Study of the semiconducting properties of Cu2ZnSnS4 thin films grown by ultrasonic spray pyrolysis of water-dissolved precursors

Abstract

Cu2ZnSnS4 (CZTS) thin films were deposited on glass-slide substrates by ultrasonic spray pyrolysis at the substrate temperatures in the 330–420 °C range, using water–ethanol solutions containing CuCl2–H2O, ZnCl2, SnCl2, and (NH2)2CS (thiourea). After being deposited, CZTS films were annealed under vacuum and then characterized in regarding their structural and optical properties. The X-ray diffraction and Raman spectroscopy studies indicated that CZTS thin films with kesterite as predominant phase could be obtained. The X-ray diffraction patterns of all deposited samples displayed diffraction peaks corresponding to the planes (112), (220), and (312) of kesterite CZTS and diffraction peaks belonging to phases other than CZTS were apparently undetectable for the X-ray technique. Furthermore, their Raman spectra were featured for a widely structured Raman band in the 200–400 cm−1 wavenumber area. After being deconvoluted, Raman peaks belonging only to kesterite CZTS were revealed. However, a further analysis of the UV–Vis absorbance spectra indicated all our films strongly absorbs in this spectral region. In the low photon energy region (< 1.5 eV), Tauc plots revealed electron transitions with characteristic energy values in the 1.15–1.34 eV range, which could be attributed at the presence of tetragonal Cu2SnS3 and point defects (VS and VZn) into CZTS. All prepared CZTS films display the p-type conductivity as verified by Hall measurements.