Simultaneous Raman and fluorescence spectroscopy of single conjugated polymer chains

Simultaneous surface enhanced Raman scattering (SERS) and fluorescence is demonstrated from single conjugated polymer chains. As resonance enhancement of SERS depends on the spectral overlap of the polymer's absorption and the incident laser, resonance Raman and fluorescence effectively probe the absorbing and emitting part of the polymer, respectively. The optical phonon energies change along the polymer chain, providing a window to spatially track excited state relaxation. Whereas a mean spatial redistribution of the excitation is witnessed by a change in vibronic fingerprint following interchromophoric energy transfer, intrachromophoric exciton self-trapping leaves the vibrations unchanged.