Electronic Structure and Stability of Cs$_{2}$TiX$_{6}$ and Cs$_{2}$ZrX$_{6}$ (X$=$Br,I) Vacancy Ordered Double Perovskites

Abstract: Vacancy ordered halide perovskites have been extensively investigated as promising lead-free alternatives to halide perovskites for various opto-electronic applications. Among these Cs${2}$TiBr${6}$ has been reported as a stable absorber with interesting electronic and optical properties, such as a band-gap in the visible, and long carrier diffusion lengths. Yet, a thorough theoretical analysis of the exhibited properties is still missing in order to further assess its application potential from a materials design point of view. In this letter, we perform a detailed analysis for the established Ti-based compounds and investigate the less-known materials based on Zr. We discuss in details their electronic properties and band symmetries, highlight the similarity between the materials in terms of properties, and reveal limits for tuning electronic and optical properties within this family of vacancy ordered double perovskites that share the same electron configuration. We also show the challenges to compute accurate and meaningful quasi-particle corrections at GW level. Furthermore, we address their chemical stability against different decomposition reaction pathways, identifying stable regions for the formation of all materials, while probing their mechanical stability employing phonon calculations. We predict that Cs${2}$ZrI${6}$, a material practically unexplored to-date, shall exhibit a quasi-direct electronic band-gap well within the visible range, the smallest charge carrier effective masses within the Cs${2}$BX${6}$ (B=Ti,Zr; X=Br, I) compounds, and a good chemical stability.