Kinetics and role of C, O, and OH in low-pressure nanocrystalline diamond growth

Abstract

A simple low-pressure condition at 80 mTorr has been employed to study the kinetics and role of C, O, and OH in diamond growth by using inductively coupled CO/CH4/H2 and O2/CH4/H2 plasmas. Vacuum ultraviolet absorption spectroscopy (VUVAS) and actinometric optical emission spectroscopy (OES) were used to examine the densities of ground-state C atoms and emissive species such as OH, C2, and O, respectively. Diamond films consisting of nanocrystallites with sizes as small as 20 nm were obtained on positively biased Si substrates only when CH4 was fed. Both diamond and nondiamond growth were enhanced with increasing CO for a fixed CH4 concentration of 5%, while diamond growth was suppressed with increasing O2. Comprehensive discussion along with the VUVAS and OES results suggested that the C atoms resulting mainly from CO by electron impact dissociation had a close relation with the formation of C2 or still larger species as the precursors to nondiamond phase, while the OH radicals resulting predominantly by loss reactions of the byproduct O atoms with H2 and CH4 were highly responsible for the enhanced diamond growth. A large amount of O atoms from O2 was shown to affect the initial nucleation stage seriously. The results support the growth chemistry of diamond from H-hybridized carbon radicals fragmented from CH4 rather than from H-stripped carbon radicals.