Substrate Matters: Surface-Polariton Enhanced Infrared Nanospectroscopy of Molecular Vibrations

M. Autore, L. Mester, M. Goikoetxea and R. Hillenbrand

Nanoletters, Articles ASAP (2019)
Infrared nanospectroscopy based on Fourier transform infrared near-field spectroscopy (nano-FTIR) is an emerging nanoanalytical tool with large application potential for label-free mapping and identification of organic and inorganic materials with nanoscale spatial resolution. However, the detection of thin molecular layers and nanostructures on standard substrates is still challenged by weak signals. Here, we demonstrate a significant enhancement of nano-FTIR signals of a thin organic layer by exploiting polariton-resonant tip–substrate coupling and surface polariton illumination of the probing tip. When the molecular vibration matches the tip–substrate resonance, we achieve up to nearly one order of magnitude signal enhancement on a phonon-polaritonic quartz (c-SiO2) substrate, as compared to nano-FTIR spectra obtained on metal (Au) substrates, and up to two orders of magnitude when compared to the standard infrared spectroscopy substrate CaF2. Our results will be of critical importance for boosting nano-FTIR spectroscopy toward the routine detection of monolayers and single molecules.