Umeå University's logo

Light-emitting electrochemical cells (LECs) are promising candidates for fully solution-processed lighting applications because they can comprise a single active-material layer and air-stable electrodes. While their performance is often claimed to be independent of the electrode material selection due to the in situ formation of electric double layers (EDLs), we demonstrate conceptually and experimentally that this understanding needs to be modified. Specifically, the exciton generation zone is observed to be affected by the electrode work function. We rationalize this finding by proposing that the ion concentration in the injection-facilitating EDLs depends on the offset between the electrode work function and the respective semiconductor orbital, which in turn influences the number of ions available for electrochemical doping and hence shifts the exciton generation zone. Further, we investigate the effects of the electrode selection on exciton losses to surface plasmon polaritons and discuss the impact of cavity effects on the exciton density. We conclude by showing that we can replicate the measured luminance transients by an optical model which considers these electrode-dependent effects. As such, our findings provide rational design criteria considering the electrode materials, the active-material thickness, and its composition in concert to achieve optimum LEC performance.

Understanding “efficiency roll-off” (i.e., the drop in emission efficiency with increasing current) is critical if efficient and bright emissive technologies are to be rationally designed. Emerging light-emitting electrochemical cells (LECs) can be cost- and energy-efficiently fabricated by ambient-air printing by virtue of the in situ formation of a p-n junction doping structure. However, this in situ doping transformation renders a meaningful efficiency analysis challenging. Herein, a method for separation and quantification of major LEC loss factors, notably the outcoupling efficiency and exciton quenching, is presented. Specifically, the position of the emissive p-n junction in common singlet-exciton emitting LECs is measured to shift markedly with increasing current, and the influence of this shift on the outcoupling efficiency is quantified. It is further verified that the LEC-characteristic high electrochemical-doping concentration renders singlet-polaron quenching (SPQ) significant already at low drive current density, but also that SPQ increases super-linearly with increasing current, because of increasing polaron density in the p-n junction region. This results in that SPQ dominates singlet-singlet quenching for relevant current densities, and significantly contributes to the efficiency roll-off. This method for deciphering the LEC efficiency roll-off can contribute to a rational realization of all-printed LEC devices that are efficient at highluminance.

The concept of a metal-free and all-organic electroluminescent device is appealing from both sustainability and cost perspectives. Herein, we report the design and fabrication of such a light-emitting electrochemical cell (LEC), comprising a blend of an emissive semiconducting polymer and an ionic liquid as the active material sandwiched between two poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) conducting-polymer electrodes. In the off-state, this all-organic LEC is highly transparent, and in the on-state, it delivers uniform and fast to turn-on bright surface emission. It is notable that all three device layers were fabricated by material- and cost-efficient spray-coating under ambient air. For the electrodes, we systematically investigated and developed a large number of PEDOT:PSS formulations. We call particular attention to one such p-type doped PEDOT:PSS formulation that was demonstrated to function as the negative cathode, as well as future attempts towards all-organic LECs to carefully consider the effects of electrochemical doping of the electrode in order to achieve optimum device performance.

The initial operation of a light-emitting electrochemical cell (LEC) constitutes the in-situ formation of a p-n junction doping structure in the active material by electrochemical doping. It has been firmly established that the spatial position of the emissive p-n junction in the interelectrode gap has a profound influence on the LEC performance because of exciton quenching and microcavity effects. Hence, practical strategies for a control of the position of the p-n junction in LEC devices are highly desired. Here, we introduce a "chemical pre-doping" approach for the rational shifting of the p-n junction for improved performance. Specifically, we demonstrate, by combined experiments and simulations, that the addition of a strong chemical reductant termed "reduced benzyl viologen" to a common active-material ink during LEC fabrication results in a filling of deep electron traps and an associated shifting of the emissive p-n junction from the center of the active material towards the positive anode. We finally demonstrate that this chemical pre-doping approach can improve the emission efficiency and stability of a common LEC device.

The orientation of the emissive dipoles in thin-film devices is important since it strongly affects the light outcoupling and thereby the device emission efficiency. The light-emitting electrochemical cell (LEC) is particularly interesting in this context because its emissive dipoles are located in a high electric-field p-n junction, which is formed in situ by redistribution of bulky ions. This implies that the dipole orientation could be distinctly different in the driven LEC compared to the pristine device. This study develops the destructive-interference microcavity method for the accurate in situ determination of the orientation of the emissive dipoles during LEC operation and apply it on a common LEC device comprising an amorphous conjugated polymer termed Super Yellow as the emitter. It is found that ≈95% of the emissive dipoles are oriented in the horizontal direction with respect to the thin-film plane in both the pristine LEC and during steady-state light emission. This finding is attractive since it enables for efficient outcoupling of the generated photons, and interesting because it shows that a horizontal orientation of the emissive dipoles can remain despite the existence of a strong perpendicular electric field and the nearby motion of bulky ions during LEC operation.

Organic semiconductors that emit by the process of multi-resonance thermally activated delayed fluorescence (MR-TADF) can deliver narrowband and efficient electroluminescence while being processable from solvents and metal-free. This renders them attractive for use as the emitter in sustainable light-emitting electrochemical cells (LECs), but so far reports of narrowband and efficient MR-TADF emission from LEC devices are absent. Here, this issue is addressed through careful and systematic material selection and device development. Specifically, the authors show that the detrimental aggregation tendency of an archetypal rigid and planar carbazole-based MR-TADF emitter can be inhibited by its dispersion into a compatible carbazole-based blend host and an ionic-liquid electrolyte, and it is further demonstrated that the tuning of this active material results in a desired balanced p- and n-type electrochemical doping, a high solid-state photoluminescence quantum yield of 91%, and singlet and triplet trapping on the MR-TADF guest emitter. The introduction of this designed metal-free active MR-TADF material into a LEC, employing air-stabile electrodes, results in bright blue electroluminescence of 500 cd m−2, which is delivered at a high external quantum efficiency of 3.8% and shows a narrow emission profile with a full-width-at-half-maximum of 31 nm.

Perovskite quantum dots (PeQDs) endowed with capping ligands exhibit impressive optoelectronic properties and enable for cost-efficient solution processing and exciting application opportunities. We synthesize and characterize three different PeQDs with the same cubic CsPbBr₃ core, but which are distinguished by the ligand composition and density. PeQD-1 features a binary didodecyldimethylammonium bromide (DDAB) and octanoic acid capping ligand system, with a high surface density of 1.53 nm⁻², whereas PeQD-2 and PeQD-3 are coated by solely DDAB at a gradually lower surface density. We show that PeQD-1 endowed with highest ligand density features the highest dispersibility in toluene of 150 g/L, the highest photoluminescence quantum yield of 95% in dilute solution and 59% in a neat film, and the largest core-to-core spacing in neat thin films. We further establish that ions are released from the core of PeQD-1 when it is exposed to an electric field, although it comprises a dense coating of one capping ligand per four surface core atoms. We finally exploit these combined findings to the development of a light-emitting electrochemical cell (LEC), where the active layer is composed solely of solution-processed pure PeQDs, without additional electrolytes. In this device, the ion release is utilized as an advantage for the electrochemical doping process and efficient emissive operation of the LEC.

The position of the emission zone (EZ) in the active material of a light-emitting electrochemical cell (LEC) has a profound influence on its performance because of microcavity effects and doping- and electrode-induced quenching. Previous attempts of EZ control have focused on the two principal constituents in the active material—the organic semiconductor (OSC) and the mobile ions—but this study demonstrates that it is possible to effectively control the EZ position through the inclusion of an appropriate additive into the active material. More specifically, it is shown that a mere modification of the end group on an added neutral compound, which also functions as an ion transporter, results in a shifted EZ from close to the anode to the center of the active material, which translates into a 60% improvement of the power efficiency. This particular finding is rationalized by a lowering of the effective electron mobility of the OSC through specific additive: OSC interactions, but the more important generic conclusion is that it is possible to control the EZ position, and thereby the LEC performance, by the straightforward inclusion of an easily tuned additive in the active material.

Light-emitting electrochemical cells (LECs) comprising metal-free molecules that emit by the process of thermally activated delayed fluorescence (TADF) can be both sustainable and low cost. However, the blue emission performance of current TADF-LECs is unfortunately poor, which effectively prohibits their utilization in important applications, such as illumination and full-color displays. Here, this drawback is addressed through the development of a TADF-LEC, which delivers blue light emission (peak wavelength = 475 nm) with a high external quantum efficiency of 5.0%, corresponding to a current efficacy of 9.6 cd A^-1. It is notable that this high efficiency is attained at bright luminance of 740 cd m^-2, and that the device turn-on is very fast. It is demonstrated that this accomplishment is enabled by the blending of a carbazole-based 9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)-2-methylphenyl)-3,6-dimethyl-9H-carbazole guest emitter with a compatible carbazole-based tris(4-carbazoyl-9-ylphenyl)amine:2,6-bis(3-(carbazol-9-yl)phenyl)pyridine blend-host for the attainment of bipolar electrochemical doping, balanced electron/hole transport, and exciplex-effectuated host-to-guest energy transfer.

A light-emitting electrochemical cell (LEC) comprises mobile ions in its active material, which enable for in situ formation of a p-n junction by electrochemical doping. The position of this emissive p-n junction in the interelectrode gap is important, because it determines whether the emission is affected by constructive or destructive interference. An appealing LEC feature is that the entire device can be fabricated by low-cost solution-based printing and coating. Here, we show, somewhat unexpectedly, that the replacement of conventional vacuum-deposited indium-tin-oxide (ITO) for the positive anode with solution-processed poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) can result in an increase in the peak light-emission output by 75%. We demonstrate that this emission increase is due to that the p-n junction shifts from a position of destructive interference in the center of the interelectrode gap with ITO to a position of constructive interference closer to the anode with PEDOT:PSS. We rationalize the anodic p-n junction shift by significant anion transfer into the soft and porous PEDOT:PSS electrode during LEC operation, which is prohibited for the ITO electrode because of its compact and hard nature. Our study, thus, contributes with important design criteria for the attainment of efficient light emission from solution-processed LEC devices.