Glassy Distribution of Bi3+/Bi5+ in Bi1-xPbxNiO3 and Negative Thermal Expansion Induced by Intermetallic Charge Transfer

Kiho Nakano, Kengo Oka, Tetsu Watanuki, Masaichiro Mizumaki, Akihiko Machida, Akane Agui, Hyunjeong Kim, Jun Komiyama, Takashi Mizokawa, Takumi Nishikubo, Yuichiro Hattori, Shigenori Ueda, Yuki Sakai, Masaki Azuma

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Abstract

The valence distribution and local structure of Bi1-xPbxNiO3 (x ≤ 0.25) were investigated by comprehensive studies of Rietveld analysis of synchrotron X-ray diffraction (SXRD) data, X-ray absorption spectroscopy (XAS), hard X-ray photoemission spectroscopy (HAXPES), and pair distribution function (PDF) analysis of synchrotron X-ray total scattering data. Disproportionation of Bi ions into Bi3+ and Bi5+ was observed for all the samples, but it was a long-ranged one with distinct crystallographic sites in the P1 triclinic structure for x ≤ 0.15, while the ordering was short-ranged for x = 0.20 and 0.25. An intermetallic charge transfer between Bi5+ and Ni2+, leading to large volume shrinkage, was observed for all the samples upon heating at ∼500 K.

Original languageEnglish
Pages (from-to)6062-6067
Number of pages6
JournalChemistry of Materials
Volume28
Issue number17
DOIs
Publication statusPublished - 2016 Sep 13

ASJC Scopus subject areas

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

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    Nakano, K., Oka, K., Watanuki, T., Mizumaki, M., Machida, A., Agui, A., Kim, H., Komiyama, J., Mizokawa, T., Nishikubo, T., Hattori, Y., Ueda, S., Sakai, Y., & Azuma, M. (2016). Glassy Distribution of Bi3+/Bi5+ in Bi1-xPbxNiO3 and Negative Thermal Expansion Induced by Intermetallic Charge Transfer. Chemistry of Materials, 28(17), 6062-6067. https://doi.org/10.1021/acs.chemmater.6b01160