A2AgCrCl6 (A = Li, Na, K, Rb, Cs) halide double perovskites: a transition metal-based semiconducting material series with appreciable optical characteristics

Abstract

We have theoretically examined the geometries, electronic density of states and band structures of cubic and hexagonal A₂AgCrCl₆ (A = Cs, Rb, K, Na, Li) using meta-GGA SCAN-rVV10. The optimized lattice density was found to vary between 2.68 and 4.08 g cm⁻³ for cubic-A₂AgCrCl₆, with the fundamental electronic bandgap (direct) in the range of 0.66–0.69 eV. The cell density of hexagonal A₂AgCrCl₆ was between 2.97 and 3.93 g cm⁻³, but with an indirect bandgap of 0.93–1.02 eV. The valence band maximum and the conduction band minimum of A₂AgCrCl₆ were confirmed to be essentially of Cr(3d) character, but the contributions from the orbital states of Cl(3p) to the VBM were also appreciable. Cubic A₂AgCrCl₆ (A = Cs, Rb, K) was identified to possess genuine perovskite stoichiometry, evaluated using various geometry-based indices (viz. octahedral factor, tolerance factor, and global instability index). This was not so for A₂AgCrCl₆ (A = Na, Li), and was due to the small size of Na and Li cations that caused the critical strain of CrCl₆ octahedra and a significant decrease in the cell volume. However, all the five A₂AgCrCl₆ displayed nearly similar optical properties, including the nature of the oscillator peaks in the dielectric function, absorption coefficient, photoconductivity, reflectivity, and Tauc spectra. The zero-limit of the refractive index was calculated around 2.25 and 2.00 for cubic and hexagonal A₂AgCrCl₆, respectively, and the extinction coefficient was very small for all cases. The nature of the optical bandgap and transition peaks discussed in this study of cubic and hexagonal Cs₂AgCrCl₆ agreed well with the experiment. The examination of phonon band dispersion led to the conclusion that cubic-A₂AgCrCl₆ (A = Cs, Rb) are the only halide double perovskites of the entire series that are dynamically stable.