Bilayer light-emitting electrochemical cells are demonstrated with a top conjugated polymer (CP) emitting layer and a solid polymer electrolyte (SPE) underlayer. Fast, long-range ion transport through the planar CP/SPE interface leads to doping and junction electroluminescence in the CP layer. All bilayer cells have pairs of aluminum electrodes separated by 2 or 11 mm at their inner edges, creating the largest planar (lateral) cells that can be imaged with excellent temporal and spatial resolutions. To understand how in situ electrochemical doping occurs in the CP layer without any ionic species mixed in, the planar bilayer cells are investigated for different CPs, CP layer thickness, operating voltage, and operating temperature. The bilayer cells are much faster to turn on than control cells made from a single mixed CP/SPE layer. The cell current and the doping propagation speed exhibit a linear dependence on the operating voltage and an Arrhenius-type temperature dependence. Unexpectedly, long-range ion transport in the CP layer and across the CP/SPE interface does not impede the doping reactions. Instead, the doping reactions are limited by the bulk resistance of the extra-wide SPE underlayer. In bilayer cells with a thin red-emitting CP layer, ion transport and doping reactions can penetrate the entire CP layer in the vertical direction. In thicker MEH-PPV or the blue-emitting cells, the doping did not reach the top of the CP layer. This led to broadened emitting junctions and/or unexpected junction locations. The bilayer LECs offer unique opportunities to investigate the ion transport in pristine CPs, the CP/SPE interface, and the SPE using highly sensitive and reliable imaging techniques. Removing the inert electrolyte polymer from the semiconducting CP can potentially lead to highperformance electrochemical light-emitting/photovoltaic cells or transistors.
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