Silver–Tin Sulfide/Selenide Semiconductor for Super-Narrow-Bandgap Photovoltaics and Thermoelectric Applications: A Review

Ag-Sn-S/Se semiconductors, particularly Ag8SnS6 and Ag8SnSe6, have emerged as promising thermoelectric (TE) materials due to their intrinsically low lattice thermal conductivity and favorable electronic transport properties. Owing to their direct and super-narrow bandgaps, these semiconductors also hold significant potential for photovoltaic (PV) applications, especially in near-infrared (NIR) energy harvesting and tandem architecture. This review provides a detailed analysis of the synthesis strategies, crystallographic evolution, phase transition mechanisms, and bandgap modulation in Ag-Sn-S/Se semiconductors. Particular focus is given to the structural adaptability of argyrodite-type compounds, where intrinsic cationic disorder and halogen-assisted anion substitution collectively enable the fine-tuning of electronic transport and lattice dynamics. TE performance is evaluated in terms of carrier mobility and thermal conductivity, highlighting a significant improvement in figure of merit. The review further explores the potential of Ag-Sn-S/Se semiconductors in energy conversion PVs, particularly as photoabsorber layers and counter electrode materials. Despite initial demonstrations, systematic studies on device integration remain limited, highlighting substantial opportunities for future research aimed at optimizing their optoelectronic interfaces and overall PV performance. This review ultimately discusses the potential of Ag-Sn-S/Se semiconductors, emphasizing their tunable properties as being key to next-generation PV and thermoelectric technologies. It highlights the current achievements and unresolved challenges, outlining strategic pathways for future research and device integration.