Polar–Nonpolar Phase Transition Accompanied by Negative Thermal Expansion in Perovskite-Type Bi1–xPbxNiO3Click to copy article linkArticle link copied!
- Yuki Sakai*Yuki Sakai*E-mail: [email protected] (Y.S.).Kanagawa Institute of Industrial Science and Technology, 705-1 Shimoimaizumi, Ebina 243-0435, JapanLaboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8503, JapanMore by Yuki Sakai
- Takumi NishikuboTakumi NishikuboLaboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8503, JapanMore by Takumi Nishikubo
- Takahiro OgataTakahiro OgataLaboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8503, JapanMore by Takahiro Ogata
- Hayato IshizakiHayato IshizakiLaboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8503, JapanMore by Hayato Ishizaki
- Takashi ImaiTakashi ImaiLaboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8503, JapanMore by Takashi Imai
- Masaichiro MizumakiMasaichiro MizumakiJapan Synchrotron Radiation Research Institute, SPring-8, Sayo-gun, Hyogo 679-5198, JapanMore by Masaichiro Mizumaki
- Takashi MizokawaTakashi MizokawaDepartment of Applied Physics, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, JapanMore by Takashi Mizokawa
- Akihiko MachidaAkihiko MachidaSynchrotron Radiation Research Center, National Institutes for Quantum and Radiological Science and Technology, Sayo, Hyogo 679-5148, JapanMore by Akihiko Machida
- Tetsu WatanukiTetsu WatanukiSynchrotron Radiation Research Center, National Institutes for Quantum and Radiological Science and Technology, Sayo, Hyogo 679-5148, JapanMore by Tetsu Watanuki
- Keisuke YokoyamaKeisuke YokoyamaDepartment of Chemistry, Tokyo Institute of Technology, Meguro, Tokyo 152-8551, JapanMore by Keisuke Yokoyama
- Yoichi OkimotoYoichi OkimotoDepartment of Chemistry, Tokyo Institute of Technology, Meguro, Tokyo 152-8551, JapanMore by Yoichi Okimoto
- Shin-ya KoshiharaShin-ya KoshiharaDepartment of Chemistry, Tokyo Institute of Technology, Meguro, Tokyo 152-8551, JapanMore by Shin-ya Koshihara
- Hena DasHena DasLaboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8503, JapanWorld Research Hub Initiative, Institute of Innovative Research (IIR), Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8503, JapanMore by Hena Das
- Masaki Azuma*Masaki Azuma*E-mail: [email protected] (M.A.).Kanagawa Institute of Industrial Science and Technology, 705-1 Shimoimaizumi, Ebina 243-0435, JapanLaboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8503, JapanMore by Masaki Azuma
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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