Exploiting Anisotropy of Plasmonic Nanostructures with Polarization-Modulation Infrared Linear Dichroism Microscopy (μPM-IRLD).

Metallic nanostructures that exhibit plasmon resonances in the mid-infrared range are of particular interest for a variety of optical processes where the infrared excitation and/or emission could be enhanced. This plasmon-mediated enhancement can potentially be used towards highly sensitive detection of an analyte(s) by techniques such as surface-enhanced infrared absorption (SEIRA). To maximize the SEIRA enhancement, it is necessary to prepare highly tuned plasmonic resonances over a defined spectral range that can span over several microns. Noteworthy, nanostructures with anisotropic shapes exhibit multiple resonances that can be exploited by controlling the polarization of the input light. This study demonstrates the role of polarization-modulation infrared linear dichroism coupled to microscopy measurements (μPM-IRLD) as a powerful means to explore the optical properties of anisotropic nanostructures. Quantitative μPM-IRLD measurements were conducted on a 2 series of dendritic fractals as model structures to explore the role of structural anisotropy on the resulting surface-enhanced infrared absorption and sensing application. Once functionalized with an analyte, the μPM-IRLD SEIRA results highlight that it is possible to selectively enhance further vibrational modes of analytes making use of the structural anisotropy of the metallic nanostructure