Solar cells based on amorphous silicon (a-Si:H) exhibit a decreased fill factor if ZnO is used as front electrode instead of SnO2. This is due to a poor electric contact between the ZnO and the p-type a-SiC:H(B) layer. To gain a deeper understanding of the chemical and electronic properties of the ZnO/p interface, in-situ XPS measurements were applied to thin a-SiC:H(B) films deposited on ZnO. The effects of CO2 and H2 plasma pretreatments on clean ZnO surfaces and the influence of deposition conditions on the ZnO/a-SiC:H interface were investigated. Upon H2 plasma treatment the formation of SiOx by chemical transport of Si from the reactor walls is observed. Furthermore, a shift of all core levels towards higher binding energies indicates the formation of an accumulation layer. CO2 plasma treatments show no effects on ZnO. Depth profiling across the ZnO/a-SiC:H interface indicates SiO2 formation on ZnO. The depth profile of ZnO related core levels exhibits two features: a reduction of the ZnO at the interface, and, after longer sputter times, a core level shift towards higher binding energy due to an hydrogen induced accumulation layer in the n-type ZnO. The latter causes a depletion of the p-layer resulting in an enhanced series resistance and diminished fill factor. To reduce the depletion layer thin highly conductive microcrystalline layers were introduced, increasing the fill factor up to 74%.