Structural and optical properties of the Cu₂ZnSnSe₄ thin films grown by nano-ink coating and selenization

Quaternary semiconductor Cu₂ZnSnSe₄ (CZTSe) is a very promising alternative to semiconductors based on indium (In) and gallium (Ga) as solar absorber material due to its direct band gap, inherent high absorption coefficient (>10⁴ cm⁻¹) and abundance of cheap elements zinc (Zn) and tin (Sn). In this study, high quality CZTSe thin films were successfully synthesized by a green and low-cost solution based non-vacuum method, which involves spin coating non-toxic solvent-based CZTSe nano-inks onto Mo coated soda lime glass substrates followed by selenization with elemental Se vapor. The effect of selenization temperature on structural, morphological, compositional and optical properties of CZTSe films are investigated using X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and photoluminescence spectroscopy. XRD and Raman analysis indicates that a tetragonal stannite-type structured CZTSe is formed. Depend on the selenization temperature, the dense and compact films with grain sizes from 200 nm (500 °C) up to about 1 μm (580 °C) are obtained. EDS measurement indicates that the composition ratios of the prepared CZTSe films are copper-poor and zinc-rich nature. The CZTSe films are p-type conductivity confirmed by a hot point probe method. Photoluminescence spectrum shows slightly asymmetric narrow bands with a maximum of intensity at 0.92 eV. The dependence of the photoluminescence on the excitation temperature reveals a decrease in the intensity of the photoluminescence bands. An absorption coefficient exceeding 10⁴ cm⁻¹ and the band gap energy about 0.87 eV of the studied films are determined by an absorption spectroscopy.