Polar-Nonpolar Phase Transition Accompanied by Negative Thermal Expansion in Perovskite-Type Bi1- xPbxNiO3

Yuki Sakai, Takumi Nishikubo, Takahiro Ogata, Hayato Ishizaki, Takashi Imai, Masaichiro Mizumaki, Takashi Mizokawa, Akihiko MacHida, Tetsu Watanuki, Keisuke Yokoyama, Yoichi Okimoto, Shin Ya Koshihara, Hena Das, Masaki Azuma

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2 Citations (Scopus)

Abstract

Perovskite-oxide Bi1-xPbxNiO3 for 0.60 ≤ x ≤ 0.80 was found to show a polar orthorhombic-to-nonpolar orthorhombic phase transition accompanied by negative thermal expansion. Bi1-xPbxNiO3 showed successive crystal structure changes depending on the amount of Pb. As the amount of Pb increased, the crystal structure changed from a triclinic one with Bi3+/Bi5+ long-range ordering to an orthorhombic one with Bi3+/Bi5+ short-range ordering; then, it changed into a polar orthorhombic structure without Bi3+/Bi5+ ordering and finally to a polar LiNbO3-type one. The key to the inversion symmetry breaking in PbNiO3, where both 6s2 lone-pair and Jahn-Teller active cations are absent, is the high-valency state of Pb4+. Our results suggest that the polar orthorhombic phase can be realized by using high-valence A-site cations in addition to controlling the tolerance factor.

Original languageEnglish
Pages (from-to)4748-4758
Number of pages11
JournalChemistry of Materials
Volume31
Issue number13
DOIs
Publication statusPublished - 2019 Jul 9

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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    Sakai, Y., Nishikubo, T., Ogata, T., Ishizaki, H., Imai, T., Mizumaki, M., Mizokawa, T., MacHida, A., Watanuki, T., Yokoyama, K., Okimoto, Y., Koshihara, S. Y., Das, H., & Azuma, M. (2019). Polar-Nonpolar Phase Transition Accompanied by Negative Thermal Expansion in Perovskite-Type Bi1- xPbxNiO3 Chemistry of Materials, 31(13), 4748-4758. https://doi.org/10.1021/acs.chemmater.9b00929