title: Charge transfer enhancement in the SERS of a single molecule.
abstract: We measured the surface-enhanced Raman scattering (SERS) of individual gold nanoparticle-4-aminobenzenethiol (ABT)-gold film junctions to investigate the charge-transfer (CT) enhancement of the SERS signals. Despite the mild electromagnetic field enhancement (∼10(5)) and high surface density of the ABT-molecules (∼240 molecules/hotspot) at the junctions, we observed the clear spectral and temporal signatures of CT-enhanced single-molecule SERS (SM-SERS). The result reveals that only a small fraction of the molecules at the junction has a significant CT-enhancement of 10(1)∼10(3), whereas the rest of the molecules are nearly CT-inactive. Furthermore, the result also proves that overall (charge-transfer and electromagnetic) enhancement of 10(6)∼10(8) is sufficient to observe the SM-SERS of an electronically off-resonant molecule, which disproves the widespread belief that a minimum enhancement of ∼10(14) is required for SM-SERS.
authors.affiliation: Department of Chemistry and BK21 Division of Chemistry, Korea University, Seoul 136-701, Korea.
authors.forename: Won-Hwa
authors.initials: WH
authors.lastname: Park
authors.forename: Zee Hwan
authors.initials: ZH
authors.lastname: Kim