Effects of Octahedral Tilting on Band Structure and Thermoelectric Power Factor of Titanate Perovskites: A First-Principles Study on SrTiO₃

Abstract

Doped SrTiO_{3} and other perovskite structured titanates are attracting interest as n-type thermoelectric materials due to their relatively high thermoelectric power factor, low toxicity, and modest cost. Taking SrTiO_{3} as an example, the effects of octahedral tilting on the electronic band structure and thermoelectric power factor of titanate perovskites have been studied from first-principles calculations. By utilizing Glazer’s notation, six representative tilt systems, including three out-of-phase (a^{0}a^{0}c^{–}, a^{0}b^{-}b^{–}, and a^{–}a^{–}a^{–}) and three in-phase tilt systems (a^{0}a^{0}c^{+}, a^{0}b^{+}b^{+}, and a^{+}a^{+}a^{+}), were investigated. It is found that out-of-phase tilting improves the optimum power factor as compared to the cubic aristotype, while in-phase tilting marginally lowers the optimum power factor. The largest increase in power factor (∼100%) is obtained in the one-tilt system a^{0}a^{0}c^{–} at a tilt angle of 15°, which can be achieved with an energy cost of only 44 kJ mol^{–1} per formula unit. These findings agree with the experimental evidence that increased power factors are found in a^{0}a^{0}c^{–} and a^{–}a^{–}a^{–} tilt systems of titanate perovskites. The predicted increase of Seebeck coefficient as a function of tilt angle in the a^{–}a^{–}a^{–} tilt system of SrTiO_{3} is also consistent with the experimental increase of Seebeck coefficient in a^{–}a^{–}a^{–} titanates of La_{0.55}K_{0.45}TiO_{3} and La_{0.5}Na_{0.5}Ti_{0.9}Nb_{0.1}O_{3}. Our simulations provide valuable insights into tuning the thermoelectric power factor of titanate perovskites by controlling octahedral tilting

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