The structural basis for giant enhancement enabling single-molecule Raman scattering

We find that giant surface-enhanced Raman scattering for adsorbates on silver surfaces is present only on surfaces that exhibit self-similar fractal topology as inferred from atomic force microscopy. The fractal character results in localizing the energy of incident photons to volumes of a few nanometers on a side, millions of times smaller than the diffraction limit. Consistent with this finding, we have found an enhancement in spontaneous Raman cross section of >13 orders of magnitude for adsorbates on silver surfaces demonstrated to be fractal. The location of "hot spots" on the fractal surfaces is found to be hypersensitive to incident wavelength and polarization even though the observed Raman scattering is strictly linear in incident intensity. These observations are consistent with localization of the photon energy facilitated by the disordered nature of fractal organization through interference between the incident wave and scattered radiation from silver nanoparticle surface plasmons. We also present a surface preparation method that consistently produces fractal topologies that support single-molecule Raman scattering.