Chiral-selective carbon nanotube etching with ammonia: a quantum chemical investigation

Density functional theory is employed to demonstrate how ammonia-derived etchant radicals (H, NH, and NH2) can be used to promote particular (n,m) chirality single-walled carbon nanotube (SWCNT) caps during chemical vapor deposition (CVD) growth. We reveal that the chemical reactivity of these etchant radical species with SWCNTs depends on the SWCNT chirality. This reactivity is determined by the extent of disruption to the p-conjugation of the cap structure caused by reaction with the etchant species. H and NH2 attack single carbon atoms and preferentially react with near-zigzag SWCNT caps, whereas NH prefers to attack across C-C bonds and selectively etches near-armchair SWCNT caps. We derive a model for predicting abundances of (n,m) SWCNTs in the presence of ammonia-derived radicals, which is consistent with (n,m) distributions observed in recent CVD experiments with ferrocene and ammonia. This model also demonstrates that chiral-selective etching of SWCNTs during CVD growth can be potentially exploited for achieving chirality control in standard CVD synthesis.