Probing Local Coordination and Halide Miscibility in Single-, Double-, and Triple-Halide Perovskites Using EXAFS

Abstract

Lead-halide perovskites are a promising material platform as semiconductors in next-generation solar cells because of their solution processability, defect tolerance, and tunable optoelectronic properties. Mixed iodide–bromide perovskite compositions are attractive as wide-bandgap absorbers but suffer from significant operational instabilities. Incorporation of chloride to form triple-halide perovskites has been shown to improve both stability and performance; however, the extent of halide miscibility and chloride incorporation remains poorly understood. While bulk metrics such as diffraction-derived lattice parameters and optical bandgaps can confirm single-phase behavior, they do not establish homogeneous mixing on the halide site. Here, we use cryogenic X-ray absorption spectroscopy (XAS) to directly probe local lead-halide coordination across single-, double-, and triple-halide perovskite compositions. We show the formation of a single-phase triple-halide perovskite whose miscibility is mediated by bromide content. We identify signatures of halide mixing from the Pb L3-edge EXAFS of mixed double- and triple-halide perovskites using both quantitative fits and Cauchy wavelet transforms. Finally, using wavelet transforms of the Br K-edge EXAFS, we demonstrate halide intermixing on the single PbX6 octahedron level, exploiting forward-scattering amplified third-shell halide–bromide interactions. These results are a step forward in the understanding of local structure that is required to fully describe and optimize halide incorporation for novel perovskite compositions.