Breaking Barriers in Chalcogenide Perovskite Synthesis: A Generalized Framework for Fabrication of BaMS3 (M═Ti, Zr, Hf) Materials

Abstract

AbstractChalcogenide perovskites have garnered increasing attention as stable, non‐toxic alternatives to lead halide perovskites. However, their conventional synthesis at high temperatures (>1000 °C) has hindered widespread adoption. Recent studies have developed low‐to‐moderate temperature synthesis methods (<600 °C) using reactive precursors, yet a comprehensive understanding of the pivotal factors affecting reproducibility and repeatability remains elusive. This study delineates the critical factors in the low‐temperature synthesis of BaMS3 (M═Zr, Hf, Ti) compounds and presents a generalized framework. Innovative approaches are developed for synthesizing BaMS3 compounds using this framework involving organometallics for solution deposition. The molecular precursor routes, employing metal acetylacetonates to generate soluble metal–sulfur bonded complexes and metal–organic compounds to produce soluble metal‐thiolate, metal‐isothiocyanate, and metal‐trithiocarbonate species, are demonstrated to yield carbon‐free BaMS3. These methods have achieved the most contiguous films of BaZrS3 and BaHfS3 using solution deposition to date. Furthermore, a hybrid solution processing method involving stacking sputter‐deposited Zr and solution‐deposited BaS layers is employed to synthesize a contiguous, oxygen‐free BaZrS3 film. The diffuse reflectance measurements indicate a direct bandgap of ≈ 1.85 eV for the BaZrS3 films and ≈ 2.1 eV for the BaHfS3 film under investigation.