3D Confocal Raman Tomography to Probe Field Enhancements inside Supercluster Metamaterials

Abstract

Spherical colloidal superclusters, composed from sub-100 nm plasmonic nanoparticles, have been proposed to possess collective plasmonic modes imbued with large field enhancements and tunable spectral response extending from the visible to infrared regions. Here, we report the experimental verification of collective near-IR plasmonic modes inside single superclusters, with dimensions ranging from 0.77 μm up to 2 μm. Raman reporters, coated onto the nanoparticle building blocks, were used as local probes of the electric field enhancement inside the metamaterial. By performing diffraction-limited 3D Raman tomography we were able to build up the electric field intensity distribution within the superclusters. We demonstrate that plasmonic responses of superclusters vary according to their size and excitation wavelength, in accordance with theoretical predictions of their tunable optical properties. The existence of three-dimensional internal collective modes in these superclusters enables the excitation of a large number of electromagnetic hot-spots, validating these self-assembled structures as promising candidates for molecular spectroscopy.