Chalcogenide perovskites exhibit optoelectronic properties that position them as potential materials in the field of photovoltaics. We report a detailed investigation into the electronic structure and chemical properties of polycrystalline BaZrS₃ perovskite powder by X-ray photoelectron spectroscopy, complemented by an analysis of its long- and short-range geometric structures using X-ray diffraction and X-ray absorption spectroscopy. The results obtained for the powdered BaZrS₃ are compared to similar measurements on a sputtered polycrystalline BaZrS₃ thin film prepared through rapid thermal processing. While bulk characterization confirms the good quality of the powder, depth-profiling achieved by photoelectron spectroscopy utilizing Al K_α (1.487 keV) and Ga K_α (9.25 keV) radiations shows that, regardless of the fabrication method, the oxidation effects extend beyond 10 nm from the sample surface, with zirconium oxides specifically distributing deeper than the oxidized sulfur species. A hard X-ray photoelectron spectroscopy study on the powder and thin film detects signals with minimal contamination contributions and allows for the determination of the valence band maximum position with respect to the Fermi level. Based on these measurements, we establish a correlation between the experimental valence band spectra and the theoretical density of states derived from density functional theory calculations, thereby discerning the orbital constituents involved. Our analysis provides an improved understanding of the electronic structure of BaZrS₃ developed through different synthesis protocols by linking it to material geometry, surface chemistry, and the nature of doping. This methodology can thus be adapted for describing electronic structures of chalcogenide perovskite semiconductors in general, a knowledge that is significant for interface engineering and, consequently, for device integration.

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