Electronic structure and stability of Cs2TiX6 and Cs2ZrX6 (X = Br, I) vacancy ordered double perovskites

Vacancy ordered halide perovskites have been extensively investigated as promising lead-free alternatives to halide perovskites for various opto-electronic applications. Among these, Cs2TiBr6 has been reported as a stable absorber with interesting electronic and optical properties, such as a bandgap 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 material's 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 detail 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 the 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 Cs2ZrI6, a material practically unexplored to date, shall exhibit a quasi-direct electronic bandgap well within the visible range, the smallest charge carrier effective masses within the Cs2BX6 (B = Ti, Zr; X = Br, I) compounds, and a good chemical stability.

Automated summary

This study investigates the electronic and optical properties of Ti-based and Zr-based compounds, highlighting similarities and limitations in tuning properties within the family of vacancy ordered double perovskites. Challenges in computing accurate quasi-particle corrections at the GW level are also discussed, along with the chemical and mechanical stability of the materials. Cs2ZrI6 is predicted to have a quasi-direct electronic bandgap in the visible range, smallest charge carrier effective masses among Cs2BX6 compounds, and good chemical stability.