In all solar cells, and especially in extremely thin absorber (ETA) solar cells, proper energy band alignment is crucial for efficient photovoltaic conversion. However, available tabulated data usually do not agree with actual results, and in most cases, V-oc values lower than expected are achieved. In fact, ETA cells suffer from a very low V-oc/E-gap ratio, such as in ZnO/CdS/CuSCN cells. Here, we investigate limiting factors of ZnO/CdS/CuSCN ETA cells, applying X-ray photoelectron spectroscopy (XPS), chemically resolved electrical measurement (CREM), Kelvin probe, and I-V characterization. We show that electric fields are gradually developed in the cell upon increased absorber, thickness. Moreover, an accumulation layer, unfavorable for the solar cell function, has been revealed at the oxide-absorber interface An effective chemical treatment to prevent formation of this accumulation layer is demonstrated.