Al2O3 films are grown by atomic layer deposition (ALD) using trimethylaluminum and water as precursors on HF-last and NH3 plasma pretreatment Si substrates. The thickness, surface roughness, and density of Al2O3 films as well as the nature of their interlayers with Si substrates are characterized by x-ray reflectivity and spectroscopic ellipsometry techniques. The growth rates of Al2O3 films are 1.1 angstrom/cycle and 1.3 angstrom/cycle, respectively, on HF-last and NH3-plasma-nitrided surfaces. Al2O3 layer densities are rather independent of the number of growth cycles in all cases. The interfacial film thickness increases with the number of ALD cycles when deposited on an HF-last Si substrate. However, because SiOxNy inhibits oxygen diffusion, the interfacial film thickness is independent of the number of ALD cycles on the nitrided Si substrate.