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In light‐emitting electrochemical cells (LECs), the position of the emission zone (EZ) is not predefined via a multilayer architecture design, but governed by a complex motion of electrical and ionic charges. As a result of the evolution of doped charge transport layers that enclose a dynamic intrinsic region until steady state is reached, the EZ is often dynamic during turn‐on. For thick sandwich polymer LECs, a continuous change of the emission color provides a direct visual indication of a moving EZ. Results from an optical and electrical analysis indicate that the intrinsic zone is narrow at early times, but starts to widen during operation, notably well before the electrical device optimum is reached. Results from numerical simulations demonstrate that the only precondition for this event to occur is that the mobilities of anions (µa) and cations (µc) are not equal, and the direction of the EZ shift dictates µc > µa. Quantitative ion profiles reveal that the displacement of ions stops when the intrinsic zone stabilizes, confirming the relation between ion movement and EZ shift. Finally, simulations indicate that the experimental current peak for constant‐voltage operation is intrinsic and the subsequent decay does not result from degradation, as commonly stated.

Effects of ion concentration and active layer thickness play a critical role on the performance of light-emitting electrochemical cells. Expanding on a pioneering materials system comprising the super yellow (SY) polymer and the electrolyte trimethylolpropane ethoxylate (TMPE)/Li+CF3SO3-, it is reported that a slightly lowered salt concentration and layer thickness result in a substantial efficiency increase, and that this increase is confined to a narrow concentration and thickness range. For a film thickness of 70 nm, a blend ratio SY:TMPE:Li+CF3SO3- = 1:0.075:0.0225, and a current of 7.7 mA cm(-2) the current efficacy is 11.6 cd A(-1), on a par with SY light-emitting diodes. The optimized salt content can be explained by increased exciton quenching at higher concentrations and hindered carrier injection and conduction at lower concentrations, while the optical dependence on the layer thickness is due to weak microcavity effects. A comprehensive optical modeling study is presented, which includes the doping-induced changes of the refractive indices and self-absorption losses due the emission-absorption overlap of intrinsic and doped SY. The analysis indicates either a thickness-independent emitter position (EP) close to the anode or a thickness-dependent EP, shifted to the cathode for increased thicknesses.