Modeling the Field Emission Enhancement Factor for Capped Carbon Nanotubes Using the Induced Electron Density

• Published in: Journal of chemical information and modeling Vol. 60; no. 2; pp. 714 - 721
• Main Authors: de Castro, Caio P, de Assis, Thiago A, Rivelino, Roberto, de B. Mota, Fernando, de Castilho, Caio M. C, Forbes, Richard G
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 24.02.2020
• Subjects: Charge transfer; Conductors; Density functional theory; Electron density; Electron emission; Electrons; Emitters; Emitters (electron); Field emission; Models, Molecular; Molecular Conformation; Nanotubes, Carbon - chemistry; Quantum Theory; Single wall carbon nanotubes
• ISSN: 1549-9596; 1549-960X
• DOI: 10.1021/acs.jcim.9b00896

In many field electron emission experiments on single-walled carbon nanotubes (SWCNTs), the SWCNT stands on one of two well-separated parallel plane plates, with a macroscopic field F M applied between them. For any given location “L” on the SWCNT surface, a field enhancement factor (FEF) is defined as F L/F M, where F L is a local field defined at “L”. The best emission measurements from small-radii capped SWCNTs exhibit characteristic FEFs that are constant (i.e., independent of F M). This paper discusses how to retrieve this result in quantum-mechanical (as opposed to classical electrostatic) calculations. Density functional theory (DFT) is used to analyze the properties of two short, floating SWCNTs, capped at both ends, namely, a (6,6) and a (10,0) structure. Both have effectively the same height (∼5.46 nm) and radius (∼0.42 nm). It is found that apex values of local induced FEF are similar for the two SWCNTs, are independent of F M, and are similar to FEF values found from classical conductor models. It is suggested that these induced-FEF values are related to the SWCNT longitudinal system polarizabilities, which are presumed similar. The DFT calculations also generate “real”, as opposed to “induced”, potential-energy (PE) barriers for the two SWCNTs, for F M values from 3 V/μm to 2 V/nm. PE profiles along the SWCNT axis and along a parallel “observation line” through one of the topmost atoms are similar. At low macroscopic fields, the details of barrier shape differ for the two SWCNT types. Even for F M = 0, there are distinct PE structures present at the emitter apex (different for the two SWCNTs); this suggests the presence of structure-specific chemically induced charge transfers and related patch-field distributions.