An Intricate Balance of Ionicity and Covalency: Metal-Like Conduction in All-Inorganic Halide Double Perovskite Cs2AgSbCl6

Abstract

Halide perovskites have recently evolved as attractive materials with enormous technological significance due to synthetic control over the structure-property relationship. Halide perovskites are often realized to be either electrical insulators or semiconductors. We present an unusual metal-like conduction (thermally deactivated) in a Pb-free all-inorganic halide double perovskite, Cs<inf>2</inf>AgSbCl<inf>6</inf>. The experimental results were understood using density functional theory studies, combined with molecular dynamics simulations and electron localization function calculations, revealing retention of the predominant ionicity of the Ag-Cl bond and an increase in the covalency of the Sb-Cl bond at an elevated temperature, which resulted in a significant change of the electronic band structure, including the density of states, thereby exhibiting an intricate balance of ionicity and covalency. A significant modulation of the electrical conductivity (more than 3 orders of magnitude) without any noticeable structural change will stimulate the investigation of hitherto unknown electronic phase transitions in halide double perovskites. Additionally, light-induced unidirectional rectification of current in Cs<inf>2</inf>AgSbCl<inf>6</inf> was ascribed to a dynamic internal polarization effect. © 2025 American Chemical Society.