SnSe: A Versatile Material for Thermoelectric and Optoelectronic Applications

Tin selenide (SnSe) is a sustainable, lead-free IV–VI semiconductor whose layered orthorhombic crystal structure induces pronounced electronic and phononic anisotropy, enabling diverse energy-related functionalities. This review systematically summarizes recent progress in understanding the structure–property–processing relationships that govern SnSe performance in thermoelectric and optoelectronic applications. Key crystallographic characteristics are first discussed, including the temperature-driven Pnma–Cmcm phase transition, anisotropic band and valley structures, and phonon transport mechanisms that lead to intrinsically low lattice thermal conductivity below 0.5 W m−1 K−1 and tunable carrier transport. Subsequently, major synthesis strategies are critically compared, spanning Bridgman and vertical-gradient single-crystal growth, spark plasma sintering and hot pressing of polycrystals, as well as vapor- and solution-based thin-film fabrication, with emphasis on process windows, stoichiometry control, defect chemistry, and microstructure engineering. For thermoelectric applications, directional and temperature-dependent transport behaviors are analyzed, highlighting record thermoelectric performance in single-crystal SnSe at hi. We analyze directional and temperature-dependent transport, highlighting record thermoelectric figure of merit values exceeding 2.6 along the b-axis in single-crystal SnSe at ~900 K, as well as recent progress in polycrystalline and thin-film systems through alkali/coinage-metal doping (Ag, Na, Cu), isovalent and heterovalent substitution (Zn, S), and hierarchical microstructural design. For optoelectronic applications, optical properties, carrier dynamics, and photoresponse characteristics are summarized, underscoring high absorption coefficients exceeding 104 cm−1 and bandgap tunability across the visible to near-infrared range, together with interface engineering strategies for thin-film photovoltaics and broadband photodetectors. Emerging applications beyond energy conversion, including phase-change memory and electrochemical energy storage, are also reviewed. Finally, key challenges related to selenium volatility, performance reproducibility, long-term stability, and scalable manufacturing are identified. Overall, this review provides a process-oriented and application-driven framework to guide the rational design, synthesis optimization, and device integration of SnSe-based materials.