Probing Surface Enhancement Effect of Molecules On/Between Silver Nanoparticles in Surface Enhanced Raman Scattering

To explore the mechanisms in Surface‐enhanced Raman Scattering (SERS) measurements, silver nanoparticles (AgNPs) were first prepared by a silver mirror reaction to form different particle sizes and different distributions on glass substrates. After the resulting surfaces were probed with molecules of p‐Amino‐thiophenol (pATP), p‐Nitrothiophenol (pNTP), and p‐Mercaptobenzoic acid (pMBA) individually, the substrates were placed into reaction solutions to grow additional AgNPs. In this way, probe molecules could be trapped between two nanoparticles, possibly having the so‐called “hot spot” effect. To examine the variations of morphologies of AgNPs in each of the steps, the substrates were examined by field‐emission scanning electron microscope (FE‐SEM). The morphologies also were correlated with the SERS signals. Two bands in the SERS spectra of probe molecules were selected as indications of the enhancements from electromagnetic (EM) effect and charge‐transfer (CT). Results indicate that the SERS signals from the EM effect were increased ca. 5 times after growing additional AgNPs on the molecule‐modified AgNPs substrates. The SERS signals from CT effect were increased two orders of magnitude after growing additional AgNPs. The increase of enhancement for molecules between AgNPs was caused mostly by CT effect. Based on the effect of particle size and distribution of the AgNPs, the EM effect was strongly influenced by the particle size of the AgNPs, while the CT effect was less sensitive to the variation of the morphologies of the AgNPs.