Single-walled carbon nanotubes have been a candidate for outperforming silicon in ultrascaled transistors, but the realization of nanotube-based integrated circuits requires dense arrays of purely semiconducting species. In order to directly grow such nanotube arrays on wafers, control over kinetics and thermodynamics in tube-catalyst systems plays a key role, and further progress requires a comprehensive understanding of seemingly contradictory reports on the growth kinetics. Here, we propose a universal kinetic model that decomposes the growth rates of nanotubes into the adsorption and removal of carbon atoms on the catalysts, and we provide its quantitative verification by ethanol-based isotope labeling experiments. While the removal of carbon from catalysts dominates the growth kinetics under a low supply of precursors, resulting in chirality-independent growth rates, our kinetic model and experiments demonstrate that chiral angle-dependent growth rates emerge when sufficient amounts of carbon and etching agents are cosupplied. The kinetic maps, as a product of generalizing the model, include five types of kinetic selectivity that emerge depending on the absolute quantities of gases with opposing effects. Our findings not only resolve discrepancies existing in the literature but also offer rational strategies to control the chirality, length, and density of nanotube arrays for practical applications.
Keywords: carbon nanotubes; catalytic CVD; etching agents; growth model; isotope labeling; selective growth.