Hf metal thin films were deposited on Si substrates using a pulsed laser deposition technique in vacuum and in ammonia ambients. The films were then oxidized at 400 °C in 300 Torr of O2. Half the samples were oxidized in the presence of ultraviolet (UV) radiation from a Hg lamp array. X-ray photoelectron spectroscopy, atomic force microscopy, and grazing angle X-ray diffraction were used to compare the crystallinity, roughness, and composition of the films. It has been found that UV radiation causes roughening of the films and also promotes crystallization at lower temperatures.Furthermore, increased silicon oxidation at the interface was noted with the UVirradiated samples and was shown to be in the form of a mixed layer using angle-resolved X-ray photoelectron spectroscopy. Incorporation of nitrogen into the film reduces the oxidation of the silicon interface.