The material properties of HfO2 thin films were studied to evaluate their potential as a high-κ gate dielectric in 4H-SiC power metal-oxide-semiconductor field effect transistors. Stoichiometric HfO2 films were deposited on n-type 4H-SiC (0001) by atomic layer deposition (ALD) at substrate temperatures of 250-450°C. No significant interfacial layer formation was observed by in-situ X-ray photoelectron spectroscopy (XPS) and an abrupt interface was confirmed by high-resolution transmission electron microscopy (HRTEM). A temperature-dependent transition from amorphous layer-by-layer growth to crystalline three-dimensional island growth was identified by in-situ reflection high-energy electron diffraction (RHEED) and ex-situ atomic force microscopy (AFM). X-ray diffraction (XRD) confirmed the presence of monoclinic HfO2 domains in crystallized films.