Organized Plasmonic Clusters with High Coordination Number and Extraordinary Enhancement in Surface-Enhanced Raman Scattering (SERS)

Noble metal nanoparticles exhibit optical excitations known as surface plasmons that produce large enhancement of the local light intensity under external illumination, particularly when the nanoparticles are arranged in closely spaced configurations.1 The interparticle gap distance2 plays a critical role in the generation of hotspots with high electromagnetic fields, and thus such assembled nanoparticles find application to ultrasensitive detection, for example through surface-enhanced Raman scattering3 (SERS) and nonlinear optics, among other feats.4 Controlled assembly using colloidal chemistry is an emerging and promising field for high-yield production of metal nanoparticle clusters with small interparticle gaps.5 However, most of the reported methods rely on the use of nucleic acids or other organic molecules as linking elements,6 which yield long separation distances and thus weak plasmon coupling. Additionally, only simple clusters, such as dimers and trimers, have been efficiently synthesized. Herein, we report the controlled assembly of gold nanospheres into well-defined nanoparticle clusters with large coordination numbers (up to 7) and high symmetry. We further demonstrate ultrasensitive direct and indirect SERS sensing, thus corroborating the outstanding optical performance of these clusters with robust enhancement factors that are over three orders of magnitude higher than those of single particles.