This letter describes the fundamental process underlying the synthesis of ultrananocrystalline diamond (UNCD) films, using a new low-pressure, heat-assisted bias-enhanced nucleation (BEN)/bias enhanced growth (BEG) technique, involving H<sub>2</sub>/CH<sub>4</sub> gas chemistry. This growth process yields UNCD films similar to those produced by the Ar-rich/CH4 chemistries, with pure diamond nanograins (3–5 nm), but smoother surfaces (~6 nm rms) and higher growth rate (~1 µm/h). Synchrotron-based x-Ray absorption spectroscopy, atomic force microscopy, and transmission electron microscopy studies on the BEN-BEG UNCD films provided information critical to understanding the nucleation and growth mechanisms, and growth condition-nanostructure-property relationships.
