Nucleation and bulk film growth kinetics of nanocrystalline diamond prepared by microwave plasmaenhanced chemical vapor deposition on silicon substratesReal time spectroellipsometry has been applied to determine the deposition rate and thickness evolution of the nondiamond ͑sp 2 -bonded͒ carbon volume fraction in very thin ͑Ͻ1000 Å͒, but fully coalesced, nanocrystalline diamond films prepared on Si substrates by microwave plasma-enhanced chemical vapor deposition from gas mixtures of CO and H 2 . At a substrate temperature of ϳ800°C, high quality diamond films can be obtained over two orders of magnitude in the CO/H 2 gas flow ratio, from 0.04, the lowest value explored, to ϳ5. A well-defined minimum in the sp 2 C volume fraction ͑0.03 in a 600 Å film͒ is observed for a CO/H 2 ratio of 0.2, corresponding to the C-H-O diamond-growth phase-diagram coordinate X H/⌺ ϭ͓H͔/͕͓H͔ϩ͓C͔͖ of 0.9. Under these conditions, the deposition rate increases with increasing temperature over the range of ϳ400-800°C with an activation energy of 8 kcal/mol, behavior identical to that observed for diamond film growth from a CH 4 /H 2 ratio of 0.01. This observation shows that the dominant film precursors in the diamond growth process from CO/H 2 ϭ0.2 are hydrocarbons whose flux at the growing film surface is controlled through the reaction of excited CO with H or H 2 in the plasma. A broad subsidiary minimum in the sp 2 C content is observed, centered near a CO/H 2 ratio of 2, corresponding to an X H/⌺ value of ϳ0.5. Under these gas flow conditions, the deposition rate is a complicated function of temperature, exhibiting a peak near 550°C. This peak shifts to lower temperature with further increases in the CO/H 2 ratio above 2, suggesting a nonhydrocarbon precursor and a different growth mechanism for diamond prepared at high CO/H 2 ratio and low temperature.