Tuning Charge-Transfer States by Interface Electric Fields.

Intermolecular charge-transfer (CT) states are extended excitons with a charge separation on the nanometer scale. Through absorption and emission processes, they couple to the ground state. This property is employed both in light-emitting and light-absorbing devices. Their conception often relies on donor-acceptor (D-A) interfaces, so-called type-II heterojunctions, which usually generate significant electric fields. Several recent studies claim that these fields alter the energetic configuration of the CT states at the interface, an idea holding prospects like multicolor emission from a single emissive interface or shifting the absorption characteristics of a photodetector. Here, we test this hypothesis and contribute to the discussion by presenting a new model system. Through the fabrication of planar organic p-(i-)n junctions, we generate an ensemble of oriented CT states that allows the systematic assessment of electric field impacts. By increasing the thickness of the intrinsic layer at the D-A interface from 0 to 20 nm and by applying external voltages up to 6 V, we realize two different scenarios that controllably tune the intrinsic and extrinsic electric interface fields. By this, we obtain significant shifts of the CT-state peak emission of about 0.5 eV (170 nm from red to green color) from the same D-A material combination. This effect can be explained in a classical electrostatic picture, as the interface electric field alters the potential energy of the electric CT-state dipole. This study illustrates that CT-state energies can be tuned significantly if their electric dipoles are aligned to the interface electric field.

Efficiency Roll-Off in Light-Emitting Electrochemical Cells.

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.

Chemical doping to control the in-situ formed doping structure in light-emitting electrochemical cells.

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.

A metal-free and transparent light-emitting device by sequential spray-coating fabrication of all layers including PEDOT:PSS for both electrodes.

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.

Aggregation-Induced Emission by Molecular Design: A Route to High-Performance Light-Emitting Electrochemical Cells.

The emission efficiency of organic semiconductors (OSCs) often suffers from aggregation caused quenching (ACQ). An elegant solution is aggregation-induced emission (AIE), which constitutes the design of the OSC so that its morphology inhibits quenching π-π interactions and non-radiative motional deactivation. The light-emitting electrochemical cell (LEC) can be sustainably fabricated, but its function depends on motion of bulky ions in proximity of the OSC. It is therefore questionable whether the AIE morphology can be retained during LEC operation. Here, we synthesize two structurally similar OSCs, which are distinguished by that 1 features ACQ while 2 delivers AIE. Interestingly, we find that the AIE-LEC significantly outperforms the ACQ-LEC. We rationalize our finding by showing that the AIE morphology remains intact during LEC operation, and that it can feature appropriately sized free-volume voids for facile ion transport and suppressed non-radiative excitonic deactivation.

Controlling the Emission Zone by Additives for Improved Light-Emitting Electrochemical Cells.

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.

A tool for identifying green solvents for printed electronics.

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 .

Polymer Featuring Thermally Activated Delayed Fluorescence as Emitter in Light-Emitting Electrochemical Cells.

Semiconducting polymers that feature thermally activated delayed fluorescence (TADF) can deliver a much desired combination of high-efficiency and metal-free electroluminescence and cost-efficient solution-based fabrication. A TADF polymer is thus a very good fit for the emitting compound in light-emitting electrochemical cells (LECs) because the commonly employed air-stabile and few-layer LEC architecture is well suited for such solution-based fabrication. Herein we report on the first LEC device based on a TADF polymer as the emitting species, which delivers a luminance of 96 cd m-2 at 4 V and a current efficacy of 1.4 cd A-1 and >600 cd m-2 at 6 V, which is competitive with the performance of multilayer organic light-emitting diodes based on the same TADF polymer. We further utilize the established sensitivity of the emission of the TADF polymer to its environment to draw conclusions on the exciton populations in host-guest and host-free TADF LEC devices.

Author Correction: Design rules for light-emitting electrochemical cells delivering bright luminance at 27.5 percent external quantum efficiency.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Thermally activated delayed fluorescence with 7% external quantum efficiency from a light-emitting electrochemical cell.

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.

Oligomer Electrolytes for Light-Emitting Electrochemical Cells: Influence of the End Groups on Ion Coordination, Ion Binding, and Turn-on Kinetics.

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 cation from 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.

Optical analysis of light-emitting electrochemical cells.

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 (dal) from the anode. We further find that the emission intensity and efficiency are undulating with dal, and establish that the first emission maximum at dal ~ 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 dal ~ 300 nm is wave-guided modes.

Challenging Conventional Wisdom: Finding High-Performance Electrodes for Light-Emitting Electrochemical Cells.

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.

Publisher Correction: The Weak Microcavity as an Enabler for Bright and Fault-tolerant Light-emitting Electrochemical Cells.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has not been fixed in the paper.

The Weak Microcavity as an Enabler for Bright and Fault-tolerant Light-emitting Electrochemical Cells.

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.

Catalytic Nanotruss Structures Realized by Magnetic Self-Assembly in Pulsed Plasma.

Tunable nanostructures that feature a high surface area are firmly attached to a conducting substrate and can be fabricated efficiently over significant areas, which are of interest for a wide variety of applications in, for instance, energy storage and catalysis. We present a novel approach to fabricate Fe nanoparticles using a pulsed-plasma process and their subsequent guidance and self-organization into well-defined nanostructures on a substrate of choice by the use of an external magnetic field. A systematic analysis and study of the growth procedure demonstrate that nondesired nanoparticle agglomeration in the plasma phase is hindered by electrostatic repulsion, that a polydisperse nanoparticle distribution is a consequence of the magnetic collection, and that the formation of highly networked nanotruss structures is a direct result of the polydisperse nanoparticle distribution. The nanoparticles in the nanotruss are strongly connected, and their outer surfaces are covered with a 2 nm layer of iron oxide. A 10 µm thick nanotruss structure was grown on a lightweight, flexible and conducting carbon-paper substrate, which enabled the efficient production of H2 gas from water splitting at a low overpotential of 210 mV and at a current density of 10 mA/cm2.

3D printed water-soluble scaffolds for rapid production of PDMS micro-fluidic flow chambers.

We report a novel method for fabrication of three-dimensional (3D) biocompatible micro-fluidic flow chambers in polydimethylsiloxane (PDMS) by 3D-printing water-soluble polyvinyl alcohol (PVA) filaments as master scaffolds. The scaffolds are first embedded in the PDMS and later residue-free dissolved in water leaving an inscription of the scaffolds in the hardened PDMS. We demonstrate the strength of our method using a regular, cheap 3D printer, and evaluate the inscription process and the channels micro-fluidic properties using image analysis and digital holographic microscopy. Furthermore, we provide a protocol that allows for direct printing on coverslips and we show that flow chambers with a channel cross section down to 40 µm × 300 µm can be realized within 60 min. These flow channels are perfectly transparent, biocompatible and can be used for microscopic applications without further treatment. Our proposed protocols facilitate an easy, fast and adaptable production of micro-fluidic channel designs that are cost-effective, do not require specialized training and can be used for a variety of cell and bacterial assays. To help readers reproduce our micro-fluidic devices, we provide: full preparation protocols, 3D-printing CAD files for channel scaffolds and our custom-made molding device, 3D printer build-plate leveling instructions, and G-code.

Self-Assembled PCBM Nanosheets: A Facile Route to Electronic Layer-on-Layer Heterostructures.

We report on the self-assembly of semicrystalline [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) nanosheets at the interface between a hydrophobic solvent and water, and utilize this opportunity for the realization of electronically active organic/organic molecular heterostructures. The self-assembled PCBM nanosheets can feature a lateral size of >1 cm2 and be transferred from the water surface to both hydrophobic and hydrophilic surfaces using facile transfer techniques. We employ a transferred single PCBM nanosheet as the active material in a field-effect transistor (FET) and verify semiconductor function by a measured electron mobility of 1.2 × 10-2 cm2 V-1 s-1 and an on-off ratio of ∼1 × 104. We further fabricate a planar organic/organic heterostructure with the p-type organic semiconductor poly(3-hexylthiophene-2,5-diyl) as the bottom layer and the n-type PCBM nanosheet as the top layer and demonstrate ambipolar FET operation with an electron mobility of 8.7 × 10-4 cm2 V-1 s-1 and a hole mobility of 3.1 × 10-4 cm2 V-1 s-1.

Realizing Large-Area Arrays of Semiconducting Fullerene Nanostructures with Direct Laser Interference Patterning.

We present a laser interference patterning method for the facile fabrication of large-area and high-contrast arrays of semiconducting fullerene nanostructures, which does not rely on a tedious application of sacrificial photoresists or photomasks. A solution-deposited phenyl-C61-butyric acid methyl ester (PCBM) fullerene thin film is exposed to a spatially modulated illumination intensity, as realized by a two-beam laser interference. The PCBM molecules exposed to strong intensity are photochemically transformed into a low-solubility dimeric state, so that the nontransformed PCBM molecules can be selectively removed in a subsequent solution-based development step. Following brief exposure to green laser light (λ = 532 nm, t = 5 s, p = 0.17 W cm-2) in the designed two-beam interference setup, and a 1 min development in a tuned acetone-chloroform solution, we realize well-defined and ordered PCBM nanostripe patterns with a fwhm line width of ∼200 nm and a repetition rate of ∼2.900 lines mm-1 over a large area of 1 cm2. We demonstrate that a desired high contrast is effectuated because the initial PCBM-dimer transformation rate is dependent on the square of the illumination intensity. The semiconducting functionality of the patterned fullerene is verified in a field-effect transistor experiment, where a typical PCBM nanostripe featured an electron mobility of 5.3 × 10-3 cm2 V-1 s-1 and an on/off ratio of 3 × 103.