The chemical structure of the interface between silicon thin films and the transparent conductive oxide ZnO:Al has been investigated by hard x-ray photoelectron spectroscopy. By varying the excitation energy between 2010 and 8040 eV, we were able to probe the Si/ZnO interface buried below 12 nm Si. This allowed for the identification of changes induced by solid phase crystallization (SPC). Based on in-situ SPC annealing experiments, we find clear indications that the formation of Si-O bonds takes place at the expense of Zn-O bonds. Hence, the ZnO:Al acts as the oxygen source for the interfacial Si oxidation. © 2011 American Institute of Physics.