Robust Giant Tetragonal Distortion Coupled with High-Spin Co3+ in Electron-Doped BiCoO3

Hayato Ishizaki, Hajime Yamamoto, Takumi Nishikubo, Yuki Sakai, Shogo Kawaguchi, Keisuke Yokoyama, Yoichi Okimoto, Shin Ya Koshihara, Takafumi Yamamoto, Masaki Azuma

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)


BiCoO3 is a PbTiO3 type of perovskite oxide with a giant tetragonal distortion (c/a = 1.27) that shows a pressure-induced transition from tetragonal to orthorhombic phases accompanied by a large volume shrinkage at 3 GPa. In this study, we carried out electron doping of BiCoO3 by substituting Ti4+ for Co3+ in order to destabilize the tetragonal phase and observe a giant negative thermal expansion (NTE) at ambient pressure. BiCo1-xTixO3 (x = 0, 0.1, 0.2, and 0.25) was successfully obtained by using high-pressure synthesis. However, the c/a ratio of the tetragonal phase was almost constant against x (≤0.2), and NTE was not observed at any x, suggesting that the tetragonal distortion coupled with high-spin Co3+ is robust against electron doping. In x = 0.25, a metastable orthorhombic phase was obtained by the high-pressure synthetic process, while it partially transformed into a tetragonal phase after annealing at 600 K. The stability of the giant tetragonal phase is strongly connected with the spin state of Co3+.

Original languageEnglish
Pages (from-to)16059-16064
Number of pages6
JournalInorganic Chemistry
Issue number23
Publication statusPublished - 2019 Dec 2


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