SERS enhancement of gold nanospheres of defined size

Monodisperse, citrate‐stabilized gold nanoparticles of sizes ranging from 15 to 40 nm were synthesized and characterized by small angle X‐ray scattering and UV‐vis experiments. Identical surface properties of nanoparticles of different sizes to avoid variation in the chemical surface‐enhanced Raman scattering (SERS) enhancement, as well as selection of experimental conditions so that no aggregation took place, enabled the investigation of enhancement of individual nanospheres. Enhancement factors (EFs) for SERS were determined using the dye crystal violet (CV). EFs for individual gold nanospheres ranged from 102 to 103, in agreement with theoretical predictions. An increase of the EFs of individual spheres with size can be correlated to changes in the extinction spectra of nanoparticle solutions. This confirms that the increase in enhancement with increasing size results from an increase in electromagnetic enhancement. Beyond this dependence of EFs of isolated gold spheres on their size, EFs were shown to vary with analyte concentration as a result of analyte‐induced aggregation. This has implications for the application of nanoparticle solutions as SERS substrates in quantitative analytical tasks. Copyright © 2011 John Wiley & Sons, Ltd. Monodisperse citrate‐stabilized gold nanoparticles of defined sizes ranging from 15 to 40 nm were used to determine the size dependence of the enhancement factor in SERS. The results are in good agreement with previous theoretical predictions.