The stoichiometry and electronic properties of bulk Cu2S thin films obtained by vacuum evaporation were investigated by optical spectroscopy, X-ray diffraction and photoemission spectroscopy. The Cu2S/CdS heterojunction interface has been prepared in situ and characterized by photoelectron spectroscopy (X-ray photoemission spectroscopy and ultraviolet photoelectron spectroscopy) after each growth step under ultra high vacuum conditions. The XPS core level spectra as well as valence band spectra of the substrate Cu2S and overlayer CdS were acquired after each step. From these measurements, a large overall band bending of 0.9 eV is observed. The valence band offset is determined to be DeltaE(VB) = 1.2 eV and the conduction band offset is DeltaE(CB) = 0 +/- 0.1 eV. (C) 2003 Elsevier Science B.V. All rights reserved.