Thermodynamic and Energetic Effects on the Diameter and Defect Density in Single-Walled Carbon Nanotube Synthesis

Single-walled carbon nanotube (SWCNT) ensembles are characterized by their defect density and diameter distribution. Here, SWCNTs are grown using chemical vapor deposition with acetylene as the carbon source and cobalt as the catalyst and analyzed ex situ, without any modification or processing, using Raman spectroscopy. The defect density shows an activated temperature dependence (activation energy ∼0.8 eV or ∼80 kJ/mol) with fewer defects at high growth temperatures for a wide range of experimental parameters. This is consistent with a single activated mechanism, such as the catalytic healing of defects, possibly a single simple defect. Consistent with previous reports, we see that low growth temperatures produce smaller diameter SWCNTs than high growth temperatures. Elementary thermodynamic considerations of the strain energy in the lattice constrain the SWCNT diameter distribution and its temperature dependence and appear consistent with our observations. A “phase diagram” for SWCNT growth is constructed and suggests methods of controlling the diameter distribution. There is a trade-off here between small diameter SWCNTs and SWCNTs with low defect densities