Cluster Size Effects in the Surface-Enhanced Raman Scattering Response of Ag and Au Nanoparticle Aggregates: Experimental and Theoretical Insight

In this work we report the spectral evolution of the surface-enhanced Raman scattering (SERS) response of biotin molecules that generate the assembly of Ag and Au nanospheres (NSs) into clusters with controlled interparticle gaps during the aggregation process. The experiments are analyzed using rigorous near-field electrodynamic calculations of the enhancement produced in a close-packed cluster with a different number of NSs. Two kinetic mechanisms during the NS aggregation were identified which give rise to a different cluster size distribution and as a consequence to a different SERS response. It is found that during NS aggregation there is an initial fast growth of the SERS signals followed by a decay that reaches an almost constant value at relatively long times. These results are qualitatively explained by the trends observed in the electrodynamics calculations of the near-field enhancement as a function of the cluster size, which highlights the critical role played by radiation damping as the size ...

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