A SERS-active system based on silver nanoparticles tethered to a deposited silver film

A series of SERS-active nanostructures were produced by exposing a freshly deposited silver film (fabricated to be as free from roughness as practicable) to a solution containing a mixture of 1-decanethiol (m) and 1,9-nonanedithiol (d) of varying concentrations of m to d, then allowing colloidal silver nanoparticles to interact with the surface. Silver nanoparticles were found to bind exclusively to films which were prepared from solutions with a nonzero concentration of the dithiol implying that the nanoparticles were tethered to the silver surface by the dithiol with one of the thiolate groups bound to the nanoparticle and the other to the silver film. Intense SERS spectra were observed even from samples in which the m/d concentration ratio was so large that the adsorbed molecules in the vicinity of only approximately 8 +/- 3 nanoparticles were illuminated by the diffraction-limited focused laser beam. At such high dilution, the molecules (numbering at most approximately 330) residing in the SERS "hot spots" associated with the approximately 8 nanoparticles consisted primarily of m (although, of course, for each nanoparticle, at least one molecule in the hot spot had to be d to serve as the linker). This was corroborated by the SERS spectra. An analysis is presented, which accounts for the fact that as the concentration ratio of m/d increases, the SERS intensity associated with bands belonging to m first increases to a maximum then decreases. The nanoparticle-metal film system presented here is a simple embodiment of a more general range of SERS-active sensing platforms in which a molecular tether is used to create a SERS hot spot that (although nanosized) is large enough to accommodate analyte molecules that cannot themselves function as linkers, which are subsequently detected by SERS at the few-molecule level.