Surface Enhanced Infrared Absorption Using Single Conducting Polymer Antennas.

Infrared absorption provides the intrinsic vibrational information on chemical bonds, which is important for identifying molecular moieties. To enhance the sensitivity of infrared absorption, plasmonic antennas have been widely used to localize and concentrate mid-infrared light into nanometer-scale hotspots at desired wavelengths. Here, instead of inorganic plasmonic antennas, we have demonstrated surface-enhanced infrared absorption (SEIRA) using single plasmonic antennas based on a conducting polymer. With commercially available PEDOT:PSS (poly(ethylenedioxythiophene):poly(styrenesulfonate)), the organic plasmonic antennas are in the fashion of single PEDOT:PSS micropillars. The plasmonic resonance of single PEDOT:PSS micropillar antennas can be easily tuned by the micropillar diameter or by the interantenna gap across the mid-infrared frequencies. These organic plasmonic antennas show the ability to enhance the molecular vibrations of CBP (4,4'-bis(N-carbazolyl)-1,1'-biphenyl) molecules with a thickness of about 50 nm, illustrating the good SEIRA sensitivity (with SEIRA sensitivity up to ∼7800) at the single antenna level. Our findings provide another material choice for mid-infrared plasmonic antennas toward SEIRA applications.

Epsilon-near-zero substrate-enabled strong coupling between molecular vibrations and mid-infrared plasmons.

As the strong light-matter interaction between molecular vibrations and mid-infrared optical resonant modes, vibrational strong coupling (VSC) has the potential to modify the intrinsic chemistry of molecules, leading to the control of ground-state chemical reactions. Here, by using quartz as an epsilon-near-zero (ENZ) substrate, we have realized VSC between organic molecular vibrations and mid-infrared plasmons on metallic antennas. The ENZ substrate enables sharp mid-infrared plasmonic resonances (Q factor ∼50) which efficiently couple to the molecular vibrations of polymethyl methacrylate (PMMA) molecules with prominent mode splitting. The coupling strength is proportional to the square root of the thickness of the PMMA layer and reaches the VSC regime with a thickness of ∼300 nm. The coupling strength also depends on the polarization of the incident light, illustrating an additional way to control the molecule-plasmon coupling. Our findings provide a new, to the best of our knowledge, possibility to realize VSC with metallic antennas and pave the way to increase the sensitivity of molecular vibrational spectroscopy.