We report here on the thermodynamical stability of ultrathin, hafnium-based dielectric films, namely hafnium oxide (HfO2), silicate (HfSixOy), and aluminum silicate (AlHfxSiyOz),deposited on silicon. These materials are promising candidates to replace the well established silicon oxide and oxynitride as gate dielectric materials in advanced Si-based complementary metal-oxide-semiconductor technology. Since there are mandatory requirements on the gate dielectric material, hafnium oxide is currently being modified, by adding silicon and aluminum into the matrix, increasing its thermal stability, and improving its electrical properties. Diffusion-reaction during thermal processing was investigated using isotopic substitution together with ion beam techniques such as Rutherford backscattering spectrometry, narrow nuclear resonance profiling, and nuclear reaction analysis. The chemical changes in the films were accessed by x-ray photoelectron spectroscopy. (C) 2003 American Vacuum Society.