Influence of the sulphurization time on the morphological, chemical, structural and electrical properties of Cu2ZnSnS4 polycrystalline thin films

• Study of the sulphurization time influence on the morphological and electrical properties of CZTS.
• Investigation of temperature dependence of σ to understanding the transport phenomena.
• The annealing time improves the chemical composition and increases the crystallite size.
• The annealing time increases free holes, acceptors and donors concentration.
• These results contribute for a better optimization of the CZTS absorber layer of the solar cell.

The effects of the sulphurization annealing time on the morphological, chemical, structural and electrical properties of CZTS thin films were investigated by scanning electron microscopy, X-ray energy dispersive spectroscopy, Hall effect and electrical conductivity measurements in samples annealed during different time intervals. The increase of the annealing time was found to improve the chemical composition of the samples and to, slightly, increase the crystallite size. Small amounts of Na were measured in the samples. However, the concentration of Na does not increase significantly with the annealing time and should not modify the characteristics of the CZTS thin films. It was also found that at high temperature the electrical conductivity is dominated by thermal emission of carriers over the inter-grain potential barriers. As the temperature decreases different hopping conduction mechanisms start to dominate. At first with nearest-neighbour hopping and successively changing to variable range hopping conduction with a crossover from Mott and Efros–Shklovskii behavior. The electrical conductivity, the concentration of free holes, acceptors and donors, traps' density at the grain boundaries and the grain potential barriers height were found to increase with the annealing time. However, a significant drop in the compensation ratio from 0.8 to 0.5 was also detected.