BaZrS₃ Lights Up: The Interplay of Electrons, Photons, and Phonons in Strongly Luminescent Single Crystals

Chalcogenide perovskites have emerged as a promising class of materials for the next generation of optoelectronic applications, with BaZrS 3 attracting significant attention due to its wide bandgap, earth‐abundant composition, and thermal and chemical stability. However, previous studies have consistently reported weak and ambiguous photoluminescence (PL), regardless of synthesis method, raising questions about the intrinsic optoelectronic quality of this compound. In this work, strong, band‐to‐band‐dominated PL is demonstrated at room temperature in high‐quality BaZrS 3 single crystals, with a PL quantum yield of ∼0.005%. Despite the narrow, single‐component PL emission band, time‐resolved PL measurements reveal a carrier lifetime of 1.0 ± 0.2 ns. To understand the origin of the strong PL and short carrier lifetime, multiwavelength excitation and polarization‐dependent Raman measurements are performed, supported by first‐principles lattice dynamics calculations. All 23 theoretically predicted Raman‐active modes and their symmetries are identified, providing a comprehensive reference for future studies. These results indicate that phonon‐assisted carrier decay and nontrivial electron‐phonon interactions contribute to the short carrier lifetimes, as evidenced by Raman spectroscopy and DFT calculations. Further studies on compositional variations or partial cation/anion substitutions can mitigate electron‐phonon coupling and enhance carrier lifetimes. By establishing a detailed reference for the intrinsic vibrational and optoelectronic properties of BaZrS 3 , this work paves the way for further advancements in chalcogenide perovskites for energy and optoelectronic technologies.