The chemical interface structure between phosphorus-doped hydrogenated amorphous silicon and aluminum-doped zinc oxide thin films is investigated with soft x-ray emission spectroscopy (XES) before and after solid-phase crystallization (SPC) at 600 °C. In addition to the expected SPC-induced phase transition from amorphous to polycrystalline silicon, our XES data indicates a pronounced chemical interaction at the buried Si/ZnO interface. In particular, we find an SPC-enhanced formation of Si-O bonds and the accumulation of Zn in close proximity to the interface. For an assumed closed and homogeneous SiO2 interlayer, an effective thickness of (5±2) nm after SPC could be estimated. © 2010 American Institute of Physics.