Atomic insights into the optoelectronic properties of vacancy-ordered double perovskite halide semiconductors

Vacancy-ordered halide perovskite Cs2BX6 semiconductors are attracting an increasing level of interest for optoelectronic applications due to their high chemical stability and unique light emission properties. Here, we performed first-principles calculations to determine the energy positions and atomic orbital hybridization features of band edge states in Cs2BX6 (B = Ge, Sn, Te, Ti, Zr, Hf; X = Cl, Br, I). Our results revealed that all the Cs2BX6 perovskites, except for Cs2TeX6, have direct bandgaps at the Γ point. The indirect bandgaps of Cs2TeX6 originate from the symmetry-forbidden Te p–X p coupling at the Γ point. Both energy positions and dispersions of the band edge states of Cs2BX6 can be well modulated by varying X- and B-site ions. Our work provides a comprehensive understanding of electronic structures and optoelectronic properties of Cs2BX6 perovskites, shedding light on the design rules for high-performance perovskite optoelectronics.