A low-cost, sulfurization free approach to control optical and electronic properties of CZTS via precursor variation

Thin films of Cu2ZnSnS4 (CZTS) were synthesized via a low cost, wet chemical technique of chemical bath deposition (CBD). In the first part of this study, the chemical composition ratio S/(Cu+Zn+Sn) was varied keeping Cu/(Zn + Sn) and Zn/Sn ratios constant to study the effect of sulfur variation. Detailed electrical and optical characterization has been carried out using UV-Vis spectroscopy, x-ray diffraction, x-ray photoelectron spectroscopy, Raman spectroscopy and Kelvin probe force microscopy (KPFM) techniques. The results of the present study confirm that near ideal stoichiometry could be achieved in CZTS by adding excess thiourea in a controlled manner which eliminates the need for the normally used post-synthesis and high temperature sulfurization step. Using the stoichiometric sample as the basis, in the second part of the study Cu/(Zn+Sn) and Zn/Sn was varied and it was found that the electronic properties of CZTS in terms of band gap, work function and valence band edge position could be controlled by precursor variation. The Cu-poor, Zn-rich samples showed a better photoresponse which has been attributed to a decrease in the CuZn type defects. The study thus demonstrates a scalable and low-cost technique to grow CZTS absorber layers for solar cells with control over its electronic properties which is important for effective device operation.