Atmospheric-pressure plasma synthesis of carbon nanotubes

Abstract

An atmospheric-pressure radio-frequency discharge (APRFD) has great advantages over vacuum-oriented plasma-enhanced chemical vapour deposition (PECVD) as well as other types of atmospheric-pressure plasma sources in terms of single-walled carbon nanotube (SWCNT) growth. We first provide an overview on the recent advances in PECVD synthesis of CNTs, ranging from low pressure to atmospheric pressure, and then we present our current work focusing on the analysis of reactive species generated in the cathodic plasma sheath for further understanding of the SWCNT growth mechanism in PECVD. It was found that the plasma-generated C2H2 is the main CNT growth precursor in PECVD. Approximately 30% of the CH4 (initial feedstock) was converted into C2H6, C2H4 and C2H2. A trace amount of C2H2 enabled the synthesis of SWCNTs in the thermal chemical vapour deposition (CVD) regime. H2 is necessary to grow SWCNTs using PECVD because H2 suppresses the formation of excess amount of C2H2; however, H2 does not eliminate amorphous carbon even at H2/C2H2 ratios of 300. PECVD using a binary mixture of C2H2 and isotope-modified 13CH4 demonstrated that CH4 does not contribute to CNT growth in C2H2-assisted thermal CVD. Atmospheric-pressure PECVD performed with a He/CH4/H2 system is equivalent to C2H2-assisted thermal CVD without an etching gas. APRFD appears to produce a hidden species, which influences the CNT growth process.