BaZrS₃ Chalcogenide Perovskite Thin Films by H₂S Sulfurization of Oxide Precursors

Abstract

The earth-abundant ternary compound BaZrS₃, which crystallizes in the perovskite-type structure, has come into view as a promising candidate for photovoltaic applications. We present the synthesis and characterization of polycrystalline perovskite-type BaZrS₃ thin films. BaZrO₃ precursor layers were deposited by pulsed laser deposition and sulfurized at various temperatures in an argon-diluted H₂S atmosphere. We observe increasing incorporation of sulfur for higher annealing temperatures, accompanied by a red shift of the absorption edge, with a bandgap of <i>E</i>_g = 1.99 eV and a large absorption strength >10⁵ cm^-1 obtained for sulfurization temperatures of 1000 °C. X-ray diffraction analysis and SEM indicate enhanced crystallization at the higher annealing temperatures, but no evidence for a crystalline solid solution between the BaZrO₃ and BaZrS₃ phases is found. The charge carrier sum mobility estimated from optical-pump-terahertz-probe spectroscopy indicates increasing mobilities with increasing sulfurization temperature, reaching maximum values of up to ∼2 cm² V^-1 s^-1.