Electrogenerated Chemiluminescence Reporting on Closed Bipolar Microelectrodes and the Influence of Electrode Size

We report a fundamental study of the use of Ru(bpy)₃²⁺-based electrogenerated chemiluminescence (ECL) as an optical reporting system for the detection of redox-active analyte on closed bipolar microelectrodes, focused on gaining an in-depth understanding of the correlation between ECL emission intensity and electrochemical current. We demonstrate the significant effect that the size of the anodic and cathodic poles has on the resulting ECL signal and show how this influences the quantitative detection of analyte on a closed bipolar electrode. By carefully designing the geometry of the bipolar electrode, the detection performance of the system can be tuned to different analyte concentration ranges. We show that through a simple voltammetric study of the individual reactions, one can understand the coupled bipolar behavior and accurately predict the ECL signal response to a range of analyte concentrations, enabling the accurate prediction of calibration curves.