Revealing the Origin of Fast Delayed Fluorescence in a Donor Functionalized Bisterpyridine.

A new carbazole-substituted bisterpyridine with pronounced delayed fluorescence is presented. While the molecular donor-acceptor-donor design suggests the origin of this to be thermally activated delayed fluorescence (TADF), results from various photophysical characterizations, OLED characteristics, temperature-dependent NMR spectroscopy, and DFT calculations all point against the involvement of triplet states. The molecule exhibits blue emission at about 440 nm with two or more fast decay channels in the lower nanosecond range in both solution and thin films. The delayed emission is proposed to be caused by rotational vibrational modes. We suggest that these results are generally applicable, especially for more complex molecules, and should be considered as alternative or competitive emissive relaxation pathways in the field of organic light emitting materials.

Mesogenic Groups Control the Emitter Orientation in Multi-Resonance TADF Emitter Films.

The use of thermally activated delayed fluorescence (TADF) emitters and emitters that show preferential horizontal orientation of their transition dipole moment (TDM) are two emerging strategies to enhance the efficiency of OLEDs. We present the first example of a liquid crystalline multi-resonance TADF (MR-TADF) emitter, DiKTa-LC. The compound possesses a nematic liquid crystalline phase between 80 °C and 110 °C. Importantly, the TDM of the spin-coated film shows preferential horizontal orientation, with an anisotropy factor, a, of 0.28, which is preserved in doped poly(vinylcarbazole) films. Green-emitting (λEL =492 nm) solution-processed OLEDs based on DiKTa-LC showed an EQEmax of 13.6 %. We thus demonstrate for the first time how self-assembly of a liquid crystalline TADF emitter can lead to the so-far elusive control of the orientation of the transition dipole in solution-processed films, which will be of relevance for high-performance solution-processed OLEDs.

Spectroscopic near-infrared photodetectors enabled by strong light-matter coupling in (6,5) single-walled carbon nanotubes.

Strong light-matter coupling leads to the formation of mixed exciton-polariton states, allowing for a rigorous manipulation of the absorption and emission of excitonic materials. Here, we demonstrate the realization of this promising concept in organic photodetectors. By hybridizing the E11 exciton of semiconducting (6,5) single-walled carbon nanotubes (SWNTs) with near-infrared cavity photons, we create spectrally tunable polariton states within a photodiode. In turn, we are able to red-shift the detection peak that coincides with the lower polariton band. Our photodiodes comprise a metal cavity to mediate strong coupling between light and SWNTs and utilize P3HT and PC70BM as the electron donor and acceptor, respectively. The diodes are formed either via mixing of SWNTs, P3HT, and PC70BM to create a bulk heterojunction or by sequential processing of layers to form flat heterojunctions. The resulting near-infrared sensors show tunable, efficient exciton harvesting in an application-relevant wavelength range between 1000 nm and 1300 nm, with optical simulations showing a possible extension beyond 1500 nm.

High-Brightness Blue Polariton Organic Light-Emitting Diodes.

Polariton organic light-emitting diodes (POLEDs) use strong light-matter coupling as an additional degree of freedom to tailor device characteristics, thus making them ideal candidates for many applications, such as room temperature laser diodes and high-color purity displays. However, achieving efficient formation of and emission from exciton-polaritons in an electrically driven device remains challenging due to the need for strong absorption, which often induces significant nonradiative recombination. Here, we investigate a novel POLED architecture to achieve polariton formation and high-brightness light emission. We utilize the blue-fluorescent emitter material 4,4'-Bis(4-(9H-carbazol-9-yl)styryl)biphenyl (BSBCz), which exhibits strong absorption and a highly horizontal transition-dipole orientation as well as a high photoluminescence quantum efficiency, even at high doping concentrations. We achieve a peak luminance of over 20,000 cd/m2 and external quantum efficiencies of more than 2%. To the best of our knowledge, these values represent the highest reported so far for electrically driven polariton emission from an organic semiconductor emitting in the blue region of the spectrum. Our work therefore paves the way for a new generation of efficient and powerful optoelectronic devices based on POLEDs.

Orientation distributions of vacuum-deposited organic emitters revealed by single-molecule microscopy.

The orientation of luminescent molecules in organic light-emitting diodes strongly influences device performance. However, our understanding of the factors controlling emitter orientation is limited as current measurements only provide ensemble-averaged orientation values. Here, we use single-molecule imaging to measure the transition dipole orientation of individual emitter molecules in a state-of-the-art thermally evaporated host and thereby obtain complete orientation distributions of the hyperfluorescence-terminal emitter C545T. We achieve this by realizing ultra-low doping concentrations (10-6 wt%) of C545T and minimising background levels to reliably measure its photoluminescence. This approach yields the orientation distributions of >1000 individual emitter molecules in a system relevant to vacuum-processed devices. Analysis of solution- and vacuum-processed systems reveals that the orientation distributions strongly depend on the nanoscale environment of the emitter. This work opens the door to attaining unprecedented information on the factors that determine emitter orientation in current and future material systems for organic light-emitting devices.

Identification of the Key Parameters for Horizontal Transition Dipole Orientation in Fluorescent and TADF Organic Light-Emitting Diodes.

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.

Real-time observation of conformational switching in single conjugated polymer chains.

Conjugated polymers (CPs) are an important class of organic semiconductors that combine novel optoelectronic properties with simple processing from organic solvents. It is important to study CP conformation in solution to understand the physics of these materials and because it affects the properties of solution-processed films. Single-molecule techniques are unique in their ability to extract information on a chain-to-chain basis; however, in the context of CPs, technical challenges have limited their general application to host matrices or semiliquid environments that constrain the conformational dynamics of the polymer. We introduce a conceptually different methodology that enables measurements in organic solvents using the single-end anchoring of polymer chains to avoid diffusion while preserving polymer flexibility. We explore the effect of organic solvents and show that, in addition to chain-to-chain conformational heterogeneity, collapsed and extended polymer segments can coexist within the same chain. The technique enables real-time solvent-exchange measurements, which show that anchored CP chains respond to sudden changes in solvent conditions on a subsecond time scale. Our results give an unprecedented glimpse into the mechanism of solvent-induced reorganization of CPs and can be expected to lead to a new range of techniques to investigate and conformationally manipulate CPs.