Organic materials that exhibit thermally activated delayed fluorescence (TADF) are an attractive class of functional materials that have witnessed a booming development in recent years. Since Adachi et al. reported high-performance TADF-OLED devices in 2012, there have been many reports regarding the design and synthesis of new TADF luminogens, which have various molecular structures and are used for different applications. In this review, we summarize and discuss the latest progress concerning this rapidly developing research field, in which the majority of the reported TADF systems are discussed, along with their derived structure–property relationships, TADF mechanisms and applications. We hope that such a review provides a clear outlook of these novel functional materials for a broad range of scientists within different disciplinary areas and attracts more researchers to devote themselves to this interesting research field.

Recent advances in organic thermally activated delayed fluorescence materials.

We thank the University of St Andrews for support. EZ-C thanks the Leverhulme Trust for financial support (RPG-2016-047). and the EPSRC (EP/P010482/1) for financial support.

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Purely Organic Thermally Activated Delayed Fluorescence Materials for Organic Light-Emitting Diodes.

Thermally activated delayed fluorescence (TADF) emitters, which produce light by harvesting both singlet and triplet excitons without noble metals, are emerging as next-generation organic electroluminescent materials. In the past few years, there have been rapid advances in molecular design criteria, our understanding of the photophysics underlying TADF and the applications of TADF materials as emitters in organic light-emitting diodes (OLEDs). This topic is set to remain at the forefront of research in optoelectronic organic materials for the foreseeable future. In this Review, we focus on state-of-the-art materials design and understanding of the photophysical processes, which are being leveraged to optimize the performance of OLED devices. Notably, we also appraise dendritic and polymeric TADF emitters — macromolecular materials that offer the potential advantages of low cost, solution processable and large-area OLED fabrication. Thermally activated delayed fluorescence (TADF) emitters are promising electroluminescent materials for next-generation organic light-emitting diodes (OLEDs). In this Review, the molecular design, photophysical characteristics and OLEDs composed of small-molecule, dendritic and polymeric TADF emitters are discussed.

All-organic thermally activated delayed fluorescence materials for organic light-emitting diodes

Recently, organic thermally activated delayed fluorescence (TADF) emitters have attracted a great deal of attention because they can theoretically realize 100% internal quantum efficiency. Many TADF emitters have been developed since the first demonstration of close to 20% external quantum efficiency in the devices. Recently developed TADF emitters demonstrated close to 37% external quantum efficiency in blue, above 30% external quantum efficiency in green, and close to 18% external quantum efficiency in red devices. Therefore, TADF organic light-emitting diodes could potentially be substituted for high-efficiency phosphorescent organic light-emitting diodes. In this work, we reviewed molecular design strategies of organic-based TADF emitters by classifying them into several categories depending on the material parameters required for the TADF emitters. In addition, we proposed a future development direction of TADF emitters to make them competitive with phosphorescent emitters.

Molecular Design Strategy of Organic Thermally Activated Delayed Fluorescence Emitters

Luminescent materials that exhibit narrowband emission are vital for full-colour displays. Here, we report a thermally activated delayed-fluorescence material that exhibits ultrapure blue emission with full-width at half-maximum of just 14 nm. The emitter consists of five benzene rings connected by two boron and four nitrogen atoms and two diphenylamino substituents. The multiple resonance effect of the boron and nitrogen atoms induces significant localization of the highest occupied and lowest unoccupied molecular orbitals on different atoms to minimize not only the vibronic coupling between the ground state (S0) and the singlet excited state (S1) but also the energy gap between the S1 state and triplet excited state (T1). Organic light-emitting diode devices employing the emitter emit light at 469 nm with full-width at half-maximum of 18 nm with an external quantum efficiency of 34.4% at the maximum and 26.0% at 1,000 cd m−2. A blue emitter based on thermally activated delayed fluorescence is narrowband and efficient.

Narrowband deep-blue organic light-emitting diode featuring an organoboron-based emitter

Ultrapure blue-fluorescent molecules based on thermally activated delayed fluorescence are developed. Organic light-emitting diode (OLED) devices employing the new emitters exhibit a deep blue emission at 467 nm with a full-width at half-maximum of 28 nm, CIE coordinates of (0.12, 0.13), and an internal quantum efficiency of ≈100%, which represent record-setting performance for blue OLED devices.

Ultrapure Blue Thermally Activated Delayed Fluorescence Molecules: Efficient HOMO–LUMO Separation by the Multiple Resonance Effect

The increasing attention devoted to triangulenes and their heteroatom derivatives inspired us to explore a divergent synthesis of heteroatom-centered 4,8,12-triazatriangulenes, which involved the preparation of a nitrogen-containing macrocyclic precursor and subsequent central heteroatom introduction by electrophilic C−Li and C−H substitution. The boron-centered triangulene has a planar structure unlike the bowl-shaped phosphorus- and silicon-centered triangulenes. The described synthetic procedure can be used to fabricate a broad range of attractive functional materials, for example, for organic light-emitting diodes, based on heteroatom-centered triangulenes.

Divergent Synthesis of Heteroatom-Centered 4,8,12-Triazatriangulenes.

Palladium-catalyzed, hydroxy-group-directed C-H arylation of [1,1'-biphenyl]-2-ols with chloroarenes was performed. The reaction showed a broad substrate scope and was successfully applied to pharmaceuticals containing a chloro group. Using 2-heteroarylphenols instead of [1,1'-biphenyl]-2-ols also yielded the desired products. The arylated product was further transformed into a triphenylene derivative.

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Keisuke Kinoshita

Papers

Ultrapure Blue Thermally Activated Delayed Fluorescence Molecules: Efficient HOMO–LUMO Separation by the Multiple Resonance Effect

Divergent Synthesis of Heteroatom-Centered 4,8,12-Triazatriangulenes.

Palladium-Catalyzed C-H Arylation of [1,1'-Biphenyl]-2-ols with Chloroarenes.