Diamond films exhibiting contiguous epitaxial crystallites (∼3-4 μm) have been grown on single crystal (100) silicon by 2.45 GHz microwave plasma deposition. The diamond films were deposited by a three-step process. In the initial stage the silicon wafer was pretreated for 3 h in a 1.8% methane in hydrogen plasma at low pressure. The subsequent nucleation stage was performed, under identical processing conditions, except that a dc bias of −340 V was applied for 25 min. During this period the current increased from 38 mA at the start to 102 mA at the end of the bias. The final growth stage was performed, with an earthed substrate, utilizing a carbon monoxide/methane/hydrogen gas mixture whose composition is conducive to uniformly faceted (100) diamond growth. Scanning electron micrographs showed that a large fraction of the (100) faces of the diamond crystallites are aligned with the (100) plane of the underlying silicon lattice with the crystallite edges parallel to the (110) direction. Raman scattering was used to confirm this finding by measuring the angular dependence of the Raman backscattering intensity at 1332 cm⁻¹ using plane polarized excitation of individual crystallites within the diamond films.