“…Over the last few decades, significant advancements have been made in the performances of thin-film solar cells based on CIGS (copper indium gallium selenide), CIS (copper indium sulfide), and CdTe technology. − However, their reliance on expensive, toxic, and scarcely available elements like cadmium, tellurium, and indium poses environmental and economic challenges . In this context, kesterite Cu 2 ZnSnS 4 (CZTS) emerges as a highly promising inorganic semiconducting compound for the production of low-cost thin-film photovoltaic devices because it is composed of easily available, cheap, nonpoisonous, and earth-abundant elements. − Current performances of CZTS solar cells are well below the Shockley–Queisser limit, and this is usually ascribed to the presence of defects and secondary phases, which heavily reduce the open-circuit voltage of the device . In particular, lattice defects induce the so-called “band tailing”, − reducing the charge-carrier generation rate and favoring nonradiative recombination processes. , Even if the efficiencies of CZTS-based solar cells are lower compared to other technologies from the same family, the use of environmentally friendly materials allows targeting specific applications such as building-integrated photovoltaic, flexible, and agrivoltaic solar cells. , Moreover, characterization through advanced techniques can provide a deep understanding of defects in kesterites, unlocking their full potential and the development of efficient and affordable thin-film photovoltaic devices.…”