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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

20 Citations (Scopus)


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
Issue number13
Publication statusPublished - 2019 Jul 9

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering
  • Materials Chemistry


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