Ishida Kohdai, Tassel Cédric, Kato Daichi, Ubukata Hiroki, Murayama Kantaro, Murakami Taito, Yashima Masatomo, Higo Yuji, Tange Yoshinori, Phelan W Adam, McQueen Tyrel M, Kageyama Hiroshi
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan.
Department of Electronic Engineering, Graduate School of Engineering, Tohoku University, Sendai 987-8579, Japan.
Inorg Chem. 2022 Jul 25;61(29):11118-11123. doi: 10.1021/acs.inorgchem.2c00897. Epub 2022 Jul 8.
Transition-metal oxynitrides have a variety of functions such as visible light-responsive catalysts and dielectric materials, but acquiring single crystals necessary to understand inherent properties is difficult and is limited to relatively small sizes (<10 μm) because they easily decompose at high temperatures. Here, we have succeeded in growing platelet single crystals of TaON with a typical size of 50 × 100 × 10 μm under a high pressure and high temperature (6 GPa and 1400 °C) using a LiCl flux. Such a harsh condition, in contrast to powder samples synthesized under mild conditions, resulted in the introduction of a large amount of oxygen vacancies ( = 0.06 in TaON) into the crystal, providing a metallic behavior with a large anisotropy of ρ/ρ ∼ 10. Low-temperature oxygen annealing allows for a single-crystal-to-single-crystal transformation to obtain fully oxidized TaON (yellow) crystals. Needle-like crystals can be obtained when NHCl is used as a flux. Furthermore, black HfON single crystals are also grown, suggesting that the high-pressure flux method is widely applicable to other transition-metal oxynitrides, with extensive carrier control.
