Enhanced White-Light Emission from Self-Trapped Excitons in Antimony and Bismuth Halides through Structural Design

Abstract: Lead halide perovskites have catalyzed the rise of main-group metal halide materials as promising candidates for next-generation optoelectronics, including solar cells, light-emitting diodes, lasers, sensors, and photocatalysts. Among these, effi-cient light-emission arises from self-trapped excitons, wherein excited states induce transient lattice distortions that localize excitons. However, the complex interplay of factors, such as lattice distortions, lattice softness, and electron-phonon cou-pling dynamics, obscures the direct structure-property relationships complicating the targeted material design. In this study, we advance the understanding of self-trapped exciton (STE)-based emission in hybrid antimony and bismuth halides, em-phasizing the interplay of structural and electronic factors that enhance white-light emission. We systematically vary com-position, anion dimensionality, connectivity, and the organic cation and find that the presence of Bi/Sb and Cl in edge-sharing anion motifs promotes white-light emission and optimal electron-phonon coupling. Chlorides outperform bromides, and organic cations, such as CMA and BZA, only subtly influence optical behavior by altering lattice dynamics and rigidity, resulting in tunable emission characteristics without compromising STEs. This work deepens the understanding of the emis-sion mechanisms in hybrid halide perovskites and establishes guiding principles for tailoring optoelectronic properties, paving the way for advanced materials with enhanced white-light emission for next-generation optoelectronic applications.