Dependence of CZTS thin film properties and photovoltaic performance on heating rate and sulfurization time

Abstract

In this study, effect of heating rate and sulfurization time on the properties of CZTS thin films and their photovoltaic performances was investigated. CZTS layers were prepared by a two-stage technique comprising deposition of precursor films by sputtering on Mo-foil substrates (Mo-foil/ZnS/CuSn/Cu) and a sulfurization process utilizing Rapid Thermal Annealing (RTA) approach. Heating rates and sulfurization times at 550 °C were changed to determine the best conditions. CZTS films were characterized by several techniques. All samples showed Cu-poor and Zn-rich chemical composition regardless of the heating rate and annealing time of the sulfurization process. XRD diffraction patterns showed that only kesterite CZTS phase was formed in all samples. Although Raman spectroscopy measurements confirmed formation of kesterite CZTS phase in all samples, forming of Cu2SnS3 (CTS) secondary phase was detected in all films except for the sample prepared utilizing a relatively low heating rate of 1 °C/s and 60 s sulfurization time (CZTS-I-60). The largest crystallite size and the less micro strain and dislocation density were also found in this sample. All CZTS thin films displayed dense and compact polycrystalline surface microstructure. Optical characterizations showed that the optical band gaps of the films were in the range of 1.48–1.58 eV. PL emission spectra of the films exhibited transition from conduction band to acceptor/defect levels instead of band-to-band transition. Solar cells were fabricated and the highest Voc and conversion efficiency (4.39%) were achieved employing the film obtained with ramp rate of 1 °C/s and the sulfurization time of 60 s, because of better structural properties and purer crystal structure determined for this sample.