Optical Voltammetry of redox processes inside a nanohole with Opto-iontronic microscopy (2509.01815v1)

Abstract: Cyclic Voltammetry (CV) is the most commonly used method in electrochemistry to characterize electrochemical reactions, usually involving macroscopic electrodes. Here we demonstrate a novel optical CV technique called Opto-iontronic Microscopy, which is capable of monitoring electrochemical processes at the nanoscale. By integrating optical microscopy with nanohole electrodes, we enhance sensitivity in detecting redox reactions within volumes as small as an attoliter ($(100 \text{~nm})^{3}$). This technique uses total internal reflection (TIR) illumination, Electric-double-layer modulation, cyclic voltammetry, and lock-in detection, to probe ion dynamics inside nanoholes. We applied this method to study EDL (dis)charging coupled to ferrocenedimethanol (Fc(MeOH)$_2$) redox reactions. Experimental results were validated against a theoretical Poisson-Nernst-Planck-Butler-Volmer (PNP-BV) model, providing insights into ion concentration changes of reaction species that contribute to the optical contrast. This work opens up opportunities for high-sensitivity, label-free analysis of electrochemical reactions in nanoconfined environments, with potential applications in pure nanocrystal growth and monitoring, and potentially single-molecule electrochemistry.