Tuning the Optoelectronic Properties of Wide Bandgap Perovskites: Data‐Driven Insights from Combinatorial Synthesis and High‐Throughput Experimentation

ABSTRACT The discovery and optimization of wide‐bandgap lead halide perovskites (LHPs) is hindered by solution‐based workflows with limited scalability. Large compositional parameter spaces present an additional challenge for materials optimization. Here, we establish an integrated, combinatorial workflow based on sequential physical vapor deposition that enables independent tuning of cation (Cs/Pb) and anion (Br/Cl) compositions. Applying automated structural, compositional, and optical characterizations across >500 samples, regions of interest are rapidly screened in the quaternary Cs–Pb–Br–Cl space. From the screening, we establish a practical Cs/Pb window of 1.05–1.20 for wide bandgap perovskites, within which elevated PL yields were observed. Through in‐depth analysis of the data set, we uncover a high‐energy optical transition as a robust determinant for high PL yields. By combining mechanistic insight into the compositional origins of high PL efficiency with a fully integrated, high‐throughput screening framework, and by openly releasing the complete multimodal dataset, this work provides a broadly accessible benchmark to accelerate data‐driven discovery of wide‐bandgap perovskites.