We present a detailed characterization of thin high-k Hf-based dielectric/SiO2 stacks on Si by electrical measurements (capacitance-voltage (CV) and current-voltage (IV)), structural analysis using transmission electron microscopy (TEM) and compositional analysis using medium energy ion scattering (MEIS). We show that the electrical results are consistent with and can be explained by the structural and compositional results. Specifically, the structural results show that the effect of nitridation of the films using a decoupled plasma nitridation method is an increase in SiO2 thickness, which results in a capacitance and leakage current decrease, revealed by the electrical measurements. Nitridation also reduces the density of interface traps for these samples. The reduction is more effective in the case of nonstoichiometric hafnium silicate films (HfSiOx) than in the case of HfO2.