Katayama, Tsukasa, Chikamatsu, Akira, Hirose, Yasushi, Minohara, Makoto, Kumigashira, Hiroshi, Harayama, Isao, Sekiba, Daiichiro, Hasegawa, Tetsuya
Journal of Materials Chemistry C 6 13 3445 - 3450 2018年
A-site cation-ordered perovskite cobaltite, RBaCo2Ox (R = rare earth element), exhibits fascinating physical properties, such as spin-state ordering and high oxygen conductivity, because of the large tetragonal distortion of the Co orbital. However, the distorted coordination geometry prefers oxygen vacancies, resulting in a difficulty in obtaining the stoichiometric phase (x = 6). For example, x in YBaCo2Ox, which has largely distorted Co orbitals because of the small size of Y3+, has so far been limited to 5.52. To expand the available range of x, in this study, we performed a low-temperature topotactic oxidation of YBaCo2O5.3 epitaxial films using a strong oxidizing agent NaClO. The x value can be varied in a wide range of 5.3-6.0, maintaining the A-site cation-ordered perovskite structure, by changing the pH and temperature of NaClO. The single crystalline film with x = 6 exhibits large tetragonal distortion (c/a = 0.968) because of the small ionic radius of Y3+ and substrate-induced tensile strain. Unlike antiferromagnetic insulating YBaCo2O5.5, the fully oxidized film with x = 6 exhibits in-plane ferromagnetism and metallicity with a Curie temperature of 130 K possibly because of the double-exchange interaction between Co3+ and Co4+. Moreover, the YBaCo2O6 film exhibits huge magnetic anisotropy with a magnetic anisotropy constant of 1.5 x 10(8) erg cm(-3), demonstrating that the A-site cation-ordered perovskite structure is promising for obtaining high magnetocrystalline anisotropic materials.