Wireless Anti-Stokes Photoinduced Electrochemiluminescence at Closed Semiconducting Bipolar Electrodes

Wireless electrochemical systems constitute a rapidly developing field. Herein, photoinduced electrochemiluminescence (PECL) is studied at Si-based closed bipolar electrodes (BPEs) for designing anti-Stokes systems that can convert IR into visible photons, without direct electrical contact. We show that protection of the anodic emitting pole of the BPE allows the triggering of bright and longstanding emission under the synergetic actions of an external bias and IR illumination. Photoactive n- and p-type Si BPEs are studied with front-side and back-side illumination, respectively, and nonphotoactive n⁺-Si BPEs are studied in the dark. Two electrochemiluminescent (ECL) systems ([Ru(bpy)₃]²⁺/TPrA and L-012) are tested, and we show that the onset bias and the anti-Stokes shift can be controlled by the ECL system that is employed. These advances, rationalized by simulations, will be useful for the design of original PECL systems for chemical sensing or photodetection.