Thin layers of Sn onto Cu-Zn alloy with different component ratios were processed at different temperatures. Scrupulous comparative analyses were performed by room temperature Raman spectroscopy and X-ray-diffractometry. An excess of tin on the surface results in isothermal selenization at 450 degrees C in the hexagonal residuals of unstable SnSe2 in the well-crystallized Stannite - Cu2ZnSnSe4. In similar selenization conditions, copper-rich layers as precursors result in the Stannite phase with micro-immersions of CuSe. Low-temperature photoluminescence spectra of selenized films indicated to two Gaussian shaped bands at 0.81 and 1.16 eV. (C) 2011 Elsevier B.V. All rights reserved.