Structure-Resolved Monitoring of Single-Wall Carbon Nanotube Functionalization from Raman Intermediate Frequency Modes

Single-wall carbon nanotubes (SWCNTs) can be covalently modified to generate useful changes in their spectroscopic and photophysical properties. We report here a new method to monitor the extent of such functionalization reactions for different nanotube structures. Raman spectra are analyzed to find the intensities of structure-specific intermediate frequency mode (IFM) features in the range of ca. 350 to 650 cm-1, which are induced by introduction of sp3 defects. The IFM frequencies are found to depend on both the nanotube diameter and Raman excitation wavelength. The growth of IFM features is accompanied by a decrease in RBM intensities, so the IFM to RBM intensity ratio can provide a sensitive, structure-specific measure of nanotube functionalization.