RESUMO
Surface-enhanced Raman spectroscopy (SERS) harnesses the confinement of light into metallic nanoscale hotspots to achieve highly sensitive label-free molecular detection that can be applied for a broad range of sensing applications. However, challenges related to irreversible analyte binding, substrate reproducibility, fouling, and degradation hinder its widespread adoption. Here we show how in-situ electrochemical regeneration can rapidly and precisely reform the nanogap hotspots to enable the continuous reuse of gold nanoparticle monolayers for SERS. Applying an oxidising potential of +1.5 V (vs Ag/AgCl) for 10 s strips a broad range of adsorbates from the nanogaps and forms a metastable oxide layer of few-monolayer thickness. Subsequent application of a reducing potential of -0.80 V for 5 s in the presence of a nanogap-stabilising molecular scaffold, cucurbit[5]uril, reproducibly regenerates the optimal plasmonic properties with SERS enhancement factors ≈106. The regeneration of the nanogap hotspots allows these SERS substrates to be reused over multiple cycles, demonstrating ≈5% relative standard deviation over at least 30 cycles of analyte detection and regeneration. Such continuous and reliable SERS-based flow analysis accesses diverse applications from environmental monitoring to medical diagnostics.
RESUMO
We demonstrate the reliable creation of multiple layers of Au nanoparticles in random close-packed arrays with sub-nm gaps as a sensitive surface-enhanced Raman scattering substrate. Using oxygen plasma etching, all the original molecules creating the nanogaps can be removed and replaced with scaffolding ligands that deliver extremely consistent gap sizes below 1 nm. This allows precision tailoring of the chemical environment of the nanogaps which is crucial for practical Raman sensing applications. Because the resulting aggregate layers are easily accessible from opposite sides by fluids and by light, high-performance fluidic sensing cells are enabled. The ability to cyclically clean off analytes and reuse these films is shown, exemplified by sensing of toluene, volatile organic compounds, and paracetamol, among others.