The authors used x-ray absorption spectroscopy of the O K edge to investigate the nanocrystalline structure of thin HfO2 films deposited by remote plasma enhanced chemical vapor deposition on Ge(100). Postdeposition thermal process induced the interfacial reconstruction and the crystallization of the HfO2 in the monoclinic structure driven by the Ge(100) substrate. The substrate templating of the HfO2 crystallization is an evidence that the processing used here removes the undesired the interfacial layer and has the potential to yield interfaces with low density of defects. (C) 2010 American Vacuum Society. [DOI: 10.1116/1.3430563]