3D nanoplasmonic structure for ultrahigh enhanced SERS with less variability, polarization independence, and multimodal sensing applied to picric acid detection†

Abstract

Surface-enhanced Raman scattering (SERS) is recognized as a powerful analytical method. However, its efficacy is hindered by considerable signal variability stemming from factors like surface irregularities, temporal instability of the substrate, interference with substrate signal, polarization sensitivity and uneven molecular distribution. To address these challenges, a new strategy is employed to enhance the reproducibility of SERS signals. Initially, a periodic 3D metallic structure is utilized to achieve polarization-independent ultrahigh enhancement. Additionally, signal averaging over multiple points and normalization are implemented. The integration of these techniques enables multimodal sensing (SERS, SEF, SPR) using a plasmonic chip, demonstrating ultrahigh enhancement through the interaction of extended and localized plasmons alongside nanoantenna-type resonances. The chip comprises a periodic silver 2D grating adorned with Au nanocubes, behaving as a 3D metasurface to amplify plasmonic local fields, thus facilitating SERS. Its uniformity and polarization independence together with signal averaging and normalization mitigate signal variability. Fabricated via electron beam lithography, the chip's performance is evaluated for surface-enhanced fluorescence (SEF) and SERS using Rhodamine 6G as the target molecule. Results exhibit two orders of magnitude enhancement factor for SEF and 2.5 × 10⁷ for SERS. For chemical sensing, the chip is tested for picric acid detection across a concentration range from nanomolar to millimolar, demonstrating a detection limit of approximately 3 nM.