Organic light-emitting diodes (OLEDs) have attracted much attention in research and industry thanks to their capability to emit light with high efficiency and to deliver high-quality white light that provides good color rendering. OLEDs feature homogeneous large area emission and can be produced on flexible substrates. In terms of efficiency, OLEDs can compete with highly efficient conventional light sources but their efficiency typically decreases at high brightness levels, an effect known as efficiency roll-off. In recent years, much effort has been undertaken to understand the underlying processes and to develop methods that improve the high-brightness performance of OLEDs. In this review, we summarize the current knowledge and provide a detailed description of the relevant principles, both for phosphorescent and fluorescent emitter molecules. In particular, we focus on exciton-quenching mechanisms, such as triplet-triplet annihilation, quenching by polarons, or field-induced quenching, but also discuss mechanisms such as changes in charge carrier balance. We further review methods that may reduce the roll-off and thus enable OLEDs to be used in high-brightness applications.

We investigate the average orientation of the transition dipole moments of two green phosphorescent emitters Ir(ppy)3 and Ir(ppy)2(acac) embedded in a CBP matrix, using in-situ angle resolved electroluminescence spectroscopy and optical simulations. The dipole orientation of Ir(ppy)3 is nearly isotropic while 77% of the dipoles are horizontally aligned for Ir(ppy)2(acac). Optimized organic light-emitting diodes based on these emitters achieve external quantum efficiencies of 18.3% (Ir(ppy)3) and 21.7% (Ir(ppy)2(acac)). This difference is partially explained by the different dipole orientations.

In organic light‐emitting diodes (OLEDs), horizontal orientation of the emissive transition dipole moment (TDM) can improve light outcoupling efficiency by up to 50% relative to random orientation. Therefore, there have been extensive efforts to identify drivers of horizontal orientation. The aspect ratio of the emitter molecule and the glass‐transition temperature (Tg) of the films are currently regarded as particularly important. However, there remains a paucity of systematic studies that establish the extent to which these and other parameters control orientation in the wide range of emitter systems relevant for state‐of‐the‐art OLEDs. Here, recent work on molecular orientation of fluorescent and thermally activated delayed fluorescent emitters in vacuum‐processed OLEDs is reviewed. Additionally, to identify parameters linked to TDM orientation, a meta‐analysis of 203 published emitter systems is conducted and combined with density‐functional theory calculations. Molecular weight (MW) and linearity are identified as key parameters in neat systems. In host–guest systems with low‐MW emitters, orientation is mostly influenced by the host Tg, whereas the length and MW of the emitter become more relevant for systems involving higher‐MW emitters. To close, a perspective of where the field must advance to establish a comprehensive model of molecular orientation is given.

The orientation of seven iridium-based emitter molecules for OLEDs is compared and surprisingly all except Ir(ppy)3 show considerable horizontal orientation.