Non-stoichiometry effect and disorder in Cu2ZnSnS4 thin films obtained by flash evaporation: Raman scattering investigation

The cation disorder in Cu2ZnSnS4 thin films grown by flash evaporation of ZnS, CuS and SnS binary compounds has been studied by Raman spectroscopy. Process parameters such as the substrate temperature during the evaporation and the Ar pressure in the post-thermal treatment determined the samples' composition and Raman spectra. As a measure of cation disorder, the half-width and relative intensity of the Raman band peaking at 331-332 cm-1 is analysed. Comparison of the spectra for different samples of known composition showed that the relative intensity of the 331 cm-1 defect peak correlates with the previously reported theoretical prediction about enhancement of antisite defect formation in Cu2ZnSnS4 under "Cu-poor, Zn-rich" conditions. For "Cu-rich, Zn-poor" films, further experimental confirmation was obtained of the previously detected effect of the enhancement of cation disorder under intense optical excitation