Modulation of the Electronic Structure of Semiconducting Nanotubes Resulting from Different Metal Contacts

• Published in: The journal of physical chemistry. B 2005-04, Vol.109 (16), p.7601-7604
• Main Authors: Tarakeshwar, P, Kim, Dae M
• Format: Article
• Language: English
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp050525j

Examined in this paper is the role of the metal electrode influencing the structure and electronic properties of semiconducting carbon nanotubes near the interface at low bias. Specifically, we present quantum-chemical calculations of finite sections of a (8,0) semiconducting single wall nanotube contacted with gold and palladium clusters. The calculations at the density functional level of theory, which included full geometry optimizations, indicate the formation of bonds between the metal atoms of the electrode and the carbon atoms of the nanotube. The local work function of the metal electrode can be expected to exhibit significant variations as a result of this bond formation. Compared to the gold-contacted nanotubes, the palladium-contacted nanotubes have a small but interesting increase in both length and diameter. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the gold-contacted nanotube are shown localized at the edges. In contrast, the HOMO and LUMO of the palladium-contacted nanotube are extended over the entire nanotube and the metal cluster contacted to it, providing thereby a better conduction path in the contact region of the electrode and the nanotube. The involvement of the highly directional d orbitals in the interactions involving the palladium cluster leads to an enhanced π electron density in the nanotube. This enhanced π electron density is synonymous with an improved electron transmission.