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A New Cation-Ordered Structure Type with Multiple Thermal Redistributions in Co₂InSbO₆

Ji, Kunlang Solana‐Madruga, Elena Patino, Midori Amano Shimakawa, Yuichi Attfield, J. Paul 京都大学 DOI:10.1002/anie.202203062

2022.07.04

概要

Cation ordering in solids is important for controlling physical properties and leads to ilmenite (FeTiO₃) and LiNbO₃ type derivatives of the corundum structure, with ferroelectricity resulting from breaking of inversion symmetry in the latter. However, a hypothetical third ABO₃ derivative with R32 symmetry has never been observed. Here we show that Co₂InSbO₆ recovered from high pressure has a new, ordered-R32 A₂BCO₆ variant of the corundum structure. Co₂InSbO₆ is also remarkable for showing two cation redistributions, to (Co₀.₅In₀.₅)₂CoSbO₆ and then Co₂InSbO₆ variants of the ordered-LiNbO₃ A₂BCO₆ structure on heating. The cation distributions change magnetic properties as the final ordered-LiNbO₃ product has a sharp ferrimagnetic transition unlike the initial ordered-R32 phase. Future syntheses of metastable corundum derivatives at pressure are likely to reveal other cation-redistribution pathways, and may enable ABO₃ materials with the R32 structure to be discovered.

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