HfO2 films were grown on SiO2/4H-SiC and SiON/4H-SiC layers by evaporation of metallic Hf in an electron beam deposition system followed by thermal oxidation. X-ray photoelectron spectroscopy confirmed the formation of HfO2 films. There is no evidence of formation of hafnium silicide or carbon pile up at the surface as well as at the interfacial layer. Electrical measurements show the presence of fewer slow traps in the HfO2/SiON gate dielectric stack on 4H-SiC and comparable values of interface state density. The HfO2/SiON stack layer improves leakage current characteristics with a higher breakdown field and has better reliability under electrical stress.