Copper-zinc-tin-chalcogenide kesterites, Cu(2)ZnSnS(4) and Cu(2)ZnSnSe(4) (CZTS(e)) are ideal candidates for the production of thin film solar cells on large scales due to the high natural abundance of all constituents, a tunable direct band gap ranging from 1.0 to 1.5 eV, a large absorption coefficient, and demonstrated power conversion efficiencies close to 10%. However, Sn losses through desorption of SnS(e) from CZTS(e) at elevated temperatures (above 400 °C) impede the thorough control of film composition and film homogeneity. No robust and feasible fabrication process is currently available. Here we show that understanding the formation reaction of the kesterite absorber is the key to control the growth process and to drastically improve the solar cell efficiency. Furthermore, we demonstrate that this knowledge can be used to simplify the four-dimensional parameter space (spanned by the four different elements) to an easy and robust two-dimensional process. Sufficiently high partial pressures of SnS(e) and S(e) (a) prevent the decomposition reaction of the CZTS(e) at elevated temperatures and (b) introduce any missing Sn into a Sn-deficient film. This finding enables us to simplify the precursor to a film containing only Cu and Zn, whereas Sn and S(e) are introduced from the gas phase by a self-regulating process.

This work reports the in-depth resolved Raman scattering analysis with different excitation wavelengths of Cu2ZnSnS4 layers. Secondary phases constitute a central problem in this material, particularly since they cannot be distinguished by x-ray diffraction. Raman spectra measured with 325 nm excitation light after sputtering the layers to different depths show peaks that are not detectable by excitation in the visible. These are identified with Cu3SnS4 modes at the surface region while spectra measured close to the back region show peaks from ZnS and MoS2. Observation of ZnS is enhanced by resonant excitation conditions achieved when working with UV excitation.

Secondary phases like Cu2SnS3 are major obstacles for kesterite thin film solar cell applications. We prepare Cu2SnS3 using identical annealing conditions as used for the kesterite films. By x-ray diffraction, the crystal structure of Cu2SnS3 was identified as monoclinic. Polarization-dependent Raman investigations allowed the identification of the dominant peaks at 290 cm−1 and 352 cm−1 with the main A′ symmetry vibrational modes from the monoclinic Cu2SnS3 phase. Furthermore, micro-resolved Raman investigations revealed local variations in the spectra that are attributed to a secondary phase (possibly Cu2Sn3S7). This exemplifies the abilities of micro-resolved Raman measurements in the detection of secondary phases.

Alongside with Cu 2 ZnSnS 4 and SnS, the p-type semiconductor Cu 2 SnS 3 also consists of only Earth abundant and low-cost elements and shows comparable opto-electronic properties, with respect to Cu 2 ZnSnS 4 and SnS, making it a promising candidate for photovoltaic applications of the future. In this work, the ternary compound has been produced via the annealing of an electrodeposited precursor in a sulfur and tin sulfide environment. The obtained absorber layer has been structurally investigated by X-ray diffraction and results indicate the crystal structure to be monoclinic. Its optical properties have been measured via photoluminescence, where an asymmetric peak at 0.95 eV has been found. The evaluation of the photoluminescence spectrum indicates a band gap of 0.93 eV which agrees well with the results from the external quantum efficiency. Furthermore, this semiconductor layer has been processed into a photovoltaic device with a power conversion efficiency of 0.54 %, a short circuit current of 17.1 mA/cm 2 , a open circuit voltage of 104 mV hampered by a small shunt resistance, a fill factor of 30.4 %, and a maximal external quantum efficiency of just less than 60 %. In addition, the potential of this Cu 2 SnS 3 absorber layer for photovoltaic applications is discussed.

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