DC vs AC Electrokinetics-Driven Nanoplasmonic Raman Monitoring of Charged Analyte Molecules in Ionic Solutions

Electrokinetic surface-enhanced Raman spectroscopy (EK-SERS) is an emerging high-order analytical technique that combines the plasmonic sensitivity of SERS with the electrode interfacial molecular control of electrokinetics. However, previous EK-SERS works primarily focused on non-Faradaic direct current (DC) operation, limiting the understanding of the underlying mechanisms. Additionally, developing reliable EK-SERS devices with electrically connected plasmonic hotspots remains challenging for achieving high sensitivity and reproducibility in EK-SERS measurements. In this study, we investigated the use of two-tier nanolaminate nano-optoelectrode arrays (NL-NOEAs) for DC and alternating current (AC) EK-SERS measurements of charged analyte molecules in ionic solutions. The NL-NOEAs consist of Au/Ag/Au multilayered plasmonic nanostructures on conductive nanocomposite nanopillar arrays (NC-NPAs). We demonstrate that the NL-NOEAs exhibit high SERS enhancement factors (EFs) of ∼10