Influence of Local Cation Order on Electronic Structure and Optical Properties of Cation-Disordered Semiconductor AgBiS₂

Abstract Site disorder exists in some practical semiconductors and can significantly impact their intrinsic properties both beneficially and detrimentally. However, the uncertain local order and structure pose a challenge for experimental and theoretical research. Especially, it hinders the investigation of the effects of the diverse local atomic environments resulting from the site disorder. We employ the special quasi-random structure method to perform first-principles research on connection between local site disorder and electronic/optical properties, using cation-disordered AgBiS 2 (rock salt phase) as an example. We predict that cation-disordered AgBiS 2 has a bandgap ranging from 0.6 to 0.8 eV without spin-orbit coupling and that spin-orbit coupling reduces this by approximately 0.3 eV. We observe the effects of local structural features in the disordered lattice, such as the one-dimensional chain-like aggregation of cations that results in formation of doping energy bands near the band edges, formation and broadening of band-tail states, and the disturbance in the local electrostatic potential, which significantly reduces the bandgap and stability. The influence of these ordered features on the optical properties is confined to alterations in the bandgap and does not markedly affect the joint density of states or optical absorption. Our study provides a research roadmap for exploring the electronic structure of site-disordered semiconductor materials, suggests that the ordered chain-like aggregation of cations is an effective way to regulate the bandgap of AgBiS 2 , and provides insight into how variations in local order associated with processing can affect properties.