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We fabricate and experimentally characterize the electrical properties of metal-semiconductor (MS) and metal-oxide-semiconductor (MOS) structures where the metal is single-walled carbon nanotube (CNT) film and the semiconductor is a Si substrate. Our results suggest that for the MS devices thermionic emission is the main high-temperature current transport mechanism, while tunneling becomes the dominant mechanism for MOS devices with thermally grown thin oxide layers between the CNT film and Si. In addition, the CNT film workfunction, a key parameter for the performance of CNT film-based devices, is obtained from the capacitance-voltage measurements on the MOS structures.