Kesterite is an attractive material for absorber layers in thin film photovoltaics. Solar cells based on kesterite have shown a substantial progress over the last decade; nevertheless, further improvements in device efficiency are pending due to the open‐circuit voltage (Voc) deficit (i.e., difference between the maximum V oc that can be achieved according to Shockley–Queisser limit and actual V oc from the device). In this study, the optoelectronic properties of the author's internal record Cu2ZnSnSe4 solar cell, which shows a power conversion efficiency of 11.4%, are presented. The device measurements reveal a Voc deficit of 337 mV, which is one of the lowest V oc deficits in the literature. Moreover, an unusual behavior for kesterite is observed: (i) photon energy of the photoluminescence emission and (ii) the extrapolated V oc for 0 K are both matching the band gap region of the absorber. These results indicate a significant improvement in the recombination characteristics and absorber quality in comparison to other kesterite devices in literature.

This paper provides an overview of the physical vapor technologies used to synthesize Cu 2 ZnSn(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. A final 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. intensive research on Cu 2 ZnSn(S,Se) 4 (CZT(S,Se)) kesterite compounds as CRM-free absorber layers for PV applications is essential. This article aims at establishing a complete overview of the physical routes used for the synthesis of kesterite thin films as absorber layers in solar cells. The following sections are devoted to that objective and will take on the main issues which have been raised so far as well as how the processes have evolved through the years to meet the requirements of the market. Some major advancements in terms of deposition or post-deposition treatments are introduced. Advantages and drawbacks of each of the physical methods presented in this review are described in detail and compared to other physical or chemical synthesis routes. Physical routes: status overviewWe performed an extensive identification of the common processes and methods used for the synthesis of kesterite thin films or for the design of solar cell devices. In order to avoid unnecessary repetitions along this paper, this section first explains these well-known and commonly used experimental processes and methods. Historically, based on the similarities between kesterite and chalcopyrite compounds, the standard device structure adopted for Cu(In,Ga)(S,Se) 2 (CIGSSe) was directly extended to CZTSSe, by simply replacing the CIGSSe absorber layer with a p-type CZTSSe thin film. CZTSSe solar cells are then typically produced using a soda-lime glass (SLG) substrate coated with a sputtered Mo layer acting as rear metallic contact. Typical sputter-deposited Mo layer thickness is around 500 nm up to 1 μm [12]. The kesterite absorber is then deposited onto the Mo layer.The fabrication of this absorber consists in the deposition of a precursor layer via a physical or a chemical route, which is then annealed in a reactive atmosphere containing either S (sulfurization) or Se (selenization). As a common result of the reactive annealing, a thin Mo(S,Se) 2 layer is naturally formed at the CZTSSe/Mo interface, betw...

The selenization of stacked elemental metallic layers (CuSn–Zn) is a commonly reported approach in kesterite Cu2ZnSnSe4 (CZTSe) processing. CZTSe formation via this approach usually involves a reaction route containing binary selenides, such as SnSe2−x. The high volatility of these phases at the necessary annealing temperatures (500–550 °C) makes this reaction pathway prone to Sn loss, which makes it challenging to control the composition and quality of the grown material. Herein, an approach based on stacked elemental and alloyed precursors is reported, and the benefits of using a Zn/CuSn/Zn configuration are discussed. The absence of nonalloyed elemental Sn helps in suppressing the formation and subsequent evaporation of SnSe2−x phases, preventing Sn loss from the film during selenization. This reaction pathway involves a process scheme which 1) starts with the growth of CZTSe in a “Cu‐rich” environment, 2) includes a shift of the composition by supply of SnSe2−x vapor, and 3) terminates in the “Cu‐poor” regime, leading to device efficiencies above 10%. This composition shift in the presented process appears similar to the final stage of the commonly known CIGSe three‐stage coevaporation.

In this paper, we present our route to fabricate Cu2ZnSnSe4 (CZTSe) thin films, which allows to achieve reproducible processing of kesterite absorber, that leads to efficiencies in the range of 10%. The article mainly focuses on the annealing process and demonstrates that controlling of the reactor pressure for selenization can be reliably used to tune the losses of volatile constituents in the absorber, enabling adjustments on the properties of the film and solar cell. The findings reveal a noteworthy resilience to small changes of the process parameters in the vicinity of optimum conditions. Interestingly, a certain pressure range for optimum Zn and Sn composition exists, which results in a broad and stable process window and enables reproducible processing of CZTSe with high power conversion efficiencies. The established process also allows simple upscaling of the device area and results in a power conversion efficiency of ≈ 8% on a large area of 2.85 cm2. The highest efficiencies achieved by our process are around 11% for smaller lab scale devices.

In this manuscript, we give an overview of the main insights into our growth procedure for kesterite solar cells and show the possibilities that are provided by this approach. The importance of using Cu–Sn alloy instead of elemental Sn and Cu in the precursor is shown. We discuss how the alloy approach stabilises the composition and helps guide the process along a preferred reaction pathway. A summary of our previously reported findings in the context of our latest results on kesterite solar cells prepared from Cu–Sn alloyed precursors is drawn. The positive impact of an alloy precursor configuration on the formation pathway, process control, and process resilience is demonstrated. Furthermore, a new optimisation strategy for kesterite, based on the reported pathway, is discussed, including a smooth phase transition from Cu-rich to Cu-poor kesterite. Finally, we demonstrate results on buffer optimisation and the application of a promising hybrid buffer configuration of CdS/Zn(O,S), which can reduce the optical losses in the solar cell structure.

This study show the influence of selenium amount during annealing of kesterite on the elemental composition of absorber and on the opto-electronic properties of solar cells. Enhanced carrier collection leads to device efficiencies approaching 12%.

Molybdenum (Mo) is the most commonly used back-contact material for copper zinc tin selenide (CZTSe)-based thin-film solar cells. The effect of a pure Ar plasma and a mixed Ar–N2 plasma on the back-contact interface of CZTSe solar cells is reported in this study.

This article demonstrates a flash-type kinetic sulfurization method to introduce band-gap grading in CZTSe based photovoltaic devices. The developed approach allows to achieve a steep grading profile on kesterite thin-film surface.