The chemical and electronic properties of a-Si:H(B)/ZnO:Al and μc-Si:H(B)/ZnO:Al thin-film solar cell structures are studied by hard X-ray photoelectron spectroscopy (HAXPES). Using a combination of different X-ray excitation energies and deliberate sample design, we were able to select the probed volume, i.e., the silicon capping layer only or the silicon and zinc oxide layer (including the buried interface). For the a-Si:H(B) material, we find a higher deposition rate and a smaller value for the modified Auger parameter than for μc-Si:H(B). In addition, we find indications of a pronounced band bending limited to the very surface of the a-Si:H(B) and the μc-Si:H(B) layers, which is more distinct in the latter case. © 2012 IEEE.