polarization along the c axis below the ordering temperature of magnetic Yb3+ ions, TYb ≈ 20 K, based on the spin structure established from recent neutron diffraction experiments. While the proposed description for additional ferroelectricity, ascribed to the symmetric exchange striction between Yb3+ and Co2+/Mn4+ magnetic moments, is clearly given, anomalies of dielectric constants along the c axis are solely observed. Our interesting findings on magnetoelectric hysteresis and the possible development of additional ferroelectricity reveal notable characteristics of double perovskites and provide essential guidance for the further examination of magnetoelectric functional properties.
Similar content being viewed by others
Introduction
Condensed-matter systems with strongly coupled order parameters offer immense opportunities for a fundamental understanding of their governing interactions as well as for the utilization of new technologies. Interesting cross-coupling effects can be observed in magnetoelectric and multiferroic materials, whose interlinked electric and magnetic order parameters have inspired materials research to explore new multifunctional materials and investigate the mechanisms underlying magnetoelectiricity1,2,3,4. Research has been aimed at discovering ferroelectricity driven by a specific type of ordered magnetic state. Ferroelectric distortions have been ascribed to both symmetric and antisymmetric parts of the magnetic exchange striction5,6. Because of this origin, the substantial coupling between structural distortions and magnetic order often results in a large variation in the dielectric and ferroelectric properties through the application of magnetic fields2,3,4,7. Although various magnetic materials have been known to be magnetoelectrics or multiferroics, exploring new materials with cross-couplings is still beneficial for improving the feasibility of multiple functionalities.
Double-perovskite compounds, in which two different transition-metal ions are alternately located in octahedral environments, have been widely investigated. In such materials, combinations of mixed-valence magnetic ions reveal the intricate magnetic interactions and ionic valence/antisite disorders, which enable various fascinating physical properties, such as metamagnetism8,9,10, exchange bias11,12,13, magnetocaloric effect14,15,16,17, and multiferroicity18,19,20,21. Recent studies have also focused on the potential use of double-perovskite halides in energy devices such as photovoltaic devices22,23,24, photocatalysts25,26,27,28, UV detectors29,30, and solar energy storage31,32. Double-perovskite R2CoMnO6 (R = La, …, Lu) compounds crystallize in a monoclinic double-perovskite structure (P21/n space group), in which alternating Co2+ and Mn4+ ions are located in corner-shared octahedral O2− environments33. Co2+ and Mn4+ superexchange interactions result in a long-range ferromagnetic order, whose ordering temperature varies from 204 K for La2CoMnO6 to 67 K for Er2CoMnO6 as the size of the rare-earth ions decreases33. It has been known that the incomplete alteration of the Co2+ and Mn4+ ions results in a small portion of additional antiferromagnetic clusters with Co2+- Co2+ or Mn4+- Mn4+ pairs, which generate anti-sites of ionic disorders and/or antiphase boundaries34,35,36,37. Another valence state of Co3+- Mn3+ can be additionally formed as antiferromagnetic clusters38. In Yb2CoMnO6 (YCMO) and Lu2CoMnO6, significant distortions of O2− octrahedra owing to the smaller size of rare-earth ions induce a magnetic frustration associated with the nearest-neighbor ferromagnetic and next-nearest-neighbor antiferromagnetic exchange interactions39. These frustrated interactions lead to up-up-down-down (↑↑↓↓) spin ordering along the c axis with ordering temperatures of 52 and 48 K for YCMO and Lu2CoMnO6, respectively40.
Lu2CoMnO6 is a double-perovskite multiferroic; it is a rare example of a multiferroic that exhibits ferromagnetic-like magnetic hysteresis with net magnetization and strong coupling to the dielectric constant and ferroelectric polarization in response to external magnetic fields20,41. The ↑↑↓↓ spin arrangement formed by frustrated exchange interactions has been known to generate ferroelectric polarization perpendicular to the c axis through the cooperative O2− shifts via the symmetric exchange striction20,21,42. In Er2CoMnO6, the ferrimagnetic order activated by Er3+ moments antiparallelly aligned with ferromagnetic Co2+/Mn4+ sublattices results in an inversion of the magnetic hysteresis loop9,43. Moreover, the additional small portion of multiferroic phase coexisting with the ferrimagnetic phase has been presented as simultaneous metamagnetic and ferroelectric transitions41. Despite the clear demonstrations of correlated magnetic and ferroelectric properties in such multiferroics, the full hysteretic behavior in coupled magnetization and polarization and the role of magnetic rare-earth ions in multiferroicity still remain unclear.
In this study, we investigated the magnetic and magnetoelectric features of a frustrated antiferromagnet, YCMO. We have first observed the emergence of ferroelectricity perpendicular to the c axis in a single crystalline YCMO. Isothermal magnetization along the c axis is observed to exhibit ferromagnetic-like hysteresis with large remanent magnetization, which is strongly correlated with the isothermal dielectric constant and ferroelectric polarization perpendicular to the c axis below TN = 52 K. Based on the results of recent neutron diffraction experiments on YCMO, we proposed that the symmetric exchange striction between Yb3+ and Co2+/Mn4+ moments may lead to additional ferroelectricity along the c axis below TYb ≈ 20 K44. We note that in type-II multiferroics, multiple ferroelectricity, in which two different sorts of ferroelectricity emerge with magnetic origins, has scarcely been observed. However, the existence of additional ferroelectric polarization was not verified. Instead, dielectric anomaly along the c axis was observed. Our findings indicate distinct characteristics of the double-perovskite multiferroic and lay important groundwork for investigating materials with improved magnetoelectric functionalities.
Results and discussion
YCMO crystallizes in a monoclinic P21/n structure with lattice parameters a = 5.177 Å, b = 5.548 Å, and c = 7.418 Å with β = 89.648°41. The magnetic properties of YCMO were examined based on the temperature (T) dependence of magnetic susceptibility, defined as magnetization (M) divided by the magnetic field (H), χ = M/H, measured at H = 0.2 T on warming after zero-H-cooling (ZFC) and on cooling at the same H (FC). Figure 1a and b shows the anisotropic χ curves at T = 2–100 K for the two different orientations, H//c and H \(\perp \) c, respectively. As T decreases from 100 K, both the ZFC and FC χ curves along the c axis increase smoothly with a nearly identical shape; they show a sharp anomaly at TN = 52 K, which is considered to be the emergence of the ↑↑↓↓-type spin order41,44. Upon further cooling below TN, the χ curves decrease considerably and begin to split around TH ≈ 37 K, which indicates the onset of thermally hysteretic behavior similar to that of Lu2CoMnO645. Additional and much larger splitting occurs below TYb ≈ 20 K, where the Yb3+ moments are ordered. The χ values for H//c and H \(\perp \) c indicate strong anisotropy, consistent with the spins primarily aligned along the c axis.
In Fig. 1c, the dielectric constant (ε′) perpendicular to the c axis, measured at f = 100 kHz and H = 0, 1.25, 1.5, 1.75, 2.0, and 3.0 T along the c axis, is plotted. At zero H, ε′ decreases almost linearly from 100 K and starts to increase near TN = 52 K. It exhibits a broad peak at TH, followed by a slight slope change around TYb. As H along the c axis is increased, the broad peak at TH is progressively suppressed, and the slope change at TYb becomes clearer. The peak completely disappears at 3.0 T. The heat capacity divided by the temperature (C/T) also shows a sharp anomaly at TN, indicating a long-range order of the Co2+ and Mn4+ moments (Fig. 1d), consistent with that observed in Lu2CoMnO621. An additional increase in C/T is found at TYb, and a broad peak below TYb implies the long-range antiferromagnetic order of Yb3+ spins (Fig. 1d)44.
A previous neutron diffraction experiment on isostructural Lu2CoMnO6 established the magnetic structure of alternating Co2+ and Mn4+ moments as ↑↑↓↓-type spin configurations along the c axis46. The ↑↑↓↓ spin arrangement is driven by the nearest-neighbor ferromagnetic exchange interaction frustrated with comparable next-nearest-neighbor antiferromagnetic interactions. This system is called a frustrated antiferromagnet because the magnetic moments between ↑↑ and ↓↓ spin layers are canceled out, similar to an A-type antiferromagnet. A recent neutron diffraction study on YCMO has shown the same ↑↑↓↓-type arrangement of Co2+ and Mn4+ moments41. Figure 2a depicts the two types of frustrated antiferromagnetic domains of YCMO projected onto the bc plane. In the ↑↑↓↓ spin configuration as one type of domain, the parallel spin pairs of Co2+ and Mn4+ ions tend to contract, while the antiparallel spin pairs tend to expand, based on the exchange striction, which prefers ferromagnetic nearest-neighbor coupling. As a result, the contraction and expansion of the spin pairs distort between O2− ions with cooperative displacements to the left and generate ferroelectric polarization (P) along the b axis, + P. For the other type of domains with the ↑↓↓↑ spin configuration, the exchange striction induces displacements of O2− ions to the right and thus produces − P.
The full magnetic curve for H//c was recorded at 3 K after ZFC up to ± 6 T, as shown in Fig. 2b. The ↑↑↓↓-type spin order exhibits a ferromagnetic-like hysteresis loop with remanent M, Mr = 5.1 μB/f.u., and magnetic coercive field, Hc = 1.4 T. The initial curve increases slowly and shows a sudden jump at ~ 3.8 T, indicating a change in the spin state from ↑↑↓↓ to ↑↑↑↑. Above this value, M increases linearly without saturation. The value of M at 6 T is found to be ~ 6.5 μB/f.u., ascribed to the magnetic moments of Yb3+ ions in addition to the M value of 6 μB for the Co2+ (S = 3/2) and Mn4+ (S = 3/2) moments in a formula unit. Upon decreasing H from 6 T, M reduces progressively until it shows an abrupt decrease at approximately –0.8 T with the formation of the ↑↑↓↓-type magnetic domains. As H is further decreased, another step arises at –3.8 T for the change in the spin state to ↓↓↓↓. The antisymmetric shape of the loop is accomplished by sweeping H in the other direction.
The magnetoelectrically hysteretic behavior of YCMO was examined through the isothermal ferroelectric P, obtained by integrating the pyroelectric current density measured after poling in an electric field (E = 100 V or E = 2.3 kV/cm) perpendicular to the c axis and H up to ± 6 T along the c axis. In Fig. 2c, P was measured at 3 K by sweeping H without removing E after poling. The magnitude of P at 0 T was 4.3 μC/m2. P in the initial curve disappears at 3.8 T, consistent with the change in the spin state from ↑↑↓↓ to ↑↑↑↑. By decreasing H from 6 T, P is still zero until it shows a sudden jump at –0.8 T owing to the almost recovery of the ↑↑↓↓ state. P is reduced to zero again at –3.8 T for the change in the spin state to ↓↓↓↓. A similar hysteretic behavior was observed for the other directions of H. In Fig. 2d, P was measured by sweeping H at E = 0 V after poling. The P value at 0 T was reduced to 1.6 μC/m2, which suggests the incorporation of a considerable portion of the ↑↓↓↑-type antiferromagnetic domains with the opposite sign of P. The overall value of P was diminished, but a similar hysteretic behavior was detected. In addition, peak anomalies were observed when P was reduced to zero and recovered. In Fig. 2e, the magnetodielectric (MD) effect, described by the variation in ε′ by applying H and defined as MD (%) = \(\frac{{\varepsilon }^{^{\prime}}\left(H\right)-{\varepsilon }^{^{\prime}}(0 \mathrm{T})}{{\varepsilon }^{^{\prime}}(0 \mathrm{T})}\times 100\), was measured at f = 100 kHz and T = 3 K perpendicular to the c axis up to ± 6 T along the c axis. ε′ reveals a hysteretic behavior similar to that of P, which reflects the ferroelectric domain motion.
To examine the behavior of full magnetoelectric hysteresis in detail, the T evolution of various physical properties was measured. Figure 3 shows a comparison among isothermal P (measured at E = 100 V) and MD effect perpendicular to the c axis, and M along the c axis at H up to ± 6 T and T = 5, 10, 20, 30, and 40 K. As T is increased, the hysteretic behavior is gradually suppressed. At 5 K, the area within the magnetic hysteresis loop is reduced (Fig. 3a), accompanied by a large reduction in Mr = 1.73 μB/f.u. and Hc = 0.78 T, in comparison with M at 3 K (Fig. 2b). Owing to the narrowed hysteresis loop, double-step variations in M occur at H = 0.24 and –3.07 T upon sweeping H from 6 T. At 10 K, the magnetic hysteresis narrows further with Mr = 0.23 μB/f.u. and Hc = 0.17 T (Fig. 3b). As T increases further, the area of the magnetic hysteresis loop of M rapidly shrinks, and Mr and Hc are nearly suppressed. At 40 K, the magnetic hysteresis in M almost disappears, while the double-step transitions remain (Fig. 3e). As shown in Fig. 3f, P at 5 K shows a hysteretic behavior similar to M following the appearance and disappearance of ferroelectricity at the double steps, which suggests a strong correlation between the magnetic and ferroelectric properties. As T increases further, the hysteretic behavior of P is reduced, but the magnitude of P is considerably enhanced up to 20 K (Fig. 3g and h). The maximum P values at 10 and 20 K were found to be 10.71 and 13.74 μC/m2, respectively. Above 20 K, the magnitude of P decreases with further reduction in the hysteretic behavior (Fig. 3i and j). The MD also tends to behave akin to P, which reflects the H-driven variations in ferroelectricity (Fig. 3k–o). The variation in MD is progressively enhanced as T increases. At 30 and 40 K, the maximum MD values were observed as − 6.68% and − 5.26%, respectively, at 6 T. These large variations arise at the T regime close to TH ≈ 37 K, at which the broad peak of ε′ occurs (Fig. 1c). A recent X-ray photon correlation spectroscopy study on Lu2CoMnO6 clarified that the ↑↑↓↓-type arrangement, which is slightly incommensurate (ICM) with k = (0.0223(8), 0.0098(7), 0.5)46, emerges at TN = 48 K and commensurate (CM) spin order corresponding to k = (0, 0, 0.5) arises below TH = 30 K, while the ICM order still remains47. This suggests that the strong magnetic hysteresis originates from the simultaneous presence of the ICM and CM orders. The comprehensive behavior of strong magnetoelectric hysteresis in YCMO is demonstrated in the H-T phase diagram constructed from T dependence of M, and H dependence of M and P, as shown in Fig. 4. The data points for the phase boundaries were attained from the maximum slopes of H dependence of M and P. The onset of magnetoelectric hysteresis emerges at TH ≈ 37 K, below which the hysteretic regime expands continuously. The red regime in which the corresponding magnetic state relies on magnetic hysteresis is clearly presented. The P is zero in the green colored region, corresponding to ↑↑↑↑ or ↓↓↓↓ Co2+/Mn4+ spin configuration due to the large magnetoelectric hysteresis at low T regime.
In a recent neutron diffraction study on YCMO, in addition to the ↑↑↓↓-type arrangement of Co2+ and Mn4+ moments, the ordering of Yb3+ spins has been observed41. From the spin structure attained from this previously investigated neutron diffraction, we propose schematic spin configurations forming four types of magnetoelectric domains and possible activation of the symmetric exchange striction between Yb3+ and Co2+/ Mn4+ moments, which generates an additional ferroelectric P along the c axis, as shown in Fig. 5. All spin configurations are established within the magnetic Pa21 symmetry, consistent with that of Lu2CoMnO6. In such a symmetry, Yb3+ spins are distinguished as two different sites. For Yb1 sites, Yb3+ spins turn out to be strongly disordered because of the formation of strong internal fields from the neighboring ferromagnetic arrangement of Co2+/ Mn4+ spins between the upper and lower layers, which inhibits the antiferromagnetic coupling of Yb3+ spins41. By contrast, at the Yb2 sites, the cancelation of the internal fields from neighboring antiferromagnetic arrangement enables the Yb3+ spins to be ordered41. In Fig. 5a, the Yb3+ moments in the Yb2 sites are ordered antiferromagnetically aside from the ↑↑↓↓ spin arrangement of the Co2+ and Mn4+ ions; they also prefer to align antiferromagnetically to the neighboring Co2+/ Mn4+ moments. In such configuration, the down (↓) Yb3+ spin tends to shift to the upward direction and the up (↑) Yb3+ spin also shifts to the upward direction owing to the exchange striction that prefers the antiparallel alignment between Yb3+ and Co2+/Mn4+ spins. Thus, the net ferroelectric P is produced along the c axis. Similarly, oppositely aligned ferroelectric P occurs in the spin configuration, as shown in Fig. 5b. The other two types of magnetoelectric domains are depicted in Fig. 5c and d. Accompanied by the ↑↓↓↑ spin arrangement of the Co2+ and Mn4+ ions, the antiferromagnetic order of Yb3+ spins also leads to + P and − P along the c axis, respectively. As a result, four different types of magnetoelectric domains form depending on both P directions, i.e., (Pb, Pc) = (+ , +), (+ , −), (− , +), and (− , −).
To evaluate the potential occurrence of additional ferroelectricity along the c axis, we measured the electric properties. Contrary to the overall negative MD perpendicular to the c axis (Figs. 2e and 3k–o), the MD effect along the c axis with H up to ± 6 T along the c axis appears to be positive, and the magnitude of MD is largely reduced, as shown in Fig. 6. At 3 K, the initial curve exhibits a step-like jump in accordance with the spin-state variation from ↑↑↓↓ to ↑↑↑↑ (Fig. 6a). Following the magnetically hysteretic behavior, a rapid decrease in MD is observed at a negative value of H. A further decrease in H leads to a sudden jump, indicating the magnetic transition to the ↓↓↓↓ state. As T increases further, the magnitude of MD is continually reduced, which is different from the T evolution of the MD effect perpendicular to the c axis (Fig. 6b–d). Despite the observed positive MD effect with a strong dielectric anomaly, the presence of the proposed additional ferroelectricity has not been clearly proven because no measurable electric P was detected within the accuracy of our pyroelectric current measurement. Note that our measurement is highly sensitive to the P magnitude, as shown in the measured P perpendicular to the c axis (Figs. 2c, d, and 3f–j).
Conclusion
In summary, we explored the anisotropic magnetoelectric properties of the frustrated antiferromagnet YCMO. Ferroelectric polarization was found to occur perpendicular to the c axis, originating from the exchange strictive shifts of O2− ions of the ↑↑↓↓-type Co2+/Mn4+ spin order along the c axis. The magnetoelectric hysteresis observed below TH ≈ 37 K revealed an interesting correlation between the magnetic and ferroelectric properties. We also proposed that the magnetic order of Yb3+ moments below TYb ≈ 20 K could lead to an additional ferroelectric polarization along the c axis with the formation of four different types of magnetoelectric domains. Our findings provide insights into fundamental magnetic and magnetoelectric interactions in the frustrated antiferromagnets of the double-perovskite family, inspiring the discovery of new compounds for functional magnetoelectric applications.
Methods
Single crystals of double-perovskite YCMO were synthesized by the conventional flux method using Bi2O3 as a flux40. A polycrystalline specimen was first prepared by a solid-state reaction. High-purity powders of Yb2O3, Co3O4, and MnO2 were mixed in a stoichiometric ratio and ground in a mortar, followed by pelletizing and calcining at 1000 °C for 12 h in a furnace. The calcined pellets were reground and sintered at 1100 °C for 24 h. The same sintering procedure was repeated at 1200 °C for 48 h. A mixture of polycrystalline powder and Bi2O3 flux in a 1:12 ratio was heated to 1300 °C and melted in a Pt crucible. It was then slowly cooled to 850 °C at a rate of 1.5 °C/h and then cooled further to room temperature while the furnace was turned off.
The temperature and magnetic-field dependences of the DC magnetizations were measured using a vibrating sample magnetometer (VSM) at T = 2–100 K and H = − 9–9 T in a physical properties measurement system (PPMS, Quantum Design, Inc.). The specific heat was measured using the standard relaxation method in the PPMS. The temperature and magnetic-field dependences of the dielectric constant were measured at f = 100 kHz using an LCR meter (E4980, Agilent). The temperature and magnetic-field dependences of electric polarization were obtained by integrating pyro- and magneto-electric currents, respectively, measured after poling in a static electric field, E = 2.3 kV/cm.
References
AJ Hearmon 2012 Electric field control of the magnetic chiralities in ferroaxial multiferroic RbFe(MoO4)2 Phys. Rev. Lett. 108 237201 https://doi.org/10.1103/PhysRevLett.108.237201
V Kocsis 2019 Magnetization-polarization cross-control near room temperature in hexaferrite single crystals Nat. Commun. 10 1247 https://doi.org/10.1038/s41467-019-09205-x
YJ Choi CL Zhang N Lee SW Cheong 2010 Cross-control of magnetization and polarization by electric and magnetic fields with competing multiferroic and weak-ferromagnetic phases Phys. Rev. Lett. 105 097201 https://doi.org/10.1103/PhysRevLett.105.097201
N Lee 2013 Giant tunability of ferroelectric polarization in GdMn2O5 Phys. Rev. Lett. 110 137203 https://doi.org/10.1103/PhysRevLett.110.137203
S-W Cheong M Mostovoy 2007 Multiferroics: A magnetic twist for ferroelectricity Nat. Mater. 6 13 20 https://doi.org/10.1038/nmat1804
M Fiebig T Lottermoser D Meier M Trassin 2016 The evolution of multiferroics Nat. Rev. Mater. 1 16046 https://doi.org/10.1038/natrevmats.2016.46
AB Sushkov 2014 Spectral origin of the colossal magnetodielectric effect in multiferroic DyMn2O5 Phys. Rev. B 90 054417 https://doi.org/10.1103/PhysRevB.90.054417
G Cao 2014 Novel magnetism of Ir5+(5d4) ions in the double perovskite Sr2YIrO6 Phys. Rev. Lett. 112 056402 https://doi.org/10.1103/PhysRevLett.112.056402
MK Kim 2019 Strong magnetoelectric coupling in mixed ferrimagnetic-multiferroic phases of a double perovskite Sci. Rep. 9 5456 https://doi.org/10.1038/s41598-019-41990-9
X Ding 2019 Magnetic properties of double perovskite Ln2CoIrO6 (Ln=Eu, Tb, Ho): Hetero-tri-spin 3d–5d−4f systems Phys. Rev. B 99 014438 https://doi.org/10.1103/PhysRevB.99.014438
R Pradheesh HS Nair V Sankaranarayanan K Sethupathi 2012 Exchange bias and memory effect in double perovskite Sr2FeCoO6 Appl. Phys. Lett. 101 142401 https://doi.org/10.1063/1.4756792
W Liu 2014 Griffiths phase, spin-phonon coupling, and exchange bias effect in double perovskite Pr2CoMnO6 J. Appl. Phys. 116 193901 https://doi.org/10.1063/1.4902078
JK Murthy A Venimadhav 2017 4f–3d exchange coupling induced exchange bias and field induced Hopkinson peak effects in Gd2CoMnO6 J. Alloys Compd. 719 341 346 https://doi.org/10.1016/j.jallcom.2017.05.203
JY Moon 2018 Anisotropic magnetic properties and giant rotating magnetocaloric effect in double-perovskite Tb2CoMnO6 Phys. Rev. B 98 174424 https://doi.org/10.1103/PhysRevB.98.174424
JY Moon MK Kim YJ Choi N Lee 2017 Giant anisotropic magnetocaloric effect in double-perovskite Gd2CoMnO6 single crystals Sci. Rep. 7 16099 https://doi.org/10.1038/s41598-017-16416-z
C Ganeshraj R Pradheesh PN Santhosh 2012 Structural, magnetic, transport and magnetocaloric properties of metamagnetic DyMn0.5Co0.5O3 J. Appl. Phys. 111 07A914 https://doi.org/10.1063/1.3672067
M Balli P Fournier S Jandl KD Truong MM Gospodinov 2014 Analysis of the phase transition and magneto-thermal properties in La2CoMnO6 single crystals J. Appl. Phys. 116 073907 https://doi.org/10.1063/1.4893721
N Terada 2015 Ferroelectricity induced by ferriaxial crystal rotation and spin helicity in a B-site-ordered double-perovskite multiferroic In2NiMnO6 Phys. Rev. B 91 104413 https://doi.org/10.1103/PhysRevB.91.104413
G Sharma J Saha SD Kaushik V Siruguri S Patnaik 2013 Magnetism driven ferroelectricity above liquid nitrogen temperature in Y2CoMnO6 Appl. Phys. Lett. 103 012903 https://doi.org/10.1063/1.4812728
S Chikara 2016 Electric polarization observed in single crystals of multiferroic Lu2MnCoO6 Phys. Rev. B 93 180405 https://doi.org/10.1103/PhysRevB.93.180405
N Lee 2014 Strong ferromagnetic-dielectric coupling in multiferroic Lu2CoMnO6 single crystals Appl. Phys. Lett. 104 112907 https://doi.org/10.1063/1.4869479
AH Slavney T Hu AM Lindenberg HI Karunadasa 2016 A bismuth-halide double perovskite with long carrier recombination lifetime for photovoltaic applications J. Am. Chem. Soc. 138 2138 2141 https://doi.org/10.1021/jacs.5b13294
L Schade 2019 Structural and optical properties of Cs2AgBiBr6 double perovskite ACS Energy Lett. 4 299 305 https://doi.org/10.1021/acsenergylett.8b02090
G Longo 2020 Understanding the performance-limiting factors of Cs2AgBiBr6 double-perovskite solar cells ACS Energy Lett. 5 2200 2207 https://doi.org/10.1021/acsenergylett.0c01020
Z Zhang 2019 Stable and highly efficient photocatalysis with lead-free double-perovskite of Cs2AgBiBr6 Angew. Chem. Int. Ed. 58 7263 7267 https://doi.org/10.1002/anie.201900658
T Wang D Yue X Li Y Zhao 2020 Lead-free double perovskite Cs2AgBiBr6/RGO composite for efficient visible light photocatalytic H2 evolution Appl. Catal. B 268 118399 https://doi.org/10.1016/j.apcatb.2019.118399
L Zhou Y-F Xu B-X Chen D-B Kuang C-Y Su 2018 Synthesis and photocatalytic application of stable lead-free Cs2AgBiBr6 perovskite nanocrystals Small 14 1703762 https://doi.org/10.1002/smll.201703762
Z Liu 2021 Synthesis of lead-free Cs2AgBiX6 (X = Cl, Br, I) double perovskite nanoplatelets and their application in CO2 photocatalytic reduction Nano Lett. 21 1620 1627 https://doi.org/10.1021/acs.nanolett.0c04148
M Wang P Zeng Z Wang M Liu 2020 Vapor-deposited Cs2AgBiCl6 double perovskite films toward highly selective and stable ultraviolet photodetector Adv. Sci. 7 1903662 https://doi.org/10.1002/advs.201903662
J Luo 2018 Cs2AgInCl6 double perovskite single crystals: Parity forbidden transitions and their application for sensitive and fast UV photodetectors ACS Photon. 5 398 405 https://doi.org/10.1021/acsphotonics.7b00837
M Ghasemi 2020 Dual-ion-diffusion induced degradation in lead-free Cs2AgBiBr6 double perovskite solar cells Adv. Func. Mater. 30 2002342 https://doi.org/10.1002/adfm.202002342
K Prabhu AK Chandiran 2020 Solar energy storage in a Cs2AgBiBr6 halide double perovskite photoelectrochemical cell Chem. Commun. 56 7329 7332 https://doi.org/10.1039/D0CC02743J
MK Kim 2015 Investigation of the magnetic properties in double perovskite R2CoMnO6 single crystals (R = rare earth: La to Lu) J. Phys. Condens. Matter 27 426002 https://doi.org/10.1088/0953-8984/27/42/426002
HS Nair T Chatterji AM Strydom 2015 Antisite disorder-induced exchange bias effect in multiferroic Y2CoMnO6 Appl. Phys. Lett. 106 022407 https://doi.org/10.1063/1.4906204
RC Sahoo 2017 Antisite-disorder driven large exchange bias effect in phase separated La1.5Ca0.5CoMnO6 double perovskite J. Magn. Magn. Mater. 428 86 91 https://doi.org/10.1016/j.jmmm.2016.12.018
RI Dass JB Goodenough 2003 Multiple magnetic phases of La2CoMnO6−δ (0<~δ<~0.05) Phys. Rev. B. 67 014401 https://doi.org/10.1103/PhysRevB.67.014401
VA Khomchenko 2006 Metamagnetic behaviour in TbCo0.5Mn0.5O3.06 perovskite J. Phys. Condens. Matter 18 9541 9548 https://doi.org/10.1088/0953-8984/18/42/001
AN Vasiliev 2008 Valence states and metamagnetic phase transition in partially B-site-disordered perovskite EuMn0.5Co0.5O3 Phys. Rev. B 77 104442 https://doi.org/10.1103/PhysRevB.77.104442
RP Madhogaria 2019 Evidence of long-range ferromagnetic order and spin frustration effects in the double perovskite La2CoMnO6 Phys. Rev. B 99 104436 https://doi.org/10.1103/PhysRevB.99.104436
HY Choi JY Moon JH Kim YJ Choi N Lee 2017 Single crystal growth of multiferroic double perovskites: Yb2CoMnO6 and Lu2CoMnO6 Curr. Comput. Aided Drug Des. 7 67
J Blasco 2017 Magnetic order and magnetoelectric properties of R2CoMnO6 perovskites (R=Ho, Tm, Yb, and Lu) Phys. Rev. B 96 024409 https://doi.org/10.1103/PhysRevB.96.024409
JT Zhang XM Lu XQ Yang JL Wang JS Zhu 2016 Origins of ↑↑↓↓ magnetic structure and ferroelectricity in multiferroic Lu2CoMnO6 Phys. Rev. B 93 075140 https://doi.org/10.1103/PhysRevB.93.075140
A Banerjee J Sannigrahi S Giri S Majumdar 2018 Magnetization reversal and inverse exchange bias phenomenon in the ferrimagnetic polycrystalline compound Er2CoMnO6 Phys. Rev. B 98 104414 https://doi.org/10.1103/PhysRevB.98.104414
J Blasco 2015 Evidence of large magneto-dielectric effect coupled to a metamagnetic transition in Yb2CoMnO6 Appl. Phys. Lett. 107 012902 https://doi.org/10.1063/1.4926403
VS Zapf 2016 Magnetization dynamics and frustration in the multiferroic double perovskite Lu2MnCoO6 Phys. Rev. B 93 134431 https://doi.org/10.1103/PhysRevB.93.134431
S Yáñez-Vilar 2011 Multiferroic behavior in the double-perovskite Lu2MnCoO6 Phys. Rev. B 84 134427 https://doi.org/10.1103/PhysRevB.84.134427
A Carr 2021 Dynamics of a fractal set of first-order magnetic phase transitions in frustrated Lu2CoMnO6 Phys. Rev. B 103 L060401 https://doi.org/10.1103/PhysRevB.103.L060401
Acknowledgements
This work was supported by the National Research Foundation of Korea (NRF) through grants NRF-2017R1A5A1014862 (SRC program: vdWMRC center), NRF-2019R1A2C2002601, and NRF-2021R1A2C1006375.
Author information
Authors and Affiliations
Contributions
N.L. and Y.J.C. designed the experiments. J.H.K. synthesized the single crystals. J.H.K., K.W.J., D.G.O., H.J.S., J.M.H., J.S.K., J.Y.M., and N.L. performed magnetization, heat capacity, dielectric constant, and polarization measurements. J.H.K., N.L., and Y.J.C. analyzed the data and prepared the manuscript. All the authors have read and approved the final version of the manuscript.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher's note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
About this article
Cite this article
Kim, J.H., Jeong, K.W., Oh, D.G. et al. Behavior of magnetoelectric hysteresis and role of rare earth ions in multiferroicity in double perovskite Yb2CoMnO6. Sci Rep 11, 23786 (2021). https://doi.org/10.1038/s41598-021-03330-8
Received:
Accepted:
Published:
DOI: https://doi.org/10.1038/s41598-021-03330-8
- Springer Nature Limited
This article is cited by
-
Structural, electrical properties of bismuth and niobium-doped LaNiO3 perovskite obtained by sol–gel route for future electronic device applications
Indian Journal of Physics (2024)
-
AC Conductivity and Dielectric Behavior of a New Double Perovskite PrNaMnMoO6 System
Journal of Low Temperature Physics (2023)