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Niobium was deposited by physical vapor deposition (PVD) using e-beam evaporation on bare (100) silicon substrates and SiO2 surfaces. The formation of niobium silicide was investigated by annealing PVD Nb films in the temperatures range 400-1000°C. At all elevated annealing temperatures the resistivity of Nb silicide is substantially higher than that of Nb. The Nb silicidation as a function of temperature has been investigated and different NbxSiy compounds have been characterized. It has been observed that the annealing of the Nb film on Si is accompanied by a strong volume expansion of about 2.5 of the resulting reacted film. The films' structural properties were studied using X-Ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), and atomic force microscopy (AFM), which was not previously presented in the context of the extant NbSi literature. The X-Ray diffraction characterization of the Nb on Si sample annealed at 1000°C, showed the presence of hexagonal Nb5Si3 phases, with a dominant peak at the (200) plane, and NbSi2 phases. Fractal dimension calculations indicate a distinct transition from Stranski-Krastanov to Volmer-Weber film growth for NbSi formation at the annealing temperature of 600°C and above. [ABSTRACT FROM AUTHOR]