Nanoscale Imaging of Plasmonic Hot Spots and Dark Modes with the Photothermal-Induced Resonance Technique

The collective oscillation of conduction electrons, responsible for the localized surface plasmon resonances, enables engineering nanomaterials by tuning their optical response from the visible to terahertz as a function of nanostructure size, shape, and environment. While theoretical calculations helped tremendously in understanding plasmonic nanomaterials and optimizing their light matter interaction, only a few experimental techniques are available to study these materials with high spatial resolution. In this work, the photothermal-induced resonance (PTIR) technique is applied for the first time to image the dark plasmonic resonance of gold asymmetric split ring resonators (A-SRRs) in the mid-infrared (IR) spectral region with nanoscale resolution. Additionally, the chemically specific PTIR signal is used to map the local absorption enhancement of poly(methyl methacrylate) coated on A-SRRs, revealing hot spots with local enhancement factors up to approximate to 30 at 100 nm lateral resolution. We argue that PTIR nanoscale characterization will facilitate the engineering and application of plasmonic nanomaterials for mid-IR applications.