The attoliter volumes
and confinement abilities of zero-dimensional nanopore-electrode arrays
(NEAs) hold considerable promise for examining the behavior of single
nanoparticles. In this work, we use surface-enhanced Raman scattering
(SERS) in tandem with amperometry in order to monitor single Ag Raman-sentinel
nanoparticles transported to and captured in single nanopores. To
that end, highly ordered solid-state NEAs were fabricated to contain
periodic arrays of nanopores, each housing a single recessed Au-ring
electrode. These were used to electrostatically capture and trap single
silver nanoparticles (AgNPs) functionalized with the electrochemically
stable Raman reporter, 1,4-bis(2-methylstyryl)benzene (bis-MSB). Transport
and capture of the bis-MSB-tagged AgNPs in the nanopores was followed
by simultaneous amperometry and SERS signals characteristic of AgNP
oxidation and enhanced Raman scattering by bis-MSB at silver–gold
hot spots, respectively. The frequency and magnitude of oxidation-current
spikes increased with stepwise increases in DC voltage, and characteristic
bis-MSB SERS spectra were observed. Under AC excitation, on the other
hand, two distinctly different types of SERS signals were observed,
independent of frequency and amplitude: (1) strong, transient (<10
s) spectra and (2) slow (>100 s) monotonically diminishing spectra.
We hypothesize that the former behavior results from AgNP aggregates,
whereas the latter occurs as a result of multiple incomplete AgNP-oxidation
events in succession. These results show that attoliter-volume NEAs
are competent for acquiring concurrent SERS spectra and for amperometry
of single nanoparticles and that together these measurements can illuminate
the collision dynamics of nanoparticles in confined environments.