Hybrid Improper Ferroelectricity in Columnar (NaY)MnMnTi4 O12

Rebecca Scatena; Ran Liu; Vladimir V Shvartsman; Dmitry D Khalyavin; Yoshiyuki Inaguma; Kazunari Yamaura; Alexei A Belik; Roger D Johnson

doi:10.1002/anie.202305994

Hybrid Improper Ferroelectricity in Columnar (NaY)MnMnTi₄ O₁₂

Angew Chem Int Ed Engl. 2023 Jul 17;62(29):e202305994. doi: 10.1002/anie.202305994. Epub 2023 Jun 13.

Authors

Rebecca Scatena^{1

2}, Ran Liu^{3

4}, Vladimir V Shvartsman⁵, Dmitry D Khalyavin⁶, Yoshiyuki Inaguma⁷, Kazunari Yamaura^{3

4}, Alexei A Belik³, Roger D Johnson²

Affiliations

¹ Department of Physics, Clarendon Laboratory, University of Oxford, Parks Road, Oxford, OX1 3PU, UK.
² Department of Physics and Astronomy, University College London, Gower Street, London, WC1E 6BT, UK.
³ Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba, Ibaraki, 305-0044, Japan.
⁴ Graduate School of Chemical Sciences and Engineering, Hokkaido University, North 10 West 8, Kita-ku, Sapporo, Hokkaido, 060-0810, Japan.
⁵ Institute for Materials Science and CENIDE-Centre for Nanointegration Duisburg-Essen, University of Duisburg-Essen, 45141, Essen, Germany.
⁶ ISIS Facility, Rutherford Appleton Laboratory, Didcot, OX11 0QX, UK.
⁷ Department of Chemistry, Faculty of Science, Gakushuin University, 1-5-1 Mejiro, Toshima-ku, Tokyo, 171-8588, Japan.

PMID: 37199102
DOI: 10.1002/anie.202305994

Abstract

We show that cation ordering on A site columns, oppositely displaced via coupling to B site octahedral tilts, results in a polar phase of the columnar perovskite (NaY)MnMnTi₄ O₁₂ . This scheme is similar to hybrid improper ferroelectricity found in layered perovskites, and can be considered a realisation of hybrid improper ferroelectricity in columnar perovskites. The cation ordering is controlled by annealing temperature and when present it also polarises the local dipoles associated with pseudo-Jahn-Teller active Mn²⁺ ions to establish an additional ferroelectric order out of an otherwise disordered dipolar glass. Below T_N ≈12 K, Mn²⁺ spins order, making the columnar perovskites rare systems in which ordered electric and magnetic dipoles may reside on the same transition metal sublattice.

Keywords: Columnar Perovskites; Ferroelectrics; Hybrid Improper Ferroelectricity; Multiferroics; Perovskite.

Abstract

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