We investigated the electronic structures of chemically modified carbon nanotube tips under electric fields using density functional calculations. Hydrogen, oxygen, and hydroxyl group-terminated nanotubes have been considered as field emitters or probe tips. In the case of the open-ended tubes, the field emission originates primarily from the dangling-bond states localized at the edge, whereas the pentagonal defects are the main source of the field emission in the capped tubes. The open-ended nanotube with a zigzag edge is an efficient field emitter because of the localized electronic states around the Fermi level and the atomic alignment of carbon-carbon bonds along with external electric fields. Tip functionalization alters the local density of states as well as the chemical selectivity of nanotubes in various ways. The correlations between atomic geometries of chemically functionalized tips and their electronic structures are further discussed. We propose that a hydrogen-terminated tube would be a promising probe tip for selective chemical imaging.

• Received 6 May 2003

DOI:https://doi.org/10.1103/PhysRevB.68.115403