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.

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 .

Surface-Bulk Interplay in Vapor-Deposited Glasses: Crossover Length and the Origin of Front Transformation.

Thin film stable glasses transform into a liquid by a moving front that propagates from surfaces or interfaces with higher mobility. We use calorimetric data of vapor-deposited glasses of different thicknesses and stabilities to identify the role of glassy and liquid dynamics on the transformation process. By invoking the existence of an ultrathin intermediate layer whose transformation strongly depends on the properties of both the liquid and the glass, we show that the recovery to equilibrium is driven by the mismatch in the dynamics between glass and liquid. The lifetime of this intermediate layer associated with the moving front is the geometric mean between the bulk transformation time and the alpha relaxation time. Within this view, we explain the observed dependencies of the growth front velocity and the crossover length with both stability and temperature. Extrapolation of these results points towards ordinary thin film glasses transforming via a frontlike transformation mechanism if heated sufficiently fast, establishing a close connection between vapor-deposited and liquid-cooled glasses.

Kinetic arrest of front transformation to gain access to the bulk glass transition in ultrathin films of vapour-deposited glasses.

Physical vapour deposition has emerged as the technique to obtain glasses of unbeatable stability. However, vapour deposited glasses exhibit a different transformation mechanism to ordinary glasses produced from liquid. Vapour deposited glasses of different thermodynamic stability, from ultrastable to those similar to ordinary glasses, transform into the liquid state via front propagation starting at the most mobile surfaces/interfaces, at least for the first stages of the transformation, eventually dynamiting the high thermal stability achieved for some of these glasses. A previous study showed that it was possible to avoid this transformation front by capping the films with a higher Tg material. We show here fast calorimetry measurements on TPD and IMC vapour deposited glasses capped respectively with TCTA and TPD. This capped configuration is very effective in suppressing the heterogeneous transformation of the stable glasses into the supercooled liquid and shifts the devitrification temperature to much higher values, where the bulk homogeneous mechanism becomes active. This approach may be useful to further study the bulk glass transition in thin films.

High-performance organic light-emitting diodes comprising ultrastable glass layers.

Organic light-emitting diodes (OLEDs) are one of the key solid-state light sources for various applications including small and large displays, automotive lighting, solid-state lighting, and signage. For any given commercial application, OLEDs need to perform at their best, which is judged by their device efficiency and operational stability. We present OLEDs that comprise functional layers fabricated as ultrastable glasses, which represent the thermodynamically most favorable and, thus, stable molecular conformation achievable nowadays in disordered solids. For both external quantum efficiencies and LT70 lifetimes, OLEDs with four different phosphorescent emitters show >15% enhancements over their respective reference devices. The only difference to the latter is the growth condition used for ultrastable glass layers that is optimal at about 85% of the materials' glass transition temperature. These improvements are achieved through neither material refinements nor device architecture optimization, suggesting a general applicability of this concept to maximize the OLED performance, no matter which specific materials are used.

The role of thermodynamic stability in the characteristics of the devitrification front of vapour-deposited glasses of toluene.

Physical vapour deposition (PVD) has settled in as an alternative method to prepare glasses with significantly enhanced properties, providing new insights into the understanding of glass transition. One of the striking properties of some PVD glasses is their transformation into liquid via a heterogeneous mechanism that initiates at surfaces/interfaces. Here, we use membrane-based fast-scanning nanocalorimetry (104 K s-1) to analyse the variables that govern the transformation mechanism of vapour-deposited toluene glasses with different stabilities. Thin films ranging from 20 to 250 nm were prepared at deposition temperatures between 0.70 and 1.15 times the glass transition temperature. We show how a propagating growth front is the initial transformation mechanism in all the vapour deposited samples, revealing a clear tendency to faster front velocities for less stable samples. Contrary to other glass-formers such as indomethacin, toluene shows a one-to-one relationship between limiting fictive temperature and front velocity. We associate this behaviour with the much simpler molecular geometry of toluene, which would prevent the presence of strong preferential molecular arrangements in the glass. However, the propagation distance of the growth front before the homogenous transformation mechanism dominates the transition is found to be dependent on the preparation conditions rather than on the thermal stability of the glass. Understanding the link between the growth variables and the properties of PVD glasses is crucial for finding and developing potential applications of this type of glass.

Transformation kinetics of vapor-deposited thin film organic glasses: the role of stability and molecular packing anisotropy.

While ordinary glasses transform into supercooled liquid via a homogeneous bulk mechanism, thin film glasses of higher stability transform heterogeneously by a front propagating from the surface and/or the interfaces. In this work, we use quasi-adiabatic fast scanning nanocalorimetry to determine the heat capacity of thin glassy layers of indomethacin vapor-deposited in a broad temperature range of 110 K below the glass transition temperature. Their variation in fictive temperature amounts to 40 K. We show that a propagating front is the initial transformation mechanism in all cases. Using an ad hoc surface normalization procedure we determine the corresponding growth front velocity for the whole range of deposition temperatures. Although the transformation rate changes by a factor of 10 between the most and less stable samples, the relation between the mobility of the front and the thermodynamic stability of the glass is not uniquely defined. Glasses grown above 280 K, which are at equilibrium with the supercooled liquid, present a different dependence of the growth front velocity on fictive temperature compared to glasses grown out of equilibrium at Tdep < 250 K. These glasses transform faster with increasing Tf. Our data clarify previous reports and support the evidence that the fictive temperature alone is not an absolute indicator of the properties of the glass, at least when its structure is not completely isotropic. To interpret the data, we propose that the growth front velocity depends on three terms: the mobility of the liquid at a given temperature, the mobility of the glass and the arrangement of the molecules in the glass.

Evaluation of growth front velocity in ultrastable glasses of indomethacin over a wide temperature interval.

Ultrastable thin film glasses transform into supercooled liquid via propagating fronts starting from the surface and/or interfaces. In this paper, we analyze the consequences of this mechanism in the interpretation of specific heat curves of ultrastable glasses of indomethacin for samples with varying thickness from 20 nm up to several microns. We demonstrate that ultrastable films above 20 nm have identical fictive temperatures and that the apparent change of onset temperature in the specific heat curves originates from the mechanism of transformation and the normalization procedure. An ad hoc surface normalization of the heat capacity yields curves which collapse into a single one irrespective of their thickness. Furthermore, we fit the surface-normalized specific heat curves with a heterogeneous transformation model to evaluate the velocity of the growth front over a much wider temperature interval than previously reported. Our data expands previous values up to Tg + 75 K, covering 12 orders of magnitude in relaxation times. The results are consistent with preceding experimental and theoretical studies. Interestingly, the mobility of the supercooled liquid in the region behind the transformation front remains constant throughout the thickness of the layers.