Defect Tolerance to Intolerance in the Vacancy-Ordered Double Perovskite Semiconductors Cs2SnI6 and Cs2TeI6

Vacancy-ordered double perovskites of the general formula A2BX6 are a family of perovskite derivatives composed of a face-centered lattice of nearly isolated [BX6] units with A-site cations occupying the cuboctahedral voids. Despite the presence of isolated octahedral units, the close-packed iodide lattice provides significant electronic dispersion, such that Cs2SnI6 has recently been explored for applications in photovoltaic devices. To elucidate the structure–property relationships of these materials, we have synthesized solid-solution Cs2Sn1–xTexI6. However, even though tellurium substitution increases electronic dispersion via closer I–I contact distances, the substitution experimentally yields insulating behavior from a significant decrease in carrier concentration and mobility. Density functional calculations of native defects in Cs2SnI6 reveal that iodine vacancies exhibit a low enthalpy of formation, and that the defect energy level is a shallow donor to the conduction band rendering the material ...