Insights into carbon nanotube nucleation: Cap formation governed by catalyst interfacial step flow

TL;DR

This study reveals that carbon nanotube nucleation begins with cap formation driven by catalyst interfacial step flow, which influences nanotube helicity and can be controlled via catalyst facet orientation.

Contribution

It provides new insights into the nucleation process of CNTs, highlighting the role of catalyst step flow and cap formation in determining nanotube helicity.

Findings

Cap formation is the initial stage of CNT nucleation.

Step flow on the catalyst surface governs cap and nanotube growth.

Catalyst facet orientation affects nanotube curvature and helicity.

Abstract

In order to accommodate an increasing demand for carbon nanotubes (CNTs) with desirable characteristics one has to understand the origin of helicity of their structures. Here, through in situ microscopy we demonstrate that the nucleation of a carbon nanotube is initiated by the formation of the carbon cap. Nucleation begins with the formation of a graphene embryo that is bound between opposite step-edges on the nickel catalyst surface. The embryo grows larger as the step-edges migrate along the surface, leading to the formation of a curved carbon cap when the steps flow across the edges of adjacent facets. Further motion of the steps away from the catalyst tip with attached rims of the carbon cap generates the wall of the nanotube. Density Functional Theory calculations bring further insight into the process, showing that step flow occurs by surface self diffusion of the nickel atoms via a step-edge attachment-detachment mechanism. Since the fact that cap forms first in the sequence of stages involved in nanotube growth, we suggest that it originates the helicity of the nanotube. Therefore, the angular distribution of catalyst facets could be exploited as a new parameter for controlling the curvature of the cap and, presumably, the helicity of the nanotube.