A precursor‐annealing process based on a Cu‐rich precursor that has a maximum power conversion efficiency of 7.5% for pure selenide kesterite cells is presented. The Cu‐rich step is beneficial for the transport properties. Nanometer‐sized domains of ZnSe are found in all films.
We use atom probe tomography (APT) for resolving nanometer scale compositional fluctuations in Cu2ZnSnSe4 (CZTSe) thin-films prepared by co-evaporation and post-deposition annealing. We detect a complex, nanometer–sized network of CZTSe and ZnSe domains in these films. Some of the ZnSe domains contain precipitates having a Cu- and Sn-rich composition, where the composition cannot be assigned to any of the known equilibrium phases. Furthermore, Na impurities are found to be segregated at the CZTSe/ZnSe interface. The insights given by APT are essential for understanding the growth of CZTSe absorber layers for thin-film solar cells and for optimizing their optoelectronic properties.
Secondary phases, such as ZnSe, occur in Cu2ZnSnSe4 and can be detrimental to the resulting solar cell performance. Therefore, it is important to have simple tools to detect them. We introduce subband gap defect excitation room temperature photoluminescence of ZnSe as a practical and non-destructive method to discern the ZnSe secondary phase in the solar cell absorber. The PL is excited by the green emission of an Ar ion laser and is detected in the energy range of 1.2–1.3 eV. A clear spatial correlation with the ZnSe Raman signal confirms this attribution.
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