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Cu2ZnSnS4 thin films have been produced via rapid thermal evaporation of off-stoichiometric kesterite powder followed by annealing in an Ar atmosphere. Different heating rates were applied during the thermal treatments. The chemical composition and structural properties of the deposited layers as well as the distribution of the elements through the kesterite thin film have been investigated. The initial growth of a SnS secondary phase during evaporation led to the formation of this secondary phase next to the Mo back contact. Solar cell power conversion efficiencies were limited to values about 3 % due to this secondary phase. Furthermore, an increased open circuit voltage was demonstrated by using a Zn(O,S) buffer layer ; This work was supported by DAAD project (INTERKEST, Ref: 57050358), Marie Curie-ITN (KESTCELLS, GA: 316488) and MINECO project (SUNBEAM, ENE2013-49136-C4-3-R). RC and ES acknowledge financial support from Spanish MINECO within the Ramón y Cajal program (RYC-2011-08521) and (RYC-2011-09212) respectively. SG also thanks the Government of Spain for the FPI fellowship (BES-2014-068533).

This work has been published in Solar Energy 198 (2020) 696–703 (DOI:10.1016/j.solener.2020.02.009). In this work, we report the effect of an ultra-thin Al2O3 layer (down to 3 nm) as interface passivation strategy for the improvement of the performance of Cu2ZnSnS4/CdS based solar cells. After an initial optimization, the Al2O3 deposited by thermal evaporation is proved to improve the properties of the p-n junction. The fabricated devices showed an increment in Voc depending on the composition of the absorber, and an improvement in fill factor (FF) apparently related to the insulation of possible shunt-paths. Also, the impact on other optoelectronic parameters is discussed. ; This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 712949 (TECNIOspring PLUS) and the Government of Catalonia's Agency for Business Competitiveness (ACCIÓ). This research has also been supported by the H2020 Programme under the project INFINITE-CELL (H2020-MSCA-RISE-2017-777968), by the Spanish Ministry of Science, Innovation and Universities under the IGNITE project (ENE2017-87671-C3-1-R), and by the European Regional Development Funds (ERDF, FEDER Programa Competitivitat de Catalunya 2007–2013). Authors from IREC and the University of Barcelona belong to the SEMS (Solar Energy Materials and Systems) Consolidated Research Group of the "Generalitat de Catalunya" (Ref.2017 SGR 862). M.P. thanks the Government of Spain for the Ramon y Cajal Fellowship (RYC-2017-23758). This research was also supported by Consejo Nacional de Ciencia y Tecnología (CONACYT) with the scholarship No. 433146 and with the project CB-CONACYT-255062. Finally, this research was also supported by Programa de Fortalecimiento de la Calidad Educativa (PFCE 2019) and by Project VIEP 2019.

This paper provides an overview of the physical vapor technologies used to synthesize Cu2ZnSn(S,Se)4 thin films as absorber layers for photovoltaic applications. Through the years, CZT(S,Se) thin films 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 and monograin growth by the molten salt method were developed as alternative methods 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 the main issues limiting this efficiency and of the experimental pathways designed to prevent or limit these issues is provided and discussed as well. 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 ; 1. R Caballero and M León acknowledge financial support via the Spanish Ministry of Science, Innovation and Universities project (WINCOST, ENE2016-80788-C5-2-R) and thank H2020 EU Programme under the project INFINITE-CELL (H2020-MSCA-RISE-2017-777968). 2. S Canulescu and J Schou acknowledge the support from Innovation Fund Denmark. 3. D-H Kim acknowledges financial support via the DGIST R&D Program of the Ministry of Science and ICT, KOREA (18-BD-05). 4.C. Malerba acknowledges the support from the Italian Ministry of Economic development in the framework of the Operating Agreement with ENEA for the Research on the Electric System. 5.A Redinger acknowledges financial support via the FNR Attract program, Project : SUNSPOT, Nr.11244141. 6. E Saucedo thanks H2020 EU Programme under the projects STARCELL (H2020-NMBP-03-2016-720907) and INFINITE-CELL (H2020-MSCA-RISE-2017-777968), the Spanish Ministry of Science, Innovation and Universities for the IGNITE project (ENE2017-87671-C3-1-R), and the European Regional Development Funds (ERDF, FEDER Programa Competitivitat de Catalunya 2007–2013). IREC belong to the SEMS (Solar Energy Materials and Systems) Consolidated Research Group of the 'Generalitat de Catalunya' (Ref. 2017 SGR 862). 7. Taltech acknowledges financial support via the Estonian Ministry of Education and Research funding project IUT19-28 and the European Union Regional Development Fund, Project TK141. 8. B Vermang has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (Grant Agreement No 715027)