Anew five-source PVD system was developed for the deposition of Cu(ln(1-x)Ga(x))(Se(1-y)Sy)(2) (CIGSS) thin films. The system allows the independent and controlled deposition of all five elements. In the first part of this paper, we investigate CIGSS formation via a double-layer process of depositing a Cu-S or Cu-Se layer on top of an In-Ga-Se or In-Ga-S layer, respectively. Incomplete intermix of two different chalcopyrite species is observed. In one case, additionally, an enrichment of Ga at the interface between those two layers is observed. In the second part of the paper, films within the complete compositional range of 0 < x < 1, and 0 < y < 1 were deposited on Mo-coated soda lime glass. The incorporation of sulfur in the films depends strongly on the sulfur concentration in the vapor phase, the substrate temperature, and the Cu/In ratio. The films were analyzed by means of EDS, XRD, Rutherford backscattering spectroscopy (RBS), and AES. Solar cells were fabricated and characterized by I-V measurements. We show results for a series of solar cells deposited group-Ill rich on the equal-gap line E-gap = 1.5 eV for various S and Ga contents. The best cells show an efficiency near 10%. The highest open circuit voltage is 854 mV at sulfur contents of S/(Se+S)=0.26. (c) 2004 Elsevier B.V. All rights reserved.