Umeå University's logo

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.

The emerging field of printed electronics uses large amounts of printing and coating solvents during fabrication, which commonly are deposited and evaporated within spaces available to workers. It is in this context unfortunate that many of the currently employed solvents are non-desirable from health, safety, or environmental perspectives. Here, we address this issue through the development of a tool for the straightforward identification of functional and "green" replacement solvents. In short, the tool organizes a large set of solvents according to their Hansen solubility parameters, ink properties, and sustainability descriptors, and through systematic iteration delivers suggestions for green alternative solvents with similar dissolution capacity as the current non-sustainable solvent. We exemplify the merit of the tool in a case study on a multi-solute ink for high-performance light-emitting electrochemical cells, where a non-desired solvent was successfully replaced by two benign alternatives. The green-solvent selection tool is freely available at: www.opeg-umu.se/green-solvent-tool.

The photochemical coupling of fullerene molecules into covalently connected oligomeric or polymeric structures can result in drastically lowered solubility in common solvents with retained semiconductor properties. Here, we exploit this combination of properties for the utilization of fullerenes as a negative photoresist material with electronic functionality. Specifically, we develop an easily tunable exposure system, essentially comprising a laser and a computer-controlled spatial light modulator (SLM) featuring >8 million independently controlled pixels, for the spatially selective photochemical transformation of nanometer-thin C60 fullerene films. With a carefully designed laser-SLM-exposure/solvent-development cycle, we are able to realize well-resolved two-dimensional hexagonal or square patterns of circular C60 microdots with a center-to-center distance of 1–5 μm and a maximum thickness of 20–35 nm over several square-millimeter-sized areas on a substrate. The functionality of such a hexagonal C60 pattern was demonstrated by its inclusion in between the transparent electrode and the active material in a light-emitting electrochemical cell, which featured an enhanced light output by >50% in comparison to a reference device void of the patterned C60 layer.

The electrolyte is an essential constituent of the light-emitting electrochemical cell (LEC), since its operating mechanism is dependent on the redistribution of mobile ions in the active layer. Recent developments of new ion transporters have yielded high-performance devices, but knowledge about the interactions between the ionic species and the ion transporters and the influence of these interactions on the LEC performance is lacking. We therefore present a combined computational and experimental effort that demonstrates that the selection of the end group in a star-branched oligomeric ion transporter based on trimethylolpropane ethoxylate has a paramount influence on the ionic interactions in the electrolyte and thereby also on the performance of the corresponding LECs. With hydroxyl end groups, the the salt is strongly coordinated to the ion transporter, which leads to suppression of ion pairing, but the penalty is a hindered ion release and a slow turn-on for the LEC devices. With methoxy end groups, an intermediate coordination strength is seen together with the formation of contact ion pairs, but the LEC performance is very good with fast turn-on. Using a series of ion transporters with alkyl carbonate end groups, the ion transporter:cation coordination strength is lowered further, but the turn-on kinetics are slower than what is seen for devices comprising the methoxy end-capped ion transporter.

We are in the midst of a technological revolution that permeates nearly all human activities; artificial light is one of the most visible contributors in this societal change. If more efficient, green, and versatile light sources can be developed, they might improve the life of millions of people around the world while causing minimal damage to our climate and environment. The unique operational mechanism of the light-emitting electrochemical cell (LEC) makes it an ideal fit for some unconventional and emerging uses of light, in for example medicine and security.

By exploiting this operational mechanism, in which mobile ions enable electrochemical doping of a luminescent polymer, we have designed and fabricated new bilayer LEC architectures. The bilayer LEC features patterned light emission that is easily adjustable during fabrication, and that can be configured to suit new applications of light. Given the light-emitting nature of the LEC, it is somewhat surprising that the optical understanding of its operation is rather limited. To fill this knowledge gap, we investigate how the optical properties of the luminescent polymer respond to electrochemical doping. We find that the complex-refractive index spectrum in the active layer of an LEC, as a direct result of the doping, varies in both space and time. The thin-film structure of an LEC implies that computational predictions of its luminous output need to consider internal reflections and interference. Finally, we implement a doping dependent optical thin-film simulation model. It enables us to precisely replicate the experimental luminance and angle-dependent emission spectrum for a range of LECs with different thicknesses. Using the model we can also identify and quantify many of the different optical loss mechanisms in LECs, which has not previously been done. The insights that we have collected on the path towards our present model will be useful for computational determination of device parameters that are otherwise difficult to acquire.

The improved understanding of the optical operation of LECs is important for the maturation of the technology, as it facilitates formulation of relevant and accurate research questions. Hopefully, our results will accelerate the development of the field, so that useful products based on this technology can become available in the not too distant future.

Just nu pågår en teknologisk revolution som genomsyrar nära nog alla samhällsfunktioner, och där artificiellt ljus har en påfallande viktig roll. Nya ljuskällor, som är mer miljövänliga, effektiva och mångsidiga, skulle kunna förbättra livskvaliten för miljoner människor över hela världen, utan att för den skull skapa problem för vår miljö och vårt klimat. Den ljusemitterande elektrokemiska cellen (LEC) är en teknik som fungerar på ett unikt sätt. Det gör att den är lämplig för nya och okonventionella användningsområden av ljus, exempelvis inom medicin och säkerhetsprodukter.

Vi har kunnat designa och tillverka en ny sorts dubbellagers-LEC genom att utnyttja den interna funktionen i en LEC. Den innebär att rörliga joner möjliggör elektrokemiska oxidations- och reduktionsprocesser (dopning) av en lysande polymer. En dubbellagers-LEC lyser i mönster som enkelt kan anpassas utefter önskemål, och skulle kunna användas i nya sorters ljusapplikationer. Med tanke på att en LEC är en lysande komponent är förståelsen för dess optik förvånansvärt begränsad. För att förbättra dessa kunskaper börjar vi med att undersöka hur den lysande polymerens optiska egenskaper förändras när den dopas. Vi finner att dess optiska egenskaper varierar i tid och rum i det aktiva skiktet i en LEC, som en direkt följd av dopningen. För att sedan med hjälp av de optiska egenskaperna kunna beräkna hur mängden ljus påverkas, måste vi också ta hänsyn till att ljus i tunna skikt kan reflekteras vid gränsytor och interagera med sig själv. Slutligen implementerar vi en dopningsberoende optisk beräkningsmodell för tunna skikt, och lyckas återskapa den experimentellt uppmätta luminansen och de vinkelberoende ljusspektrumen för en serie LECer med olika tjocklek. Utifrån modellen kan vi också identifiera och kvantifiera många av de olika optiska förlustkanalerna i en LEC, vilket inte gjorts tidigare. Vägen fram till den nuvarande modellen har bjudit oss på en rad insikter som gör att vi beräkningsmässigt kan uppskatta komponentegenskaper som annars skulle förbli okända, då de inte går att mäta med direkta metoder.

Den förbättrade optiska förståelsen för LEC-tekniken är viktig för forskningen inom fältet. Våra resultat kan förhoppningsvis accelerera utvecklingen mot bra och användbara produkter, så att dessa blir tillgängliga inom en inte alltför avlägsen framtid.

The light-emitting electrochemical cell (LEC) is a contender for emerging applications of light, primarily because it offers low-cost solution fabrication of easily functionalized device architectures. The attractive properties originate in the in-situ formation of electrochemically doped transport regions that enclose an emissive intrinsic region, but the understanding of how this intricate doping structure affects the optical performance of the LEC is largely lacking. We combine angle- and doping-dependent measurements and simulations, and demonstrate that the emission zone in our high-performance LEC is centered at ~30% of the active-layer thickness (d_al) from the anode. We further find that the emission intensity and efficiency are undulating with d_al, and establish that the first emission maximum at d_al ~ 100 nm is largely limited by the lossy coupling of excitons to the doping regions, whereas the most prominent loss channel at the second maximum at d_al ~ 300 nm is wave-guided modes.

We report on light-emitting electrochemical cells, comprising a solution-processed single-layer active material and air-stabile electrodes, that exhibit efficient and bright thermally activated delayed fluorescence. Our optimized devices delivers a luminance of 120 cd m⁻² at an external quantum efficiency of 7.0%. As such, it outperforms the combined luminance/efficiency state-of-the art for thermally activated delayed fluorescence light-emitting electrochemical cells by one order of magnitude. For this end, we employed a polymeric blend host for balanced electrochemical doping and electronic transport as well as uniform film formation, an optimized concentration (<1 mass%) of guest for complete host-to-guest energy transfer at minimized aggregation and efficient emission, and an appropriate concentration of an electrochemically stabile electrolyte for desired doping effects. The generic nature of our approach is manifested in the attainment of bright and efficient thermally activated delayed fluorescence emission from three different light-emitting electrochemical cells with invariant host:guest:electrolyte number ratio.

The light-emitting electrochemical cell (LEC) exhibits capacity for efficient charge injection from two air stable electrodes into a single-layer active material, which is commonly interpreted as implying that the LEC operation is independent of the electrode selection. Here, we demonstrate that this is far from the truth and that the electrode selection instead has a strong influence on the LEC performance. We systematically investigate 13 different materials for the positive anode and negative cathode in a common LEC configuration with the conjugated polymer Super Yellow as the electroactive emitter and find that Ca, Mn, Ag, Al, Cu, indium tin oxide (ITO), and Au function as the LEC cathode, whereas ITO and Ni can operate as the LEC anode. Importantly, we demonstrate that the electrochemical stability of the electrode is paramount and that particularly electrochemical oxidation of the anode can prohibit the functional LEC operation. We finally report that it appears preferable to design the device so that the heights of the injection barriers at the two electrode/active material interfaces are balanced in order to mitigate electrode-induced quenching of the light emission. As such, this study has expanded the set of air-stable electrode materials available for functional LEC operation and also established a procedure for the evaluation and design of future efficient electrode materials.

The light-emitting electrochemical cell (LEC) is functional at substantial active-layer thickness, and is as such heralded for being fit for low-cost and fault-tolerant solution-based fabrication. We report here that this statement should be moderated, and that in order to obtain a strong luminous output, it is fundamentally important to fabricate LEC devices with a designed thickness of the active layer. By systematic experimentation and simulation, we demonstrate that weak optical microcavity effects are prominent in a common LEC system, and that the luminance and efficiency, as well as the emission color and the angular intensity, vary in a periodic manner with the active-layer thickness. Importantly, we demonstrate that high-performance light-emission can be attained from LEC devices with a significant active-layer thickness of 300 nm, which implies that low-cost solution-processed LECs are indeed a realistic option, provided that the device structure has been appropriately designed from an optical perspective.

We report on the in situ measured evolution of the spectral complex refractive index of a prototypical conjugated polymer, a phenyl-substituted poly (para-phenylenevinylene) copolymer (Ph-PPV, “Super Yellow”), during electrochemical p- and n-type doping. We find that the real part of the refractive index is lowered in a significant and continuous fashion over essentially the entire visible range with doping, as exemplified by a drop in the peak value at ∼480 nm from 2.1 for pristine Ph-PPV to 1.8 at a p-type doping concentration of 0.2 dopants per repeat unit and an n-type doping concentration of 0.6 dopants per repeat unit. The imaginary part features a concomitant distinct bleaching of the high-energy π–π* transition and the emergence of a low-energy polaron band. Interestingly, we observe that the optical response of Ph-PPV to p-type and n-type doping is highly asymmetric, with the former resulting in much stronger changes and a distinct blue-shift of all optical transitions. We tentatively attribute this difference in response to larger effective size of the p-type polaron compared to the n-type polaron. We anticipate that the presented results should be of value for the rational design of emerging optical devices that utilize the doping capacity of conjugated polymers.