Oxysulfide perovskites: reduction of the electronic band gap of RbTaO₃ by sulfur substitution

Abstract

In this study, the effects of sulfur substitution on the structural, mechanical, electronic, optical, and thermodynamic properties of RbTaO3-xSx have been investigated using the WIEN2k code in the framework of density functional theory (DFT). The cubic phase of RbTaO3 transforms to tetragonal for RbTaO2S and RbTaOS2; the latter transforms again to a cubic phase with added sulfur for RbTaS3. The results show that substituting S for O anions in RbTaO3 effectively decreased the band gap [calculated using TB-mBJ functional] from 2.717 eV to 1.438 eV, 0.286 eV, and 0.103 eV for the RbTaO3, RbTaO2S, RbTaOS2, and RbTaS3 compounds, respectively. The optical constants such as dielectric constant, refractive index, absorption coefficient, photoconductivity, reflectivity, and loss function have been calculated and analyzed. The elastic constants and moduli and their anisotropic nature were also investigated. Finally, the Debye temperature, thermal conductivity, melting temperature, specific capacities, and thermal expansion coefficients were computed and analyzed using established formalisms. The reduced band gap (1.438 eV) and high absorption coefficient (~106 cm-1) of RbTaO2S, make it suitable for solar cell applications and for other visible light devices. Both ordered structure and super-cell have been used to cross-check results for RbTaO2S and RbTaOS2 compositions.