The impact of atomic defects on high-temperature stability and electron transport properties in Sr2Mg1−xNixMoO6–δ solid solutions

Journal of Alloys and Compounds. 2021. Vol. 883. Article 160821.

Tolstov K. Y., Politov B. V., Zhukov V. P., E.V. Chulkov, Kozhevnikov V. L.

The computational modeling within a density functional theory was applied for simulations of electronic spectra and calculations of structural and energy characteristics of the cubic double perovskite oxides Sr2Mg1−xNixMoO6–δ, where x = 0, 0.5, and 1. The oxygen stoichiometric molybdates are antiferromagnetic semiconductors with an energy gap near 2 eV. The energy-based arguments show that anti-site cation disorder may contribute to the structural stability of the molybdates. It is found that nickel doping is favorable for mitigated chemical expansion. The replacement of magnesium by nickel is accompanied by the contribution of Ni3d states to the valence band while leaving hybrid Mo4d-O2p states in the conduction band virtually unchanged. It is shown that the compounds under study are thermodynamically unstable in heavily reducing conditions which is confirmed by experimental results. The appearance of oxygen deficiency in Sr2Mg1−xNixMoO6–δ results in the formation of oxygen vacancy associated donor states near the bottom of the conduction band and the transition from the intrinsic to degenerate semiconductor. It is suggested that the influence of nickel dopants on the energy and density of the donor states may help to explain variations of the conducting properties with doping level.

Keywords: дефекты кристаллической структуры, electronic structures, Electrical conductivity, density functional theory, электронная структура, crystal structure defects, метод функционала плотности, Thermodynamic stability, термодинамическая стабильность, электрическая проводимость