Thin films of aluminum oxide were deposited on clean Si(100) substrates using trimethylaluminum and oxygen at 300°C. Infrared spectroscopic and x-ray photoelectron spectroscopic analyses of these films showed no aluminum silicate or SiO2 phase formation at the film/substrate interface. The O/Al ratio in the as deposited film was found to be higher than that in stoichiometric Al2O3. On annealing the as deposited samples in Ar at higher temperatures, a peak due to the transverse optical phonon for the Si-O-Si stretching mode appeared in the infrared spectra. A combination of Z-contrast imaging and electron energy loss spectroscopy in the scanning transmission electron microscope confirmed that the annealed samples developed a layer of silicon dioxide at the aluminum oxide-Si interface. Z-contrast images and electron energy loss spectra, obtained while heating the sample inside the scanning transmission electron microscope were used to follow the interfacial SiO2 formation.