Diamond crystallites and continuous films were deposited on (100) silicon with various surface treatments by microwave plasma assisted CVD at times varying from 2 min to 1600 min. In each experiment, the average diameter of the crystallites increased linearly with time, while the density of crystallites was essentially constant. Thus, nucleation of the diamond occurred within a short time interval early in the deposition process. After the nucleation event, only growth occurred. Various surface treatments were used: untreated, polished with 1 μm diamond, scratched with 350 mesh SiC, scratched with 1 μm alumina, wiped with 350 mesh graphite powder, and spin coated with polymethyl methacrylate. Only the diamond polishing affected the crystallite density, and none of the surface treatments had any effect on crystallite morphology or growth rate. Growth rates were determined by least squares fits to average diameter versus time for crystals and average thickness versus time for films. The growth rate data extrapolate to zero size at zero deposition time. Applying the Volmer–Weber model, an activation energy for nucleation of diamond on silicon was calculated to be 52 kcal/mole.