Adsorption on carbon nanotubes studied using polarization-modulated infrared reflection-absorption spectroscopy

Single-wall carbon nanotubes (SWNTs), deposited onto an Al substrate from a liquid suspension, have been cleaned by annealing in ultrahigh vacuum. The effects of exposing the sample in situ to atomic H (or D) and/or to dimethyl methylphosphonate DMMP, (CH(3)O)(2)(CH(3))P=O] were then studied using polarization-modulated infrared reflection-absorption spectroscopy. Atomic H reacts preferentially near strained or defective regions in the nanotube wall to produce a spectrum consistent with alkane-like species (>CH(2) and -CH(3)). Only a small fraction of the >C=C< sites in the nanotube wall react with H, and there is no clear evidence for monohydride >C(H)-C(H)< species. For DMMP, data were obtained under steady-state conditions in reagent pressures in excess of half the room-temperature vapor pressure. Adsorption occurs via the P=O group with a coverage that depends on the ambient pressure. Varying the DMMP coverage by changing the pressure causes changes in the spectrum that can be related to the strength of the DMMP/SWNT interaction. Preadsorbed H is seen to have little or no effect on the subsequent adsorption of DMMP. For DMMP, the molecular features are superimposed on a broad, smoothly varying background that can be related to adsorption-induced changes in the Drude parameters characterizing the SWNT free-carrier density and scattering lifetime.