Metamaterial-enhanced infrared attenuated total reflection spectroscopy

The use of Fourier transform infrared spectroscopy with attenuated total reflection (FTIR-ATR) allows solid or liquid samples to be characterised directly without specific sample preparation. In such a system, the evanescent waves generated through total internal reflection within a crystal interact with the sample under test. In this work we explore the use of a mid-infrared metasurface to enhance the interaction between molecular vibrations and the evanescent waves. A complementary ring-resonator structure was patterned onto both silicon and SiO₂/Si substrates, and the spectral properties of both devices were characterised using a FTIR-ATR system. Minima in reflectance were observed corresponding to the resonance of the metasurface on the silicon substrate, and to the hybrid resonance of phonon modes and metasurface resonances on the SiO₂/Si substrate, in good agreement with simulations. Preliminary experiments were undertaken using mixtures containing trace amounts of butyl acetate diluted with oleic acid. Without the use of a metasurface, the minimum concentration of butyl acetate that could be clearly detected was 10%, whereas the use of the metasurface on the SiO₂/Si substrate allowed the detection of 1% butyl acetate. This demonstrates the potential of using metasurfaces to enhance trace chemical detection in FTIR-ATR systems.