Optimization of CZTSe Thin Films Using Sequential Annealing in Selenium and Tin–Selenium Environments

Cu 2 ZnSnSe 4 (CZTSe) is a promising material for thin-film solar cells due to its suitable band gap, high absorption coefficient, and composition of earth-abundant and nontoxic elements. In this study, we prepared CZTSe thin films from Cu/SnSe 2 and ZnSe stacks using a two-step annealing process. Initially, Cu–Sn–Se (CTSe) films were synthesized by sequential deposition and annealing of Cu and SnSe 2 precursors in either a selenium (Se) or tin–selenium (Sn+Se) atmosphere. After the deposition of a ZnSe layer on top of CTSe films, the stack underwent a second annealing process, again in either a Se or Sn+Se atmosphere, resulting in four distinct annealing combinations: Se→Se, Sn+Se→Se, Se→Sn+Se, and Sn+Se→Sn+Se. The first annealing step enabled the formation of CTSe, while the second annealing step, performed after ZnSe deposition, led to the formation of the CZTSe phase. Comprehensive characterization including grazing incidence X-ray diffraction (GIXRD), Raman spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and electrical measurements was conducted. GIXRD and Raman analysis revealed kesterite CZTSe phase peaks, with some samples showing a split in the main peak at ∼27° (2θ), indicating the presence of Cu x Se and ZnSe secondary phases. SEM analysis showed the impact of Sn and Se annealing on grain size, with larger grains observed in films annealed in Sn+Se atmospheres, particularly in the second heat treatment process. EDS results displayed consistent elemental composition across samples, with varying Cu/(Zn+Sn), Zn/Sn and Se/metal ratios influencing the band gap values from 1.09 to 1.63 eV. Hall measurements indicated p-type conductivity with carrier concentrations between 10 16 and 10 23 cm –3 . These results highlight the effectiveness of our two-step annealing process, particularly the Sn+Se atmosphere, in optimizing CZTSe thin films for potential use in high-efficiency thin-film solar cells.