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Article Dans Une Revue Chemistry of Materials Année : 2016

LiNbO3-type InFeO3: Room-temperature polar magnet without second-order Jahn-Teller active ions

Résumé

Great effort has been devoted to developing single-phase magnetoelectric multiferroics, but room-temperature coexistence of large electric polarization and magnetic ordering still remains elusive. Our recent finding shows that such polar magnets can be synthesized in small-tolerance-factor perovskites AFeO3 with unusually small cations at the A-sites, which are regarded as having a LiNbO3-type structure (space group R3c). Herein, we experimentally reinforce this finding by preparing a novel room-temperature polar magnet, LiNbO3-type InFeO3. This compound is obtained as a metastable quench product from an orthorhombic perovskite phase stabilized at 15 GPa and an elevated temperature. The structure analyses reveal that the polar structure is characterized by displacements of In3+ (d10) and Fe3+ (d5) ions along the hexagonal c-axis (pseudocubic [111] axis) from their centrosymmetric positions, in contrast to well-known perovskite ferroelectrics (e.g., BaTiO3, PbTiO3, and BiFeO3) where d0 transition-metal ions and/or 6s2 lone-pair cations undergo polar displacements through the so-called second-order Jahn-Teller (SOJT) distortions. Using density functional theory calculations, the electric polarization of LiNbO3-type InFeO3 is estimated to be 96 μC/cm2 along the c-axis, comparable to that of an isostructural and SOJT-active perovskite ferroelectric, BiFeO3 (90-100 μC/cm2). Magnetic studies demonstrate weak ferromagnetic behavior at room temperature, as a result of the canted G-type antiferromagnetic ordering of Fe3+ moments below TN ∼ 545 K. The present work shows the functional versatility of small-tolerance-factor perovskites and provides a useful guide for the synthesis and design of room-temperature polar magnets. © 2016 American Chemical Society.
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hal-01381124 , version 1 (02-02-2017)

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K. Fujita, T. Kawamoto, I. Yamada, O. Hernandez, N. Hayashi, et al.. LiNbO3-type InFeO3: Room-temperature polar magnet without second-order Jahn-Teller active ions. Chemistry of Materials, 2016, 28 (18), pp.6644--6655. ⟨10.1021/acs.chemmater.6b02783⟩. ⟨hal-01381124⟩
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