Electrochemical functionalisation of SWNTs with poly(3,4-ethylenedioxythiophene) evidenced by anti-Stokes/Stokes Raman spectroscopy

The capability of anti-Stokes/Stokes Raman spectroscopy to evaluate chemical interactions at the interface of a conducting polymer/carbon nanotubes is demonstrated. Electrochemical polymerisation of the monomer 3,4-ethylenedioxythiophene (EDOT) on a Au support covered with a single-walled carbon nanotube (SWNT) film immersed in a LiClO4/CH3CN solution was carried out. At the resonant optical excitation, which occurs when the energy of the exciting light coincides with the energy of an electronic transition, poly(3,4-ethylenedioxythiophene) (PEDOT) deposited electrochemically as a thin film of nanometric thickness on a rough Au support presents an abnormally intense anti-Stokes Raman spectrum. The additional increase in Raman intensity in the anti-Stokes branch observed when PEDOT is deposited on SWNTs is interpreted as resulting from the excitation of plasmons in the metallic nanotubes. A covalent functionalisation of SWNTs with PEDOT both in un-doped and doped states takes place when the electropolymerisation of EDOT, with stopping at +1.6 V versus Ag/Ag+, is performed on a SWNT film deposited on a Au plate. The presence of PEDOT covalently functionalised SWNTs is rationalised by (1) a downshift by a few wavenumbers of the polymer Raman line associated with the symmetric C-C stretching mode and (2) an upshift of the radial breathing modes of SWNTs, both variations revealing an interaction between SWNTs and the conjugated polymer. Raman studies performed at different excitation wavelengths indicate that the resonant optical excitation is the key condition to observe the abnormal anti-Stokes Raman effect. Copyright (C) 2010 John Wiley & Sons, Ltd.