Metal–oxide–semiconductor capacitors were used to study the interaction of Hf and Zr gate electrodes on SiO2, ZrSixOy, and ZrO2. A large reduction in the SiO2 equivalent oxide thickness accompanied by an increase in the leakage current was observed with Hf and Zr electrodes when subjected to anneal temperatures as low as 400 °C. The reduction in electrical thickness as observed from the capacitance–voltage measurements was attributed to the combination of (a) physical thinning of the SiO2 and (b) formation of a high-K layer. A severe instability of Zr and Hf electrodes was also observed on ZrSixOy and ZrO2 dielectrics. This behavior of Zr and Hf gates was attributed to high negative enthalpy of oxide formation and high oxygen solubility resulting in the reduction of the gate dielectric and subsequent oxygen diffusion to the gate electrode. © 2001 American Institute of Physics.