Hafnium oxide films were prepared by Pulsed Laser Deposition (PLD). The influence of laser wavelength (fundamental, second and third harmonic of a Nd:YAG laser), used for evaporation, and substrate temperature on the film morphology, chemical structure and interfacial quality were investigated yielding the following results: While the laser wavelength exhibits minor influence on layer structure, the substrate temperature plays a critical role regarding morphological and chemical structure of the produced hafnium oxide / silicon stacks. Atomic Force Microscopy (AFM) images show a clear transition from smooth layers consisting of small area crystallites to very rough surfaces characterized by large craters and regular, plane features when the growth temperature was increased. These facts suggest a chemical instability which is confirmed by X-ray Photoelectron Spectroscopy (XPS). Investigations of the hafnium and silicon core level spectra indicate the occurrence of silicon dioxide and hafnium silicide in the case the samples were produced at elevated temperatures.