Thermally activated delayed fluorescence molecules and their new applications aside from OLEDs

Thermally activated delayed fluorescence molecules (TADF) molecules have been found to undergo efficient intersystem crossing (ISC) and reverse intersystem crossing (RISC) processes, which benefit their successful applications in organic light emitting diodes (OLEDs). Due to their long-lived delayed fluorescence, TADF molecules can also be applied in time-resolved luminescence imaging. Besides their special singlet properties, their excited triplet characteristics provide their potential applications in triplet-triplet annihilation upconversion (TTA-UC), photodynamic therapy (PDT) and organic photocatalytic synthesis by used as a triplet photosensitizer.     

Peripherally Heavy-Atom-Decorated Strategy Towards High-Performance Pure Green Electroluminescence with External Quantum Efficiency over 40 %

Heavy-atom integration into thermally activated delayed fluorescence (TADF) molecule could significantly promote the reverse intersystem crossing (RISC) process. However, simultaneously achieving high efficiency, small roll-off, narrowband emission and good operational lifetime remains a big challenge for the corresponding organic light-emitting diodes (OLEDs). Herein, we report a pure green multi-resonance TADF molecule BN-STO by introducing a peripheral heavy atom selenium onto the parent BN-Cz molecule. The organic light-emitting diode device based on BN-STO exhibited state-of-the-art performance with a maximum external quantum efficiency (EQE) of 40.1 %, power efficiency (PE) of 176.9 lm W⁻¹, well-suppressed efficiency roll-off and pure green gamut. This work reveals a feasible strategy to reach a balance between fast RISC process and narrow full width at half maximum (FWHM) of MR-TADF by heavy atom effect.     

Molecular Design Tactics for Highly Efficient Thermally Activated Delayed Fluorescence Emitters for Organic Light Emitting Diodes

Recently, pure organic thermally activated delayed fluorescence (TADF) emitters have attracted considerable interest from the scientific community in the field of organic light emitting diodes (OLEDs) as they can theoretically realize 100 % of the internal quantum efficiency by exploiting both the singlet and triplet excitons via the reverse intersystem crossing enabled by small singlet‐triplet energy splitting. Currently, the external quantum efficiency of the TADF emitters is reaching the level of phosphorescent emitters. Therefore, the TADF approach is considered as a potential alternative to the low efficiency conventional fluorescent and expensive phosphorescent emitters. In this account, we summarized our recent development of blue and green TADF molecular designs to improve the device performances of the TADF devices.     

Cluster Light-Emitting Diodes Containing Copper Iodine Cube with 100 % Exciton Utilization Using Host-Cluster Synergy

Clusters combine the advantages of organic molecules and inorganic nanomaterials, which are promising alternatives for optoelectronic applications. Nonetheless, recently emerged cluster light-emitting diodes require further excited state optimization of cluster emitters, especially to reduce population of the cluster-centered triplet quenching state (³CC). Here we report that redox-active ligands enhance reverse intersystem crossing (RISC) of Cu₄I₄ cluster for triplet-to-singlet conversion, and thermally activated delayed fluorescence (TADF) host can provide an external RISC channel. It indicates that the complementarity between TADF host and cluster in RISC transitions gives rise to 100 % triplet conversion efficiency and complete singlet exciton convergence, rendering 100-fold increased singlet radiation rate constant and tenfold decreased triplet non-radiation rate constant. We achieve a photoluminescence quantum yield of 99 % and a record external quantum efficiency of 29.4 %.     

Molecular Design Strategy for Orange Red Thermally Activated Delayed Fluorescence Emitters in Organic Light-Emitting Diodes (OLEDs)

Pure organic molecules based thermally activated delayed fluorescence (TADF) emitters have been successfully developed in recent years for their propitious application in highly efficient organic light emitting diodes (OLEDs). In the case of orange red emitters, the non-radiative process is known to be a serious issue due to its lower lying singlet energy level. However, recent studies indicate that there are tremendous efforts put to develop efficient orange red TADF emitters. In addition, the external quantum efficiency (EQE) of heteroaromatic based orange red TADF OLEDs surpassed 30 %. Such heteroaromatic type emitters showed wide emission spectra; therefore, more attention is being paid to develop highly efficient orange red TADF emitters along with good color purity. Herein, the recent progress of orange red TADF emitters based on molecular structures, such as cyanobenzene, heteroaromatic, naphthalimide, and boron-based acceptors, are reviewed. Further, our insight on these acceptors has been provided by their photophysical studies and device performances. Future perspectives of orange red TADF emitters for real practical applications are discussed.     

Dithia[3.3]paracyclophane Core: A Versatile Platform for Triplet State Fine‐Tuning and Through‐Space TADF Emission

Thermally activated delayed fluorescence (TADF) based on through‐space donor and acceptor interactions constitute a recent and promising approach to develop efficient TADF emitters. Novel TADF isomers using a dithia[3.3]‐paracyclophane building block as a versatile 3D platform to promote through‐space interactions are presented. Such a 3D platform allows to bring together the D and A units into close proximity and to probe the effect of their orientation, contact site and distance on their TADF emission properties. This study provides evidence that the dithia[3.3]paracyclophane core is a promising platform to control intramolecular through‐space interactions and obtain an efficient TADF emission with short reverse‐intersystem crossing (RISC) lifetimes. In addition, this study demonstrates that this design can tune the energy levels of the triplet states and leads to an upconversion from ³CT to ³LE that promotes faster and more efficient RISC to the ¹CT singlet state.     

Understanding and Designing Thermally Activated Delayed Fluorescence Emitters: Beyond the Energy Gap Approximation

In this article recent progress in the development of molecules exhibiting Thermally Activated Delayed Fluorescence (TADF) is discussed with a particular focus upon their application as emitters in highly efficient organic light emitting diodes (OLEDs). The key aspects controlling the desirable functional properties, e. g. fast intersystem crossing, high radiative rate and unity quantum yield, are introduced with a particular focus upon the competition between the key requirements needed to achieve high performance OLEDs. The design rules required for organic and metal organic materials are discussed, and the correlation between them outlined. Recent progress towards understanding the influence of the interaction between a molecule and its environment are explained as is the role of the mechanism for excited state formation in OLEDs. Finally, all of these aspects are combined to discuss the ability to implement high level design rules for achieving higher quality materials for commercial applications. This article highlights the significant progress that has been made in recent years, but also outlines the significant challenges which persist to achieve a full understanding of the TADF mechanism and improve the stability and performance of these materials.     

Highly Efficient Thermally Activated Delayed Fluorescence from Pyrazine-Fused Carbene Au(I) Emitters

Metal-based thermally activated delayed fluorescence (TADF) is conceived to inherit the advantages of both phosphorescent metal complexes and purely organic TADF compounds for high-performance electroluminescence. Herein a panel of new TADF Au(I) emitters has been designed and synthesized by using carbazole and pyrazine-fused nitrogen-heterocyclic carbene (NHC) as the donor and acceptor ligands, respectively. Single-crystal X-ray structures show linear molecular shape and coplanar arrangement of the donor and acceptor with small dihedral angles of <6.5°. The coplanar orientation and appropriate separation of the HOMO and LUMO in this type of molecules favour the formation of charge-transfer excited state with appreciable oscillator strength. Together with a minor but essential heavy atom effect of Au ion, the complexes in doped films exhibit highly efficient (Φ∼0.9) and short-lived (<1 μs) green emissions via TADF. Computational studies on this class of emitters have been performed to decipher the key reverse intersystem crossing (RISC) pathway. In addition to a small energy splitting between the lowest singlet and triplet excited states (ΔE_ST), the spin-orbit coupling (SOC) effect is found to be larger at a specific torsion angle between the donor and acceptor planes which favours the RISC process the most. This work provides an alternative molecular design to TADF Au(I) carbene emitters for OLED application.     

Molecular engineering on all ortho-linked carbazole/oxadiazole hybrids toward highly-efficient thermally activated delayed fluorescence materials in OLEDs

All ortho-linked D-A and D-A-D molecules exhibit non-TADF feature due to broad spatial overlap at triplet excited state for large △E_ST,while A-D-A compounds show strong TADF property owing to efficient spatial separation for small △E_ST.     

Modulation of Thermally Activated Delayed Fluorescence in Waterborne Polyurethanes via Charge‐Transfer Effect

Here, we designed several waterborne polyurethanes (WPUs) with efficient thermally activated delayed fluorescence (TADF) via serving charge‐transfer (CT) states as a mediate bridge between singlet and triplet states to boost reverse intersystem crossing (RISC). By tuning substituents of diphenyl sulfone (DS), we found that O,O′‐ and S,S′‐substituted DS covalently incorporated in WPUs solely show typical fluorescence emission with lifetimes in the nanosecond range. Interestingly, TADF appears by replacing the substituent with the nitrogen atom, of which lifetimes are up to ≈10 microseconds and ≈1 millisecond in air and vacuum, respectively, even though the energy gap between singlet and triplet states (ΔE_ST) is still large for generating TADF. To explain this phenomenon, an energy level mode based on CT states and an ³(n‐π*) receiver state was proposed. By the rational modulation of CT states, it is possible to tune the ΔE_ST to render TADF‐based materials suitable for versatile applications.     

Benzimidazobenzothiazole‐Based Bipolar Hosts to Harvest Nearly All of the Excitons from Blue Delayed Fluorescence and Phosphorescent Organic Light‐Emitting Diodes

Much effort has been devoted to developing highly efficient organic light‐emitting diodes (OLEDs) that function through phosphorescence or thermally activated delayed fluorescence (TADF). However, efficient host materials for blue TADF and phosphorescent guest emitters are limited because of their requirement of high triplet energy levels. Herein, we report the rigid acceptor unit benzimidazobenzothiazole (BID‐BT), which is suitable for use in bipolar hosts in blue OLEDs. The designed host materials, based on BID‐BT, possess high triplet energy and bipolar carrier transport ability. Both blue TADF and phosphorescent OLEDs containing BID‐BT‐based derivatives exhibit external quantum efficiencies as high as 20 %, indicating that these hosts allow efficient triplet exciton confinement appropriate for blue TADF and phosphorescent guest emitters.     

Nearly 100% exciton utilization in highly efficient red OLEDs based on dibenzothioxanthone acceptor

Improving the utilization of excitons has always been an important topic for the development of electroluminescence devices. In this work, we designed and synthesized three red TADF emitters TPA-DBT12, TPA-DBT3 and DTPA-DBT by employing dibenzothioxanthone (DBT) acceptor framework to stabilize the locally excited triplet state to participate in the reverse intersystem crossing (RISC) process. The fast RISC process and singlet radiation decay process gave rise to evidently enhanced exciton utilization. All of the red OLEDs based on these materials showed maximum EQE over 11% and high exciton utilization close to 100%. This work not only extend the acceptor framework for red materials but also provide a new perspective for the design of highly efficient red TADF materials with 100% exciton utilization by managing locally excited triplet state.     

Molecular engineering on all ortho-linked carbazole/oxadiazole hybrids toward highly-efficient thermally activated delayed fluorescence materials in OLEDs

The highest efficiency thermally activated delayed fluorescence(TADF) emitters in OLEDs are mostly based on twisted donor/acceptor(D/A) type organic molecules.Herein,we report the rational molecular design on twisted all ortho-linked carbazole/oxadiazole(Cz/OXD) hybrids with tunable D-A interactions by adjusting the numbers of donor/acceptor units and electron-donating abilities.Singlet-triplet energy bandgaps(ΔE_(ST)) are facilely tuned from～0.4,0.15 to～0 eV in D-A,D-A-D to A-D-A type compounds.This variation correlates well with triplet-excited-state frontier orbital spatial separation efficiency.NonTADF feature with solid state photoluminescence quantum yield(PLQY)10% is observed in D-A type2 CzOXD and D-A-D type 4 CzOXD.Owing to the extremely low ΔE_(ST) for efficient reverse intersystem crossing,strong TADF with PLQY of 71%-92% is achieved in A-D-A type 4 CzDOXD and 4 tCzDOXD.High external quantum efficiency from 19.4% to 22.6% is achieved in A-D-A typed 4 CzDOXD and 4 tCzDOXD.     

Novel thioxanthone host material with thermally activated delayed fluorescence for reduced efficiency roll-off of phosphorescent OLEDs

A symmetrical host material, 2,7-di(9,9-dimethyl-9H-fluoren-1-yl)-9H-thioxanthen-9-one (DMBFTX), with TADF property was firstly developed. The red phosphorescent OLED based on this TADF host displays a lower EQEs rolloff of 38.8% at a luminance of 10 000 cd/m² as compared to 71.2% of commercial mCP host, which is resulted from the upconversion of DMBFTX from triplet to singlet.     

Thermally Activated Delayed Fluorescence in an Organic Cocrystal: Narrowing the Singlet–Triplet Energy Gap via Charge Transfer

Harvesting non‐emissive spin‐triplet charge‐transfer (CT) excitons of organic semiconductors is fundamentally important for increasing the operation efficiency of future devices. Here we observe thermally activated delayed fluorescence (TADF) in a 1:2 CT cocrystal of trans‐1,2‐diphenylethylene (TSB) and 1,2,4,5‐tetracyanobenzene (TCNB). This cocrystal system is characterized by absorption spectroscopy, variable‐temperature steady‐state and time‐resolved photoluminescence spectroscopy, single‐crystal X‐ray diffraction, and first‐principles calculations. These data reveal that intermolecular CT in cocrystal narrows the singlet–triplet energy gap and therefore facilitates reverse intersystem crossing (RISC) for TADF. These findings open up a new way for the future design and development of novel TADF materials.     

Highly Twisted Thermally Activated Delayed Fluorescence (TADF) Molecules and Their Applications in Organic Light-Emitting Diodes (OLEDs)

Thermally activated delayed fluorescence (TADF) materials have attracted great potential in the field of organic light-emitting diodes (OLEDs). Among thousands of TADF materials, highly twisted TADF emitters have become a hotspot in recent years. Compared with traditional TADF materials, highly twisted TADF emitters tend to show multi-channel charge-transfer characters and form rigid molecular structures. This is advantageous for TADF materials, as non-radiative decay processes can be suppressed to facilitate efficient exciton utilization. Accordingly, OLEDs with excellent device performances have also been reported. In this Review, we have summarized recent progress in highly twisted TADF materials and related devices, and give an overview of the molecular design strategies, photophysical studies, and the performances of OLED devices. In addition, the challenges and perspectives of highly twisted TADF molecules and the related OLEDs are also discussed.     

Thermally Activated Delayed Fluorescence Materials: Towards Realization of High Efficiency through Strategic Small Molecular Design

Thermally activated delayed fluorescence (TADF) is one of the most intriguing and promising discoveries towards realization of highly-efficient organic light emitting diodes (OLED) utilizing small molecules as emitters. It has the capability of manifesting all excitons generated during the electroluminescent processes, consequently achieving 100 % of internal quantum efficiency. Since the report of the first efficient OLED based on a TADF small molecule in 2012 by Adachi et al., the quest for optimal TADF materials for OLED application has never stopped. Various TADF molecules bearing different design concepts and strategies have been designed and produced, with the aim to boost the overall performances of corresponding OLEDs. In this minireview, the general principles of TADF molecular design based on three basic categories of TADF species: twisted intramolecular charge transfer (TICT), through-space charge transfer (TSCT) and multi-resonance induced TADF (MR-TADF) are discussed in detail. Several key aspects with respect to each category, as well as some effective methods to enhance the efficiency of TADF materials and corresponding OLEDs from the molecular engineering perspectives, are summarized and discussed to exhibit a general landscape of TADF molecular design to a wide variety of scientific researchers within this particular disciplinary area.     

Red/NIR Thermally Activated Delayed Fluorescence from Aza-BODIPYs

The search for long-lived red and NIR fluorescent dyes is challenging and hitherto scarcely reported. Herein, the viability of aza-BODIPY skeleton as a promising system for achieving thermal activated delayed fluorescent (TADF) probes emitting in this target region is demonstrated for the first time. The synthetic versatility of this scaffold allows the design of energy and charge transfer cassettes modulating the stereoelectronic properties of the energy donors, the spacer moieties and the linkage positions. Delayed emission from these architectures is recorded in the red spectral region (695–735 nm) with lifetimes longer than 100 μs in aerated solutions at room temperature. The computational-aided photophysical study under mild and hard irradiation regimes disclose the interplay between molecular structure and photonic performance to develop long-lived fluorescence red emitters through thermally activated reverse intersystem crossing. The efficient and long-lasting NIR emission of the newly synthesized aza-BODIPY systems provides a basis to develop advanced optical materials with exciting and appealing photonic response.     

Thermally Activated Delayed Near-Infrared Photoluminescence from Functionalized Lead-Free Nanocrystals

As an analogue to thermally activated delayed fluorescence (TADF) of organic molecules, thermally activated delayed photoluminescence (TADPL) observed in molecule-functionalized semiconductor nanocrystals represents an exotic mechanism to harvest energy from dark molecular triplets and to obtain controllable, long-lived PL from nanocrystals. The reported TADPL systems have successfully covered the visible spectrum. However, TADF molecules already emit very efficiently in the visible, diminishing the technological impact of the less-efficient nanocrystal-molecule TADPL. Here we report bright, near-infrared TADPL in lead-free CuInSe₂ nanocrystals functionalized with carboxylated tetracene ligands, which results from efficient triplet energy transfer from photoexcited nanocrystals to ligands, followed with thermally activated reverse energy transfer from ligand triplets back to nanocrystals. This strategy prolonged the nanocrystal exciton lifetime from 100 ns to 60 μs at room temperature.     

Highly Efficient Au(I) Alkynyl Emitters: Thermally Activated Delayed Fluorescence and Solution-Processed OLEDs

Two-coordinate donor-metal-acceptor type coinage metal complexes displaying efficient thermally activated delayed fluorescence (TADF) have been unveiled to be highly appealing candidates as emitters for organic light-emitting diodes (OLEDs). Herein a series of green to yellow TADF gold(I) complexes with alkynyl ligands has been developed for the first time. The complexes exhibit high photoluminescence quantum yields (PLQYs) of up to 0.76 in doped films (5 wt % in PMMA) at room temperature. The modifications of alkynyl ligands with electron-donating amino groups together with the use of electron-deficient carbene ligands induce ligand-to-ligand charge transfer excited states that give rise to TADF emission. Spectroscopic and density functional theory (DFT) calculations reveal the roles of electron-donating capability of the alkynyl ligand in tuning the excited-state properties. Solution-processed organic light-emitting diodes (OLEDs) using the present complexes as emitters achieve maximum external quantum efficiency (EQE) of up to 20 %.