Sum-of-Squares Bounds on Surface-Enhanced Raman Scattering

Abstract: Surface-enhanced Raman scattering (SERS) is a critical tool for chemical sensing and spectroscopy, and a key question is how to optimally design nanostructures for maximizing SERS. We present fundamental limits on spatially-averaged SERS via periodic metasurfaces, derived using sum-of-squares (SOS) programming. This work represents the first use of SOS techniques to optics, overcoming difficulties that prior bounding techniques have with regards to non-linear photonic processes with higher order figures of merit. Our bounds on the $\int \lVert \mathbf{E} \rVert^4 \text{d} \mathbf{r}$ SERS enhancement factor for 2D examples demonstrate remarkable tightness when compared with inverse-designed dielectric and metallic structures for both electrical field out-of-plane ($E_z$) and in-plane ($H_z$) polarizations. We show that delocalized high-Q guided modes can achieve significant, theoretically diverging SERS enhancement even in the presence of material loss. For metallic structures, we demonstrate a fundamental performance limitation for $E_z$ polarized drive fields due to surface plasmon excitation restrictions. By varying the separation between Raman-active molecules and the metasurface design region, we also find material-dependent bounds on the maximum strength of field singularities. Our results offer insights into optimal metasurface design strategies for enhancing light-matter interactions, and our methodology may be adapted to the study of other nonlinear photonics design problems.