Ludvig Edman

Ambient fabrication of flexible and large-area organic light-emitting devices using slot-die coating

The grand vision of manufacturing large-area emissive devices with low-cost roll-to-roll coating methods, akin to how newspapers are produced, appeared with the emergence of the organic light-emitting diode about 20 years ago. Today, small organic light-emitting diode displays are commercially available in smartphones, but the promise of a continuous ambient fabrication has unfortunately not materialized yet, as organic light-emitting diodes invariably depend on the use of one or more time- and energy-consuming process steps under vacuum. Here we report an all-solution-based fabrication of an alternative emissive device, a light-emitting electrochemical cell, using a slot-die roll-coating apparatus. The fabricated flexible sheets exhibit bidirectional and uniform light emission, and feature a fault-tolerant >1-μm-thick active material that is doped in situ during operation. It is notable that the initial preparation of inks, the subsequent coating of the constituent layers and the final device operation all could be executed under ambient air.

The dynamic organic p-n junction

Static p-n junctions in inorganic semiconductors are exploited in a wide range of todays electronic appliances. Here, we demonstrate the in situ formation of a dynamic p-n junction structure within an organic semiconductor through electrochemistry. Specifically, we use scanning kelvin probe microscopy and optical probing on planar light-emitting electrochemical cells (LECs) with a mixture of a conjugated polymer and an electrolyte connecting two electrodes separated by 120 microm. We find that a significant portion of the potential drop between the electrodes coincides with the location of a thin and distinct light-emission zone positioned >30 microm away from the negative electrode. These results are relevant in the context of a long-standing scientific debate, as they prove that electrochemical doping can take place in LECs. Moreover, a study on the doping formation and dissipation kinetics provides interesting detail regarding the electronic structure and stability of the dynamic organic p-n junction, which may be useful in future dynamic p-n junction-based devices.

A Unifying Model for the Operation of Light-Emitting Electrochemical Cells

The application of doping in semiconductors plays a major role in the high performances achieved to date in inorganic devices. In contrast, doping has yet to make such an impact in organic electronics. One organic device that does make extensive use of doping is the light-emitting electrochemical cell (LEC), where the presence of mobile ions enables dynamic doping, which enhances carrier injection and facilitates relatively large current densities. The mechanism and effects of doping in LECs are, however, still far from being fully understood, as evidenced by the existence of two competing models that seem physically distinct: the electrochemical doping model and the electrodynamic model. Both models are supported by experimental data and numerical modeling. Here, we show that these models are essentially limits of one master model, separated by different rates of carrier injection. For ohmic nonlimited injection, a dynamic p-n junction is formed, which is absent in injection-limited devices. This unification is demonstrated by both numerical calculations and measured surface potentials as well as light emission and doping profiles in operational devices. An analytical analysis yields an upper limit for the ratio of drift and diffusion currents, having major consequences on the maximum current density through this type of device.

Flexible and Metal-Free Light-Emitting Electrochemical Cells Based on Graphene and PEDOT-PSS as the Electrode Materials

We report flexible and metal-free light-emitting electrochemical cells (LECs) using exclusively solution-processed organic materials and illustrate interesting design opportunities offered by such conformable devices with transparent electrodes. Flexible LEC devices based on chemically derived graphene (CDG) as the cathode and poly(3,4-ethylenedioxythiophene) mixed with poly(styrenesulfonate) as the anode exhibit a low turn-on voltage for yellow light emission (V = 2.8 V) and a good efficiency 2.4 (4.0) cd/A at a brightness of 100 (50) cd/m(2). We also find that CDG is electrochemically inert over a wide potential range (+1.2 to -2.8 V vs ferrocene/ferrocenium) and exploit this property to demonstrate planar LEC devices with CDG as both the anode and the cathode.

A High-Rate Manganese Oxide for Rechargeable Lithium Battery Applications

Li x MnO 2 made by ion exchange of glycine-nitrate combustion synthesis-processed (GNP) orthorhombic Na 0.44 MnO 2 (GNP-Li x MnO 2 ) has been cycled in lithium/liquid electrolyte cell configurations at room temperature and lithium/polymer cell configurations at 85°C over one hundred times without showing capacity fading or phase conversion to spinel. At 2.5 mA/cm 2 in liquid cells (5C rate) or I mA/cm 2 (1.5C rate) in polymer cells, 80-95% of the expected capacity is delivered. The remarkable stability is attributable to the unusual double tunnel structure, which cannot easily undergo rearrangement to spinel. The enhanced rate capability of GNP-Li x MnO 2 compared to conventionally prepared materials is attributable to the shorter particle length, which allows faster diffusion of lithium ions along the tunnels.

Small-molecule light-emitting electrochemical cells: evidence for in situ electrochemical doping and functional operation

We demonstrate that non-ionic small molecules (SMs) can function as the doping and emissive compound in light-emitting electrochemical cells (LECs), and that high brightness and decent efficiency can be attained for such devices. It is plausible that the expansion of the LEC library, to include easy-to-purify and tunable non-ionic SM compounds, could represent a viable path towards improved LEC devices.

White Light from a Single-Emitter Light-Emitting Electrochemical Cell

We report a novel and generic approach for attaining white light from a single-emitter light-emitting electrochemical cell (LEC). With an active-layer comprising a multifluorophoric conjugated copolymer (MCP) and an electrolyte designed to inhibit MCP energy-transfer interactions during LEC operation, we are able to demonstrate LECs that emit broad-band white light with a color rendering index of 82, a correlated-color temperature of 4000 K, and a current conversion efficacy of 3.8 cd/A. It is notable that this single-emitter LEC configuration eliminates color-drift problems stemming from phase separation, which are commonly observed in conventional blended multiemitter devices. Moreover, the key role of the electrolyte in limiting undesired energy-transfer reactions is highlighted by the observation that an electrolyte-free organic light-emitting diode comprising the same MCP emits red light.

Separating Ion and Electron Transport: The Bilayer Light-Emitting Electrochemical Cell

The current generation of polymer light-emitting electrochemical cells (LECs) suffers from insufficient stability during operation. One identified culprit is the active material, which comprises an intimate blend between an ion-conducting electrolyte and an electron-transporting conjugated polymer, as it tends to undergo phase separation during long-term operation and the intimate contact between the ion- and electron-transporting components provokes side reactions. To address these stability issues, we present here a bilayer LEC structure in which the electrolyte is spatially separated from the conjugated polymer. We demonstrate that employing this novel device structure, with its clearly separated ion- and electron-transport paths, leads to distinctly improved LEC performance in the form of decreased turn-on time and improved light emission. We also point out that it will allow for the utilization of combinations of active materials having mutually incompatible solubilities.

NMR and Raman studies of a novel fast-ion-conducting polymer-in-salt electrolyte based on LiCF3SO3 and PAN

We report spectroscopic results from investigations of a novel solid polymeric fast-ion-conductor based on poly(acrylonitrile), (PAN, of repeat unit [CH 2 CH(CN)] n ), and the salt LiCF 3 SO 3 , From NMR studies of the temperature and concentration dependencies of 7 Li- and 1 H-NMR linewidths, we conclude that significant ionic motion occurs at temperatures close to the glass transition temperature of these polymer-in-salt electrolytes, in accordance with a recent report on the ionic conductivity. In the dilute salt-in-polymer regime, however, ionic motion appears mainly to be confined to local salt-rich domains, as determined from the dramatic composition dependence of the ionic conductivity. FT-Raman spectroscopy is used to directly probe the local chemical anionic environment. as well as the Li + - PAN interaction. The characteristic δ s (CF 3 ) mode of the CF 3 SO 3 anion at ∼ 750- 780 cm shows that the ionic substructure is highly complex. Notably, no spectroscopic evidence of free anions is found even at relatively salt-depleted compositions (e.g. N:Li ∼ 60 10:1). A strong Li + - PAN interaction is manifested as a pronounced shift of the characteristic polymer C=N stretching mode, found at ∼ 2244 cm -1 in pure PAN, to ∼ 2275 cm -1 for Li + -coordinated C=N moieties. Our proton-NMR data suggest that upon complexation of PAN with LiCF 3 SO 3 , the glass transition occurs at progressively lower temperatures.

Photo-Induced and Resist-Free Imprint Patterning of Fullerene Materials for Use in Functional Electronics

We report a novel and potentially generic method for the efficient patterning of films of organic semiconductors and demonstrate the merit of the method on the high-solubility fullerene [6,6]-phenyl C(61)-butyric acid methyl ester (PCBM). The patterning technique is notably straightforward as it requires no photoresist material and encompasses only two steps: (i) exposure of select film areas to visible laser light during which the PCBM mononer is photochemically converted into a dimeric state, and (ii) development via solvent washing after which the nonexposed portions of the PCBM film are selectively removed. Importantly, the method is highly benign in that it leaves the electronic properties of the remaining patterned material intact, which is directly evidenced by the fact that we fabricate fully functional arrays of micrometer-sized field-effect transistors with patterned PCBM as the active material.