Detection of invisible phonon modes in individual defect-free carbon nanotubes by gradient-field Raman scattering

We provide an effective method to investigate the field gradient effect in nanoconfined plasmon–matter interaction. Aligned ultralong SWNTs without defects were grown on marked substrates, followed by assembling gold nanoparticle clusters around individual nanotubes. The Raman scattering behavior of a nanotube placed in an atomic scale nanogap between adjacent nanoparticles was studied. In addition to the expected plasmon-induced Raman enhancement up to 10³, the defect-free D-mode of an individual SWNT induced by gradient field is found for the first time. When the light is confined at atomic scale, gradient field Raman scattering becomes significant and dipole-forbidden phonon modes can be activated by quadrupole Raman tensor variation, indicating breakdown of the Raman selection rules.