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This paper provides an overview of the physical vapor technologies used to synthesize Cu2ZnSn(S,Se)4 thinfilms as absorber layers for photovoltaic applications. Through the years, CZT(S,Se) thinfilms have been fabricated using sequential stacking or co-sputtering of precursors as well as using sequential or co-evaporation of elemental sources, leading to high-efficient solar cells. In addition, pulsed laser deposition of composite targets andmonograin growth by themolten saltmethodwere developed as alternativemethods for kesterite layers deposition. This review presents the growing increase of the kesterite-based solar cell efficiencies achieved over the recent years. A historical description of themain issues limiting this efficiency and of the experimental pathways designed to prevent or limit these issues is provided and discussed aswell. Afinal section is dedicated to the description of promising process steps aiming at further improvements of solar cell efficiency, such as alkali doping and bandgap grading.

Physical routes for the synthesis of kesterite