In this study, we proposed a 4-step selenization process for the RF-sputtered Cu–Zn/Sn metallic stack to prepare Cu2ZnSnSe4 (CZTSe) absorber. We applied a pre-heating treatment for the metal stack under vacuum prior to the selenization, which plays an important role to form a well inter mixed alloy with relatively smooth thin film morphology. The nucleation temperatures were controlled precisely from 150 °C to 500 °C during 4-step selenization to avoid the formation of secondary phases and to improve the crystal quality of CZTSe with a greater homogeneity in the composition. The formation of various phases during each step in 4-step selenization process were studied by X-ray Diffraction, Raman analysis and we proposed a possible reaction mechanism of the CZTSe formation with binary and ternary compounds as intermediates. We also performed optical analysis, including Uv–Visible absorption and low temperature photoluminescence, and scanning transmission electron microscope analysis for the CZTSe samples. Finally, an efficiency of 5.8% CZTSe solar cell is fabricated with an open circuit voltage of 370 mV, short circuit current of 31.99 mA/cm2, and a fill factor of 48.3%.
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