To meet challenges for a smaller transistor feature size, ultra-thin HfO2 high-k dielectric has been used to replace SiO2 for the gate dielectric. In order to accurately analyze the ultra-thin HfO2 films by grazing incidence X-ray reflectivity (GIXRR), an appropriate material model with a proper layer structure is required. However, the accurate model is difficult to obtain, since the interfaces between layers of the ultra-thin HfO2 films are not easily identified, especially when post-deposition annealing process is applied. In this paper, 3.0 nm HfO2 films were prepared by atomic layer deposition on p-type silicon wafer, and annealed in Ar environment with temperatures up to 1000 degrees C. The layer structures and the role of the interfacial layer of the films in the post-deposition annealing processes were evaluated by X-ray diffraction and X-ray photoelectron spectroscopy (XPS). The experimental results and analysis showed that layer thicknesses, crystal phases and chemical structures of the ultra-thin HfO2 films were significantly dependent on annealing temperatures. The binding energy shifts of Hf 4f, O 1s, and Si 2p elements revealed the formation of Hf silicate (Hf-O-Si bonding) with increasing annealing temperatures. Due to the silicate formation and increasing silicon oxide formation, the interface broadening is highly expected. The structure analysis of the GIXRR spectra using the modified material structure model from the XPS analysis confirmed the interfacial broadening induced by the post-deposition annealing. (C) 2011 Elsevier B. V. All rights reserved.