Photophysics in Cs₃Cu₂X₅ (X = Cl, Br, or I): Highly Luminescent Self-Trapped Excitons from Local Structure Symmetrization

Abstract

Self-trapped excitons (STEs) in metal halide materials are attracting an increasing level of interest due to their unique light emission properties. Light emission from STEs in metal halides is usually associated with excited-state structural deformation, which lowers the symmetry of local structures, as seen for the STEs in a wide range of materials systems. Here, we reveal a prototypic STE-associated structural “distortion” that, however, enhances the symmetry of local structures, in a series of all-inorganic copper(I)-based halides Cs3Cu2X5 (X = Cl, Br, or I). We further find that the emission peaks of Cs3Cu2X5 blue-shift when the halogen changes from Cl to Br to I, which is the opposite of the trends found in traditional halide perovskites. This phenomenon is attributed to a synergetic combination of the significant change in band gap associated with structural deformation and a strong excitonic effect. Due to the highly localized electron and hole upon photoexcitation, Cs3Cu2Cl5 shows an extremely long and temperature-sensitive photoluminescence (PL) lifetime among metal halide materials with STEs. Remarkably, strong green emission with a PL quantum yield exceeding 90% is found in Cs3Cu2Cl5, opening the way to designing light emission compounds based on local symmetry-enhancing STE mechanisms.