Tuning Surface-Enhanced Raman Scattering (SERS) via Filling Fraction and Period in Gold-Coated Bullseye Gratings

Surface-enhanced Raman scattering (SERS) is a highly sensitive analytical technique capable of single-molecule detection, yet its performance strongly depends on the underlying plasmonic architecture. In this study, we developed a robust SERS platform based on long-range–ordered bullseye plasmonic nano-gratings with tunable period and filling fraction, fabricated via electron beam lithography and reactive ion etching and uniformly coated with a thin gold film. These concentric nanostructures support efficient surface plasmon resonance and radial SPP focusing, enabling intense electromagnetic field enhancement across the substrate. Using this platform, we achieved quantitative detection of Rhodamine 6G with enhancement factors of 105. Notably, our results reveal a previously unrecognized mechanistic insight: the geometric configuration producing the strongest local electric fields does not yield the highest SERS enhancement, due to misalignment between the dominant field orientation and the molecular polarizability tensor. This finding explains the non-monotonic dependence of SERS performance on grating geometry and introduces a new design principle in which both field strength and field–molecule alignment must be co-optimized. Overall, this work provides a mechanistic framework for rationally engineering plasmonic substrates for sensitive and quantitative molecular detection.