Polyelectrolyte induced controlled assemblies for the backbone of robust and brilliant Raman tags

Near-field and far-field optical properties of plasmonic materials can be tailored by coupling the existing structures. However, fabricating 3D coupled structures in the solution by molecular linkers may suffer from low yield, low stability (particle aggregates), long reaction time, complex surface modification or multiple purification steps. In this report, stable 3D plasmonic core-satellite assemblies (CSA) with a ~1 nm interior gap accompanied by high field enhancement (|E/Einc|>200) are formed in a few seconds through a single polyelectrolyte linker layer. In addition, by covalently binding different reporter molecules and core particles, three distinct Raman tags based on this CSA backbone are demonstrated and compared with conventional fluorophores in terms of stability. This general assembly method can be applied to any type of colloidal particles carrying stable surface charge, even non-plasmonic nanoparticles. It will facilitate the development of various robust Raman tags for multiplexed biomedical imaging/sensing by efficiently combining constituent particles of differing size/shape/composition. The CSA backbone with an embedded high field not only makes the brightness of Raman tags more comparable to the fluorophores and can also be utilized in the platform of molecule-light quantum strong coupling.