Abstract

Charge injection at a metal/semiconductor interface is of paramount importance for many chemical and physical processes. The dual injection of electrons and holes, for example, is necessary for electroluminescence in organic light-emitting devices. In an electrochemical cell, charge transfer across the electrode interface is responsible for redox reactions and Faradic current flow. In this work, we use polymer light-emitting electrochemical cells (PLECs) to visually assess the ability of metals to inject electronic charges into a luminescent polymer. Silver, aluminum, and gold microdisks are deposited between the two driving electrodes of the PLEC in the form of a horizontal array. When the PLEC is polarized, the individual disks functioned as bipolar electrodes (BPEs) to induce redox p- and n-doping reactions at their extremities, which are visualized as strongly photoluminescence-quenched growth in the luminescent polymer. The three metals initially generate highly distinct doping patterns that are consistent with differences in their work function. Over time, the doped regions continue to grow in size. Quantitative analysis of the n/p area ratio reveals an amazing convergence to a single value for all 39 BPEs, regardless of their metal type and large variation in the size of individual doped areas. We introduce the concept of a dynamic BPE, which transforms from an initial metal disk of a fixed size to one that is a composite of p- and n-doped polymer joined by the initial metallic BPE. The internal structure of the dynamic BPE, as measured by the n/p area ratio, reflects the properties of only the mixed conductor of the PLEC active layer itself when the area ratio converges.

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