AbstractWe report on the chemical deposition and electronic properties of CuInS₂/Zn(S,O) interfaces. The Zn(S,O) buffer was grown by a new chemical bath deposition (CBD) process that allows the tailoring of the S/O ratio in the films. Resulting Zn(S,O) films exhibit transparencies above 80% (for λ>390 nm) and an optical energy band gap of 3.9 eV which decreases to 3.6 eV after annealing in air at 200°C. Production line CuInS₂ (CIS) absorbers provided by Sulfurcell Solartechnik GmbH are used as substrates for the investigation of the CIS/Zn(S,O) interface and the chemical composition of Zn(S,O). A ZnS/(ZnS+ZnO) ratio of 0.5 is found by X-ray photoelectron spectroscopy and X-ray excited Auger electron spectroscopy (XPS and XAES). The valence band offset between the heterojunction partners (ΔE_V = 1.8 ± 0.2 eV) has been determined by means of XPS and ultraviolet photoelectron spectroscopy (UPS). Considering the energy band gap of the CIS absorber and the measured band gap of Zn(S,O), the conduction band offset (ΔE_C) is calculated as: resulting in a spike of 0.5±0.3 eV in the conduction band at the heterojunction before annealing. After the heat treatment, the valence band offset is reduced to 1.5±0.2 eV and the calculated conduction band offset remains at 0.5±0.3 eV.