Plasmon-Induced Selective Oxidation Reaction at Single-Walled Carbon Nanotubes

Local surface plasmon resonance (LSPR)-induced oxidation of semiconducting and metallic single-walled nanotubes (SWNTs) on the nanometer scale was investigated using surface-enhanced Raman scattering (SERS) measurements. An isolated SWNT was supported on a well-defined Au nanodimer structure that possesses an LSPR field at the nanogap under light irradiation, and highly intense SERS spectra of the SWNT at the gap region were measured. SERS analysis under O₂-saturated solutions and the addition of reactive oxygen species inhibitors demonstrated that condensed singlet oxygen (¹O₂), which is one of the reactive oxygen species, was efficiently generated from a semiconducting SWNT at the nanogap by the LSPR field and led to the local oxidation of the tube. In contrast to the semiconducting SWNT, no defect formation was observed in a metallic SWNT, probably because of rapid quenching of the photoexcited state. This selective local defect formation by LSPR-induced oxidation of a semiconducting SWNT would provide novel nanoprocessing and nanofunctionalization methods for the fabrication of future SWNT-based nanodevices.