The conduction and valence band offsets between amorphous and silicon have been determined from x-ray photoelectron spectroscopy measurements. These films, which are free of interfacial were made by molecular-beam deposition. The band line-up is type I with measured band offsets of 1.8±0.2 eV for electrons and 3.2±0.1 eV for holes. The band offsets are independent of the doping concentration in the silicon substrate as well as the amorphous film thickness. These amorphous films have a bandgap of
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