Hyperbolic-enhanced Raman scattering in van der Waals MoOCl2: from Fano resonances to picomolar detection

Abstract

Natural van der Waals (vdW) crystals with hyperbolic dispersion challenge artificial metamaterials but remain confined to the mid-infrared. The emergence of MoOCl2, a quasi-one-dimensional metal with in-plane hyperbolicity, overcomes this spectral limit, shifting the focus to the practical visible range. Here, using angle-resolved polarized Raman spectroscopy, we uncover pronounced polarization-dependent Fano lineshapes that reveal coupling between phonons and the anisotropic metallic continuum, together with strong wavelength-dependent reshaping of the Raman polarization patterns governed by the anisotropic optical response of MoOCl2. Harnessing this optical anisotropy, we demonstrate "Hyperbolic-Enhanced Raman" (HypER) scattering, where MoOCl2 provides polarization-tunable analytical enhancement factors exceeding 10^7 and picomolar-level detection of Rhodamine 6G down to 100 pM, without deliberate surface nanostructuring. These results establish air-stable MoOCl2 as a simple, wafer-compatible platform for visible-range hyperbolic nanophotonics and lithography-free sensing.

25 pages, 5 figures