Influence of surface plasmon resonance wavelength on SERS activity of naturally grown silver nanoparticle ensemble

We present experimental results to quantify and optimize the surface‐enhanced Raman scattering (SERS) activity of naturally grown silver nanoparticles. Ag nanoparticle ensembles with mean equivalent radii ranging from 10.6 to 20.3 nm were prepared under ultrahigh vacuum conditions by Volmer–Weber growth on quartz plates. A tuning of the localized surface plasmon polariton resonance wavelength from 453 to 548 nm was performed by varying the morphology of the silver nanoparticles. The dependence of the SERS activity on the plasmon resonance wavelength was investigated with a Raman set‐up containing a microsystem light source with an emission line at 488 nm. Shifted excitation Raman difference spectroscopy was applied to remove the fluorescence‐based background from the SERS spectra of pyrene in water using two slightly different emission wavelengths (487.61 and 487.91 nm) of the microsystem light source. We demonstrate that the Raman activities for all SERS substrates are available in the nanomolar range in a water sample. However, the Raman activity crucially depends on the plasmon resonance wavelength of the nanoparticle ensembles. Although for an on‐resonance ensemble the limit of detection for pyrene in water is very low and was estimated to be 2 nmol/L, it increases rapidly to several tens of nanomol for slightly off‐resonance ensembles. Hence, the highest SERS activity was obtained with a nanoparticle ensemble exhibiting a plasmon resonance wavelength at 491 nm, which almost coincides with the excitation wavelengths. Copyright © 2012 John Wiley & Sons, Ltd.