Dielectric metasurface-assisted cavity ring-down spectroscopy for thin-film circular dichroism analysis

Chiral molecules show differences in their chemical and optical properties due to different spatial arrangements of the atoms in the two enantiomers. A common way to optically differentiate them is to detect the disparity in the absorption of light by the two enantiomers, i.e. the absorption circular dichroism (CD). However, the CD of typical molecules is very small, limiting the sensitivity of chiroptical analysis based on CD. Cavity ring-down spectroscopy (CRDS) is a well-known ultrasensitive absorption spectroscopic method for low-absorbing gas-phase samples because the multiple reflections of light in the cavity greatly increase the absorption path. By inserting a prism into the cavity, the optical mode undergoes total internal reflection (TIR) at the prism surface and the evanescent wave (EW) enables the absorption detection of condensed-phase samples within a very thin layer near the prism surface, called EW-CRDS. Here, we propose an ultrasensitive chiral absorption spectroscopy platform using a dielectric metasurface-assisted EW-CRDS. We theoretically show that, upon linearly polarized and oblique incidence, the metasurface exhibits minimum scattering and absorption loss, introduces negligible polarization change, and locally converts the linearly polarized light into near fields with finite optical chirality, enabling CD detection with EW-CRDS that only works with linearly polarized light. We evaluate the ring-down time in the presence of chiral molecules and determine the sensitivity of the cavity as a function of total absorption from the molecules. The findings open the avenue for an ultrasensitive thin film detection of the chiral molecules using the CRDS techniques.

Automated summary

Chiral molecules exhibit differences in chemical and optical properties due to different spatial arrangements. Optical differentiation is commonly achieved through detection of absorption circular dichroism (CD). However, CD in typical molecules is limited by its small magnitude. Cavity ring-down spectroscopy (CRDS) is an ultrasensitive absorption spectroscopic method for low-absorbing gas-phase samples. In this study, we propose a metasurface-assisted EW-CRDS platform for ultrasensitive chiral absorption spectroscopy, enabling CD detection with linearly polarized light. The findings open up possibilities for highly-sensitive thin film detection of chiral molecules using CRDS techniques.