Single layers and combined layer systems with Cu(In,Ga)(S,Se) sub(2), ZnS-nanodot (nd) and In sub(2)S sub(3) layers were investigated by surface photovoltage spectroscopy in the Kelvin-probe arrangement and compared with the open-circuit voltage (V sub(OC)) of solar cells. The In sub(2)S sub(3) and ZnS-nd layers were prepared by the spray ion layer gas reaction (ILGAR) technique from Indium chloride (InCl sub(3)), Indium acetylacetonate (In(acac) sub(3)) and Zinc acetylacetonate, respectively. The surface photovoltage signals of Cu(In,Ga)(S,Se) sub(2) were larger for the Cu(In,Ga)(S,Se) sub(2)/ZnS-nd/In sub(2)S sub(3) than for the Cu(In,Ga)(S,Se) sub(2)/In sub(2)S sub(3) layer system showing that a ZnS-nd layer additionally passivated the Cu(In,Ga)(S,Se) sub(2) surface. ILGAR In sub(2)S sub(3) deposition from InCl sub(3) precursor solution led to a modification of surface defects of ZnS-nd and to generation of defect states below the band gap of Cu(In,Ga)(S,Se) sub(2), which has not been observed for deposition from Indium acetylacetonate precursor. Defect generation during ILGAR In sub(2)S sub(3) deposition with InCl sub(3) precursor resulted in a lower V sub(OC) of Cu(In,Ga)(S,Se) sub(2)/ZnS-nd/In sub(2)S sub(3)/ZnO:Al solar cells. Copyright copyright 2012 John Wiley & Sons, Ltd. ZnS nanodots deposited on Cu(In,Ga)(S,Se) sub(2) absorber and surface photovoltage (SPV) spectra of Mo / ZnS-nd / In sub(2)S sub(3) for In sub(2)S sub(3) deposited by spray ILGAR from chloride and acetylacetonate solutions demonstrating the decreased (increased) SPV signal related to defects below (absorption above) the bandgap of ZnS-nd / In super(2)S super(3) (acac).