journal article·2019-07-09

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

Chemistry of Materials· Volume 31· Issue 13
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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.
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Research context

OpenAlex topics: Thermal Expansion and Ionic Conductivity · Ferroelectric and Piezoelectric Materials · Multiferroics and related materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Kanagawa Institute of Industrial Science and Technology, 705-1 Shimoimaizumi, Ebina 243-0435, Japan

Laboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8503, Japan

Japan Synchrotron Radiation Research Institute, SPring-8, Sayo-gun, Hyogo 679-5198, Japan

Department of Applied Physics, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan

Synchrotron Radiation Research Center, National Institutes for Quantum and Radiological Science and Technology, Sayo, Hyogo 679-5148, Japan

Department of Chemistry, Tokyo Institute of Technology, Meguro, Tokyo 152-8551, Japan

World Research Hub Initiative, Institute of Innovative Research (IIR), Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8503, Japan

Funding

Ministry of Education, Culture, Sports, Science and Technology · Japan Society for the Promotion of Science · Kanagawa Institute of Industrial Science and Technology

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