Stone-Wales defects can cause a metal-semiconductor transition in carbon nanotubes depending on their orientation

TL;DR

This study demonstrates that the orientation of Stone-Wales defects in carbon nanotubes significantly influences their electronic properties, with circumferential defects inducing a bandgap and longitudinal defects not affecting the band structure.

Contribution

It provides a detailed analysis of how defect orientation affects electronic structure and doping in carbon nanotubes using density functional theory, highlighting the role of symmetry breaking.

Findings

Circumferential defects open a small bandgap in CNTs.

Longitudinal defects do not significantly alter the band structure.

Circumferential defects dominate electronic properties when both defect types are present.

Abstract

It has been shown that the two different orientations of Stone-Wales (SW) defects, i.e. longitudinal and circumferential SW defects, on carbon nanotubes (CNTs) result in two different electronic structures. Based on density functional theory we have shown that the longitudinal SW defects do not open a bandgap near the Fermi energy, while a relatively small bandgap emerges in tubes with circumferential defects. We argue that the bandgap opening in the presence of circumferential SW defects is a consequence of long-range symmetry breaking which can spread all the way along the tube. Specifically, the distribution of contracted and stretched bond lengths due to the presence of defects, and hopping energies for low-energy electrons, i.e. the 2pz electrons, show two different patterns for the two types of defects. Interplay between the geometric features and the electronic properties of the tubes have also been studied for different defect concentrations. Considering $\pi$-orbital charge density, it has also been shown that the deviations of bond lengths from their relaxed length result in different doping for two defect orientations around the defects -- electron-rich for a circumferential defect and hole-rich for a longitudinal one. We have also shown that, in the tubes having both types of defects, circumferential defects would dominate and impose their electronic properties.