[60]-fullerene and single-walled carbon nanotube-based ultrathin films stepwise grafted onto a self-assembled...

A step-by-step method was used to prepare homogeneous ultrathin films composed of [60]-fullerene (C60) and single-walled carbon nanotubes (SWNTs), grafted onto the functional surface of an alkylsilane self-assembled monolayer (SAM) on an ITO substrate with an ITO-C60-SWNT sequence using amine addition across a double bond in C60 followed by amidation coupling with acid-functionalized SWNTs. Atomic force microscope and scanning electron microscope images of the resulting composite film showed two-component ball-tube microstructures with high-density coverage, where C60 was homogeneously distributed in the SWNT forest. The attachment of SWNTs to the residual amine units in the SAM on the ITO substrate (SAM-ITO) as well as on the C60 sphere results in the C60 molecules in the aggregated clusters being more separately dispersed, which forms a densely packed composite film as a result of the pi-pi interaction between the C60 buckyballs and the SWNT walls. It was found using ferrocene as an internal redox probe that the oxidative and reductive processes at the film-solution surface were effectively retarded because of obstruction from the densely packed film and the electronic effect of SWNT and C60. In addition, the electrochemical properties of C60 on SAM-ITO plates observed by cyclic voltammetry were significantly modified by chemical anchorage using SWNTs. X-ray photoelectron spectroscopy (XPS) analysis also indicated the successful grafting of C60 and SWNT. The XPS chemical shift of the binding energy showed the presence of electronic interactions between C60, SWNT, and ITO components. Such a uniformly distributed C60-SWNT film may be useful for future research in electrochemical and photoactive nanodevices.