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Thermal multiferroics in all-inorganic quasi-two-dimensional halide perovskites

Nature Materials volume 23, pages 182–188 (2024)Cite this article

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Abstract

Multiferroic materials, particularly those possessing simultaneous electric and magnetic orders, offer a platform for design technologies and to study modern physics. Despite the substantial progress and evolution of multiferroics, one priority in the field remains to be the discovery of unexplored materials, especially those offering different mechanisms for controlling electric and magnetic orders1. Here we demonstrate the simultaneous thermal control of electric and magnetic polarizations in quasi-two-dimensional halides (K,Rb)3Mn2Cl7, arising from a polar–antipolar transition, as evidenced using both X-ray and neutron powder diffraction data. Our density functional theory calculations indicate a possible polarization-switching path including a strong coupling between the electric and magnetic orders in our halide materials, suggesting a magnetoelectric coupling and a situation not realized in oxide analogues. We expect our findings to stimulate the exploration of non-oxide multiferroics and magnetoelectrics to open access to alternative mechanisms, beyond conventional electric and magnetic control, for coupling ferroic orders.

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Fig. 1: Structure evolution of K3Mn2Cl7.
Fig. 2: Magnetic properties of K3Mn2Cl7.
Fig. 3: Symmetry relationship and indirect evidence for magnetoelectric coupling in K3Mn2Cl7.
Fig. 4: Simultaneous thermal manipulation of P and M in K3–xRbxMn2Cl7.

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Data availability

Data needed to evaluate the conclusions of this paper are present in the Letter and its Supplementary Information. Additional data are available from the corresponding authors upon request.

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Acknowledgements

We thank A. Kaminaka from Tohoku University for sample preparation and S. Kawaguchi and S. Kobayashi from SPring-8, JASRI, for assistance in collecting the SXRD data (2020A0822). The NPD experiments were performed at J-Parc BL09 SPICA beamline (2019S10) and JRR-3 HERMES beamline (22602). T.Z. acknowledges the project of university-industrial collaboration (Kyoto University-Sumitomo Chemical), Japan. H.K. and T.Z. acknowledge the JSPS Core-to-Core Program (JPJSCCA202000004), and JSPS Grant-in-Aid for Specially Promoted Research ‘Hydrogen Ion Ceramics’ (JP22H04914). T.Z. and S.K. acknowledge the GIMRT Program of the Institute for Materials Research, Tohoku University (202109-RDKGE-0104). X.-Z.L. and J.M.R. were supported by the National Science Foundation under award no. DMR-2011208. Computational efforts were supported by the National Energy Research Scientific Computing Center (NERSC), a US Department of Energy, Office of Science User Facility, located at Lawrence Berkeley National Laboratory, operated under contract no. DE-AC02-05CH11231, and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by NSF (ACI-1548562). T.A. was supported by the JSPS KAKENHI (20K14396). K.F. was supported by the JSPS KAKENHI (JP20K20546 and JP22H01775), the Kazuchika Okura Memorial Foundation, the Nippon Sheet Glass Foundation for Materials Science and Engineering and the Mitsubishi Foundation.

Author information

Author notes

  1. These authors contributed equally: Tong Zhu, Xue-Zeng Lu.

Authors and Affiliations

  1. Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Japan

    Tong Zhu, Hiroshi Takatsu, Cédric Tassel & Hiroshi Kageyama

  2. Department of Materials Science and Engineering, Northwestern University, Evanston, IL, USA

    Xue-Zeng Lu & James M. Rondinelli

  3. Department of Physics, Graduate School of Science, Tohoku University, Sendai, Japan

    Takuya Aoyama & Kenya Ohgushi

  4. Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Japan

    Koji Fujita, Tatsushi Kawasaki & Takumi Terauchi

  5. Institute for Materials Research, Tohoku University, Sendai, Japan

    Yusuke Nambu, Shunsuke Kurosawa & Akihiro Yamaji

  6. Organization for Advanced Studies, Tohoku University, Sendai, Japan

    Yusuke Nambu

  7. FOREST, Japan Science and Technology Agency, Kawaguchi, Japan

    Yusuke Nambu

  8. Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), Tokai, Japan

    Takashi Saito

  9. New Industry Creation Hatchery Center (NICHe), Tohoku University, Sendai, Japan

    Shunsuke Kurosawa & Akihiro Yamaji

  10. Institute of Laser Engineering, Osaka University, Suita, Japan

    Shunsuke Kurosawa

  11. SANKEN, Osaka University, Ibaraki, Japan

    Hao-Bo Li

  12. Spintronics Research Network Division, Institute for Open and Transdisciplinary Research Initiatives, Osaka University, Suita, Japan

    Hao-Bo Li

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  1. Tong Zhu
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Contributions

T.Z., X.-Z.L., J.M.R. and H.K. designed the project. T.Z., S.K. and A.Y. synthesized the samples. X.-Z.L. performed the theoretical calculations. T.Z., Y.N., T.S. and C.T. collected the SXRD and NPD data. T.Z. performed the structural analysis, with comments from Y.N., K.F. and X.-Z.L. T.A. and K.O. performed the physical property measurements. K.F., T.K. and T.T. performed the SHG measurements. T.Z., H.T. and H.-B.L. collected and analysed the magnetization data. T.Z., X.-Z.L., J.M.R. and H.K. wrote the manuscript, with comments from other authors.

Corresponding authors

Correspondence to James M. Rondinelli or Hiroshi Kageyama.

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Supplementary information

Supplementary Information

Supplementary Sections 1–12, Figs. 1–33, Tables 1–12 and discussion.

Supplementary Data 1

Optimized computational model 1: A21am space group structure.

Supplementary Data 2

Optimized computational model 2: P42/mnm space group structure.

Supplementary Data 3

Optimized computational model 3: I4/mmm space group structure.

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Zhu, T., Lu, XZ., Aoyama, T. et al. Thermal multiferroics in all-inorganic quasi-two-dimensional halide perovskites. Nat. Mater. 23, 182–188 (2024). https://doi.org/10.1038/s41563-023-01759-y

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