Identification of OLED Degradation Scenarios by Kinetic Monte Carlo Simulations of Lifetime Experiments.

We show how three-dimensions kinetic Monte Carlo simulations can be used to carry out an operational lifetime study of thermally activated delayed fluorescence (TADF) organic light-emitting diodes (OLEDs) and to deduce the sensitivity to various degradation scenarios. The approach is demonstrated for an experimentally well-characterized efficient green-emitting device. The simulation workflow includes an equilibration phase, an equilibrated pristine state phase and a degradation phase. Acceleration of the simulations by extrapolation from simulations at large current densities makes the simulation time realistically feasible. Such a procedure is also often followed in experimental studies. Degradation is assumed to be triggered by exciton-polaron quenching and exciton-exciton annihilation processes. A comparison of the simulated and experimental time-dependence of the luminance decay provides the probability that a degradation-triggering event leads to the formation of a degraded molecule. For the TADF OLED that has been studied, this parameter is only weakly dependent on the assumed scenario, provided that the degraded molecules are assumed to form trap sites, and is found to be ∼ ( 0.2 - 0.7 ) × 1 0 - 9 . The approach is expected to enable systematic in silico studies of the operational lifetime and its sensitivity to the material composition, layer structure, charge carrier balance, and the use of refined device principles such as hyperfluorescence.

High energy acceptor states strongly enhance exciton transfer between metal organic phosphorescent dyes.

Exciton management in organic light-emitting diodes (OLEDs) is vital for improving efficiency, reducing device aging, and creating new device architectures. In particular in white OLEDs, exothermic Förster-type exciton transfer, e.g. from blue to red emitters, plays a crucial role. It is known that a small exothermicity partially overcomes the spectral Stokes shift, enhancing the fraction of resonant donor-acceptor pair states and thus the Förster transfer rate. We demonstrate here a second enhancement mechanism, setting in when the exothermicity exceeds the Stokes shift: transfer to multiple higher-lying electronically excited states of the acceptor molecules. Using a recently developed computational method we evaluate the Förster transfer rate for 84 different donor-acceptor pairs of phosphorescent emitters. As a result of the enhancement the Förster radius tends to increase with increasing exothermicity, from around 1 nm to almost 4 nm. The enhancement becomes particularly strong when the excited states have a large spin-singlet character.

Charge Transport by Superexchange in Molecular Host-Guest Systems.

Charge transport in disordered organic semiconductors is generally described as a result of incoherent hopping between localized states. In this work, we focus on multicomponent emissive host-guest layers as used in organic light-emitting diodes (OLEDs), and show using multiscale ab initio based modeling that charge transport can be significantly enhanced by the coherent process of molecular superexchange. Superexchange increases the rate of emitter-to-emitter hopping, in particular if the emitter molecules act as relatively deep trap states, and allows for percolation path formation in charge transport at low guest concentrations.

Molecular-scale simulation of electroluminescence in a multilayer white organic light-emitting diode.

In multilayer white organic light-emitting diodes the electronic processes in the various layers--injection and motion of charges as well as generation, diffusion and radiative decay of excitons--should be concerted such that efficient, stable and colour-balanced electroluminescence can occur. Here we show that it is feasible to carry out Monte Carlo simulations including all of these molecular-scale processes for a hybrid multilayer organic light-emitting diode combining red and green phosphorescent layers with a blue fluorescent layer. The simulated current density and emission profile are shown to agree well with experiment. The experimental emission profile was obtained with nanometre resolution from the measured angle- and polarization-dependent emission spectra. The simulations elucidate the crucial role of exciton transfer from green to red and the efficiency loss due to excitons generated in the interlayer between the green and blue layers. The perpendicular and lateral confinement of the exciton generation to regions of molecular-scale dimensions revealed by this study demonstrate the necessity of molecular-scale instead of conventional continuum simulation.