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To replace the conventionally used CdS buffers in Cu2ZnSn(S,Se)4 (CZTSSe) based thin-film solar cells, sputtered Zn(O,S) buffer layers have been investigated. Zn(O,S) layers with three different [O]/([O] + [S]) ratios (0.4, 0.7, and 0.8)—and a combination of Zn(O,S) and CdS ("hybrid buffer layer") were studied. In comparison to the CdS reference, the external quantum efficiency (EQE) of the Zn(O,S)-buffered devices increases in the short- and long-wavelength regions of the spectrum. However, the average EQE ranges below that of the CdS reference, and the devices show a low open-circuit voltage (VOC). By adding a very thin CdS layer (5 nm) between the absorber and the Zn(O,S) buffer, the VOC loss is completely avoided. Using thicker intermediate CdS layers result in a further device improvement, with VOC values above those of the CdS reference. X-ray photoelectron spectroscopy (XPS) measurements suggest that the thin CdS layer prevents damage to the absorber surface during the sputter deposition of the Zn(O,S) buffer. With the hybrid buffer configuration, a record VOC deficit, i.e., a minimum difference between bandgap energy Eg (divided by the elementary charge q) and VOC (Eg/q – VOC) of 519 mV could be obtained, i.e., the lowest value reported for kesterite solar cells to date. Thus, the hybrid buffer configuration is a promising approach to overcome one of the main bottlenecks of kesterite-based solar cells, while simultaneously also reducing the amount of cadmium needed in the device. [ABSTRACT FROM AUTHOR]

We investigate the electronic structure and the radiative recombination in wet-chemically fabricated Cu2ZnSn(S,Se)4 solar cell absorbers utilizing photoluminescence (PL) and photoluminescence excitation (PLE) spectroscopy, focusing especially on the effects of varying Cu content. This includes the impact of the latter on the band gap energy and the change in band gap energy related to the order-disorder transition. Characteristic PL and PLE parameters like the energetic position of the PL maximum and the PL yield as a function of the excitation power as well as the PLE tailing parameter do not depend on composition indicating that the nature of the radiative transition is not altered by the Cu content. However, the band gap energy Eg significantly increases as a function of decreasing Cu content. This increase is more pronounced in the disordered than in the ordered atomic arrangement of Cu and Zn atoms in the Cu-Zn planes of the kesterite crystal structure. [ABSTRACT FROM AUTHOR]

Cu2ZnSnSe4 (CZTSe) thin films are prepared by a two-step method which involves co-evaporation of Cu, Zn, Sn, and Se on molybdenum-coated soda-lime glass at low substrate temperature and a following selenization. Solar cells with efficiencies of up to 6.5% can be achieved. The influence of the selenium deposition rates during co-evaporation and the nitrogen pressure during selenization on the properties of the CZTSe films are investigated. It is found that these two parameters can significantly affect the morphology and crystallinity of the CZTSe films. The possible reasons for the experimental results are discussed. [ABSTRACT FROM AUTHOR]

We report on order-disorder related band gap changes in Cu2ZnSn(S,Se)4 solar cells which are induced by post-annealing. The band gap changes of the absorber are detected utilizing electroreflectance and analyzed by comparison with predictions of the stochastic Vineyard model. This yields a critical temperature of TC = 195°C above which the Cu2ZnSn(S,Se)4 absorber layer is entirely disordered within the Cu-Zn layers of the kesterite unit cell. The temporal evolution of the band gap during annealing shows that the equilibrium value is reached on a timescale in the order of hours, depending on the annealing temperature. In contrast to other experimental techniques, electroreflectance precisely measures the band gap and is not influenced by defect-mediated radiative recombination. [ABSTRACT FROM AUTHOR]