Potential p-FET high-work function metals, TaN, Ru, and Pt are shown to have distinct effects on the stability of Hf-based gate stacks during a thermal process. Ru and Pt promote catalytic decomposition of the underlying dielectrics, resulting in the formation of HfSix and Ru(Pt)Six at 950 (900) °C. With Ru, hydroxyl impurities are critical in silicidation which is localized in the vicinity of voids where the Si substrate is exposed through partial HfO2 and SiO2 decomposition. The degree of silicide formation is greater with Pt, occurring upon major decomposition of the underlying dielectrics with or without hydroxyl impurities. Transfer of electrons from the HfO2 oxygen vacancy to Ru and Pt may play a role in the decomposition of the dielectric films. In contrast, the thermal evolution of TaN-gate stacks is very similar to that of HfO2 stacks without any capping metal layer. With annealed HfO2 and HfO2/TaN stacks there is no detectable metal diffusion into the dielectrics, and the overall compositional stability is preserved except for the growth of interfacial SiO2.