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 ∼10⁶ and can be used to modulate the concentration and orientation of Rhodamine 6G (R6G) molecules at the electrode surface by applying DC and AC voltages. We also performed numerical simulations to investigate the ion and R6G dynamics near the electrode surface under DC and AC voltage modulation. Our results show that AC EK-SERS can provide additional insights into the dynamics of molecular transport and adsorption processes compared to DC EK-SERS. This study demonstrates the potential of NL-NOEAs for developing high-performance EK-SERS sensors for a wide range of applications.