Résumé
The influence of the temperature and precursor pressure on the defect density of singlewalled carbon nanotubes (SWCNTs) grown by catalytic chemical vapor deposition was studied for several catalyst-precursor couples. The SWCNT defect density was assessed by studying the Raman D band. In situ Raman monitoring was used to determine experimental conditions allowing the preparation of samples free of pyrolytic carbon and not altered by air exposure. The most striking feature is that the Arrhenius plots of the IG/ID ratio systematically display a convex shape, i.e. the apparent activation energy decreases with increasing temperature. From HRTEM observations and oxidation experiments, this evolution of the D band features is ascribed to the catalytic growth of long SWCNTs with few defects at high temperature and of short and defective SWCNTs and carbon structures at low temperature. The convex Arrhenius behavior is well accounted by two kinetic models: (i) a model considering a change of intermediate states as a function of the temperature (for instance due to a phase transition of the catalyst particle or a change of intermediate carbon species) and (ii) a model considering a high-temperature process of defect creation (for instance by reaction with reactive gas species).