Extremely Large Enhancement Factors in Surface-Enhanced Raman Scattering for Molecules on Colloidal Gold Clusters

In agreement with previous results reported for colloidal silver clusters, effective surface-enhanced Raman cross sections of about 10-¹⁶ cm² per molecule, corresponding to enhancement factors on the order of 10¹⁴, have also been obtained for molecules attached to colloidal gold clusters. Spatially isolated nearly spherical colloidal gold particles of about 60 nm size show maximum enhancement factors on the order of 10³ at 514 nm excitation, close to the single plasmon resonance. The enhancement factor increases by eleven orders of magnitude when colloidal gold clusters are formed by aggregation of the gold colloids and when near-infrared excitation is applied. The large effective surface-enhanced Raman cross section has been estimated by a straightforward method based on steady-state population redistribution due to the pumping of molecules to the first excited vibrational state via the strongly enhanced Raman process. Our experimental finding confirms the important role of colloidal clusters for extremely large surface-enhanced Raman scattering (SERS) enhancement factors. Simultaneously, it suggests colloidal gold clusters as a substrate for high-sensitivity surface-enhanced Raman scattering, which can provide an enhancement level sufficient for Raman single molecule detection. Due to its chemical inactivity, gold might have some advantages compared to silver, particularly in biomedical spectroscopy.