Thermally Activated Delayed Fluorescence Emitters Research Articles

Efficient Spin-Flip between Charge-Transfer States for High-Performance Electroluminescence, without an Intermediate Locally Excited State.

Thermally activated delayed fluorescence (TADF) materials with both high photoluminescence quantum yield (PLQY) and fast reverse intersystem crossing (RISC) are strongly desired to realize efficient and stable organic light-emitting diodes (OLEDs). Control of excited-state dynamics via molecular design plays a central role in optimizing the PLQY and RISC rate of TADF materials but remains challenging. Here, 3 TADF emitters possessing similar molecular structures, similar high PLQYs (89.5% to 96.3%), and approximate energy levels of the lowest excited singlet states (S1), but significantly different spin-flipping RISC rates (0.03 × 106 s-1 vs. 2.26 × 106 s-1) and exciton lifetime (297.1 to 332.8 μs vs. 6.0 μs) were systematically synthesized to deeply investigate the feasibility of spin-flip between charge-transfer excited states (3CT-1CT) transition. Experimental and theoretical studies reveal that the small singlet-triplet energy gap together with low RISC reorganization energy between the 3CT and 1CT states could provide an efficient RISC through fast spin-flip 3CT-1CT transition, without the participation of an intermediate locally excited state, which has previously been recognized as being necessary for realizing fast RISC. Finally, the OLED based on the champion TADF emitter achieves a maximum external quantum efficiency of 27.1%, a tiny efficiency roll-off of 4.1% at 1,000 cd/m2, and a high luminance of 28,150 cd/m2, which are markedly superior to those of the OLEDs employing the other 2 TADF emitters.

A dual-locked triarylamine donor enables high-performance deep-red/NIR thermally activated delayed fluorescence organic light-emitting diodes.

Deep-red/near-infrared (DR/NIR) organic light-emitting diodes (OLEDs) have attracted a great deal of attention due to their widespread application fields, such as night-vision devices, optical communication, and information-secured displays. However, most DR/NIR OLEDs show low electroluminescence efficiencies, hampering their applications. Herein, we constructed a high-performance DR/NIR thermally activated delayed fluorescence (TADF) emitter based on an advanced dual-locked triarylamine donor (D) unit. Promisingly, such a novel D segment brings numerous advantages: a larger stereoscopic architecture, an enhanced electron-donating ability, and a stiffer molecular structure. In view of these features, the newly developed emitter DCN-DSP shows redshifted emission, a narrowed ΔEST, an enhanced PLQY value and aggregation-induced emission (AIE) properties, which allows for effectively alleviating concentration quenching compared to the control compound using a conventional triarylamine derivative as D units. The DCN-DSP-based OLEDs with modulated doping concentrations exhibit champion EQEs of 36.2% at 660 nm, 26.1% at 676 nm and 21.3% at 716 nm, which are record-high efficiencies among all TADF OLEDs in the similar emission ranges. This work realizes the efficiency breakthrough of DR/NIR TADF OLEDs, and such a promising molecular design approach may inspire even better DR/NIR TADF emitters in the future.

The photophysical properties of sulfone-based TADF emitters in relation to their structural properties.

In this work, thermally activated delayed fluorescence (TADF) of a series of emitters with sulfone-based acceptor moieties was studied by density functional theory (DFT) methods. Sulfone derivatives were shown to be high performing TADF emitters over recent years. When discussing the TADF efficiency, various properties, such as the singlet-triplet energy gap (ΔEST), spin-orbit coupling (SOC) and the nature of states, stand out due to their roles in reverse intersystem crossing (RISC). Here, we mainly focused on three important structural parameters that affect the intersystem crossing (ISC) and RISC pathways and their efficiencies. These three parameters are: (1) the effect of meta- and para-conjugation, (2) the effect of rigid acceptor moieties and (3) the effect of the phenyl bridge on photophysical properties.

Conformational isomeric thermally activated delayed fluorescence (TADF) emitters: mechanism, applications, and perspectives.

Thermally activated delayed fluorescence (TADF) materials have received enormous attention and the mechanism behind them has been investigated in depth. It has been found that some donor-acceptor (D-A) type TADF emitters could obviously exhibit dual stable conformations in the ground states and their distributions significantly affect the physical properties and device performances. Therefore, professional analysis and a summary of the relationship between molecular structures and performances are very important. In this review, we first summarize the mechanism and properties of TADF emitters with conformational isomerism. We also classify their recent progress according to their different applications, and provide an outlook on their perspectives.

Thioxanthone-containing blue thermally activated delayed fluorescent emitter

Accelerating reverse intersystem crossing (RISC) without sacrificing fast radiative decay is effective in suppressing efficiency roll-off (eRO) in thermally activated delayed fluorescence (TADF)-based organic light-emitting diodes. We here report a TADF emitter, CC-TXO-I, combining a bicarbazole donor (CC) and a sulfur-containing acceptor (TXO). The CC is used to accelerate radiative decay via moderate donor-acceptor torsion angle, and the TXO is expected to provide fast RISC by the heavy-atom effect. We realized very large rate constants of RISC (k RISCs) of ∼107 s−1. Both k RISCs and rate constants of radiative decay of CC-TXO-I increased with increasing doping concentration, resulting in improved eROs.

Tailoring thermally activated delayed fluorescence emitters for efficient electrochemiluminescence with tripropylamine as coreactant.

Using a unified metal-free procedure, a selection of Thermally Activated Delayed Fluorescence (TADF) emitters has been synthesized and characterized. Different acceptor and donor moieties have been explored in order to develop red emitting dyes with reduction potentials suitable for the application in ECL using tri-propylamine as coreactant. The most promising compound shows terephthalonitrile as the acceptor and diphenylamines as donors, and it displayed an ECL efficiency that is double the one of the standard [Ru(bpy)3](PF6)2. Based on such findings, a novel water-soluble TADF emitter (Na4[4DPASO3TPN]) has been synthesized and characterized to enable electrochemiluminescence in an aqueous medium.

Intramolecular locking and coumarin insertion: a stepwise approach for TADF design.

Three novel TADF (thermally activated delayed fluorescence) emitters based on the well-studied Qx-Ph-DMAC fluorophore are designed and synthesized. The photophysical properties of these materials are studied from a theoretical and experimental point of view, demonstrating the cumulative effects of multiple small modifications that combine to afford significantly improved TADF performance. First, an extra phenyl ring is added to the acceptor part of Qx-Ph-DMAC to increase the conjugation length, resulting in BQx-Ph-DMAC, which acts as an intermediate molecular structure. Next, an electron-deficient coumarin unit is incorporated to fortify the electron accepting ability, affording ChromPy-Ph-DMAC with red-shifted emission. Finally, the conjugated system is further enlarged by 'locking' the molecular structure, generating DBChromQx-DMAC with further red-shifted emission. The addition of the coumarin unit significantly impacts the charge-transfer excited state energy levels with little effect on the locally excited states, resulting in a decrease of the singlet-triplet energy gap. As a result, the two coumarin-based emitters show considerably improved TADF performance in 1 w/w% zeonex films when compared to the initial Qx-Ph-DMAC structure. 'Locking' the molecular structure further lowers the singlet-triplet energy gap, resulting in more efficient reverse intersystem crossing and increasing the contribution of TADF to the total emission.

Importance of spin-triplet excited-state character in the reverse intersystem crossing process of spiro-based TADF emitters

By fine tuning the D–A interactions, spiro-based TADF molecules show similar CT transitions in S1and five different characters in T1, which determine the physical parameters of the SOC constant andλ, thus affecting the RISC process.

Controllable construction of red thermally activated delayed fluorescence molecules based on a spiro-acridine donor.

Red and near-infrared (NIR) thermally activated delayed fluorescence (TADF) molecules show excellent potential applications in organic light-emitting diodes (OLEDs). Due to the lack of systematic studies on the relationship between molecular structures and luminescence properties, both the species and amounts of red and NIR TADF molecules are far from meeting the requirements for practical applications. Herein, four new efficient molecules (DQCN-2spAs, TPCN-2spAs, DPCN-2spAs and BPCN-2spAs) are proposed and their photophysical properties are theoretically predicted based on first-principles calculations and thermal vibration correlation function (TVCF) theory. The results show that all molecules exhibit red or NIR emissions and they have fast radiative decay rates and reverse intersystem crossing (RISC) rates, and the excellent TADF luminescence properties are predicted. Moreover, based on spiro-acridine (spAs) as the donor unit, the combination with different acceptors can change the dihedral angle between the ground state and the excited state, the bending degree of the donor is positively correlated with the reorganization energy, and this feature can have a great influence on the non-radiative process. Furthermore, based on these theoretical predictions, experimental verifications are performed and the synthesized BPCN-2spAs is confirmed to be an efficient NIR TADF molecule. Thus, the relationships between basic molecular structures and photophysical properties are revealed, a feasible design strategy is applied and four promising red and NIR TADF molecules are proposed. All these results could contribute to the development of red and NIR TADF emitters and OLEDs.

Thermally activated delayed fluorescence in a mechanically soft charge-transfer complex: role of the locally excited state.

Molecular design for thermally activated delayed fluorescence (TADF) necessitates precise molecular geometric requirements along with definite electronic states to ensure high intersystem crossing (ISC) rate and photoluminescence quantum yield (PLQY). Achieving all these requirements synchronously while maintaining ease of synthesis and scalability is still challenging. To circumvent this, our strategy of combining a crystal engineering approach with basic molecular quantum mechanical principles appears promising. A holistic, non-covalent approach for achieving efficient TADF in crystalline materials with distinct mechanical properties is highlighted here. Charge transfer (CT) co-crystals of two carbazole-derived donors (ETC and DTBC) with an acceptor (TFDCNB) molecule are elaborated as a proof-of-concept. Using temperature-dependent steady-state and time-resolved photoluminescence techniques, we prove the need for a donor-centric triplet state (3LE) to ensure efficient TADF. Such intermediate states guarantee a naturally forbidden, energetically uphill reverse intersystem crossing (RISC) process, which is paramount for effective TADF. A unique single-crystal packing feature with isolated D-A-D trimeric units ensured minimal non-radiative exciton loss, leading to a high PLQY and displaying interesting mechanical plastic bending behaviour. Thus, a comprehensive approach involving a non-covalent strategy to circumvent the conflicting requirements of a small effective singlet-triplet energy offset and a high oscillator strength for efficient TADF emitters is achieved here.

Simultaneously enhancing the planarity and electron-donating capability of donors for through-space charge transfer TADF towards deep-red emission.

Through-space charge transfer (TSCT) has been proven effective for designing thermally activated delayed fluorescence (TADF) emitters due to the separation of the frontier molecular orbitals. Although tuning of the interaction between the donor and acceptor by controlling the conformation is known to be crucial for the photophysical properties of TSCT excited states, it remains a challenge to realize efficient red and deep-red emissions. Herein, we designed two TSCT molecules, namely TPXZ-QX and TPXZ-2QX, by using oxygen-bridged triphenylamine (TPXZ) as the electron donor with enhanced planarity and electron-donating capability. With a face-to-face orientation of the donor and acceptor segments and close π-π contacts, the new emitters have strong intramolecular noncovalent donor-acceptor interactions. The emissions of TPXZ-QX and TPXZ-2QX in doped thin films lie in the red (λmax = 632 nm) to deep-red (λmax = 665 nm) region. The photoluminescence quantum yields are 41% and 32% for TPXZ-QX and TPXZ-2QX, respectively. Organic light-emitting diodes (OLEDs) based on TPXZ-QX and TPXZ-2QX show external quantum efficiencies (EQEs) of up to 13.8% and 11.4%, respectively. This work indicates that the modulation of TSCT excited states based on strong intramolecular cofacial π-stacking interactions is a viable choice for the development of high-efficiency long-wavelength TADF emitters.

A TADF Emitter with Dual Para-Positioned Donors Enables OLEDs with Improved Efficiency and CIE Coordinates Close to the Rec. 2020 Red Standard

Developing red thermally activated delayed fluorescence (TADF) emitters concurrently with high efficiency and emission color close to the BT.2020 red standard is an ongoing challenge. Herein, we developed a new red TADF emitter BCN-TPA, in which two identical donors are attached at the para-positions of one fused phenyl ring in the acceptor framework. Such an arrangement mode can lead the donors with an obvious superimposed effect comparing the conventional arrangement with edge-capped donors on the acceptor. Thus, BCN-TPA yields enhanced overall donor strength with numerous superiorities, such as high oscillator strength and narrow singlet-triplet energy difference, thus giving rise to red-shifted emission with improved overall exciton utilization. In an organic light-emitting diode, BCN-TPA presents efficient deep-red electroluminescence with a maximum external quantum efficiency of 27.6% and a peak at 656 nm, corresponding to CIE coordinates of (0.686, 0.304), which are very close to the red primary in the BT.2020 standard. To the best of our knowledge, this is one of the topmost efficiencies in the field of deep-red TADF OLEDs. This work exemplifies an easy design principle for constructing high-performance deep-red TADF emitters, providing unique molecular-level insights toward improving color quality and elevating efficiency based on conventional D-A type molecular frameworks.

A facile method to achieve red thermally activated delayed fluorescence emitters with EQE over 30% via molecular aspect ratio engineering

Bandgap narrowing via the incorporation of strong donor and/or acceptor units into the molecular structure is a well-known strategy for the design of the long-wavelength fluorophores. Due to the energy-gap law, achieving high emission quantum yield at long wavelength becomes a paradox. Therefore, the red fluorescence emitters with external quantum efficiency (EQE) over 30 % have rarely been reported in comparison with blue and green fluorophores. In this work, a series of the thermally activated delayed fluorescence (TADF) materials (PH-TPA, BZ-TPA and PO-TPA) featured with rigid skeleton demonstrated low non-radiative decay rates and high photoluminescent quantum efficiency. Importantly, the engineering of molecular aspect ratio of the TADF emitters led to high horizontal emitting dipole ratio, thus enhancing the device performance. As a result, organic light-emitting diodes based on PH-TPA, BZ-TPA and PO-TPA showed record-high EQEs of 33.0 % at 624 nm, 31.3 % at 634 nm and 34.9 % at 632 nm, respectively. This work provided a facile and yet effective method for the construction of efficient red TADFs via the integration of rigid emission core and the control of molecular aspect ratio.

Theoretical insights on the luminescent mechanism of a highly efficient green-activated delayed fluorescence emitter using the QM/MM method

The solid-state effect plays an important role in excited-state dynamics and luminescence properties of thermally activated delayed fluorescence (TADF) materials. Here, the luminescent mechanism of two novel TADF emitters, PPZTPI and PPZPPI, with aggregation-induced emission (AIE) features are theoretically studied based on the first-principles calculations. The polarisable continuum model (PCM) and the combined quantum mechanics and molecular mechanics (QM/MM) method are used to simulate the solvent environments in toluene and the solid-state effects, respectively. Our results show that both PPZTPI and PPZPPI exhibit excellent TADF and AIE properties with similar but not identical luminescence mechanisms. In the solid state, the delayed fluorescence emission of the two molecules mainly depends on the two-step reverse intersystem crossing process. The molecular radiation rates increase by 1–2 orders of magnitude due to the enhancement of intermolecular interactions in the aggregation. For PPZTPI, the solid-state environment exerts a greater influence on the molecular geometry and electronic structure, non-radiative transitions, excited state dynamics, and emission mechanism due to the substitution of tert-butyl groups and their induced steric hindrance effects. Our theoretical study reasonably elucidates the experimental results and provides valuable information for designing high-efficient AIE-TADF emitters.

New Light-Green Thermally Activated Delayed Fluorescence Polymer Based on Dimethylacridine-Triphenyltriazine Light-Emitting Unit and Tetraphenylsilane Moiety as Non-Conjugated Backbone.

In the search for solution-processable TADF materials as a light emitting layer for OLED devices, polymers have attracted considerable attention due to their better thermal and morphological properties in the film state with respect to small molecules. In this work, a new polymer (p-TPS-DMAC-TRZ) with thermally activated delayed fluorescence (TADF) light-emitting characteristics was prepared from a conjugation-break unit (TPS) and a well-known TADF core (DAMC-TRZ). This material was designed to preserve the photophysical properties of DAMC-TRZ, while improving other properties, such as thermal stability, promoted by its polymerization with a TPS core. Along with excellent solubility in common organic solvents such as toluene, chloroform and THF, the polymer (Mn = 9500; Mw = 15200) showed high thermal stability (TDT5% = 481 °C), and a Tg value of 265 °C, parameters higher than the reference small molecule DMAC-TRZ (TDT5% = 305 °C; Tg = 91 °C). The photoluminescence maximum of the polymer was centered at 508 nm in the solid state, showing a low redshift compared to DMAC-TRZ (500 nm), while also showing a redshift in solution with solvents of increasing polarity. Time-resolved photoluminescence of p-TPS-DMAC-TRZ at 298 K, showed considerable delayed emission in solid state, with two relatively long lifetimes, 0.290 s (0.14) and 2.06 s (0.50), and a short lifetime of 23.6 ns, while at 77 K, the delayed emission was considerably quenched, and two lifetimes in total were observed, 24.6 ns (0.80) and 180 ns (0.20), which was expected from the slower RISC process at lower temperatures, decreasing the efficiency of the delayed emission and demonstrating that p-TPS-DMAC-TRZ has a TADF emission. This is in agreement with room temperature TRPL measurements in solution, where a decrease in both lifetime and delayed contribution to total photoluminescence was observed when oxygen was present. The PLQY of the mCP blend films with 1% p-TPS-DMAC-DMAC-TRZ as a dopant was determined to be equal to 0.62, while in the pure film, it was equal to 0.29, which is lower than that observed for DMAC-TRZ (0.81). Cyclic voltammetry experiments showed similarities between p-TPS-DMAC-TRZ and DAMC-TRZ with HOMO and LUMO energies of -5.14 eV and -2.76 eV, respectively, establishing an electrochemical bandgap value of 2.38 eV. The thin film morphology of p-TPS-DMAC-TRZ and DMAC-TRZ was compared by AFM and FE-SEM, and the results showed that p-TPS-DMAC-TRZ has a smoother surface with fewer defects, such as aggregations. These results show that the design strategy succeeded in improving the thermal and morphological properties in the polymeric material compared to the reference small molecule, while the photophysical properties were mostly maintained, except for the PLQY determined in the pure films. Still, these results show that p-TPS-DMAC-TRZ is a good candidate for use as a light-emitting layer in OLED devices, especially when used as a host-guest mixture in suitable materials such as mCP.

Effects of Solvent Dielectric on Thermally Activated Delayed Fluorescence: A Predictive Computational Polarization Consistent Approach

We study computationally thermally activated delayed fluorescence (TADF) in donor-acceptor compounds. The relevant electronic excited states that are strongly affected by the dielectric environment are treated by a polarization consistent framework. The high fidelity potential energy surfaces are used following a quantum-mechanical Fermi's golden rule (FGR) picture to calculate rates of intersystem crossing (ISC) and reverse intersystem crossing (RISC). To demonstrate the potency of the approach, we consider isomers of benzonitrile functionalized tert-butyl-substituted dimethylacridine (DMAC-BN), which were recently found to perform well as TADF emitters. The calculated excited state energies that appear to reproduce well measured spectral trends with respect to the dielectric constant are used to parametrize ISC/RISC FGR rates. The calculated rates reproduce well measured rates, whereas semiclassical based rates are grossly underestimated. In particular, we find in agreement with the recent experimental study [Phys. Rev. Appl.2019, 12, 044021] that the ortho and meta isomers are significantly more effective as TADF emitters. The computational framework provides valuable insight at the molecular level into RISC rates and therefore can contribute to the design of materials of increased TADF efficiency.

Asymmetric intramolecular charge transfer enables highly efficient red thermally activated delayed fluorescent emitters

A feasible strategy of asymmetric donor–acceptor-second acceptor (D-A-A) structure is proposed for improving the photoluminecense (PL) and electroluminescence (EL) performance of red thermally activated delayed fluorescence (TADF) emitters. As a concept, four newly TADF emitters are designed and synthesized, D-A-A structure oTPAPO-DTPZ and pTPAPO-DTPZ and D-A-D type oDTPA-DTPZ and pDTPA-DTPZ, by using triphenylamine (TPA), dithieno[2,3-a:3′,2′-c]phenazine (DTPZ) and diphenylphosphine oxide (DPPO) groups as the donor, acceptor and second acceptor, respectively. It is demonstrated that abound intra- and inter-molecular CH···O hydrogen bonds are forming between TPA donor and DPPO acceptor for the asymmetric compounds, which effectively promote the intra- and inter-molecular charge transfer. Moreover, the steric hindrance of DPPO group availably suppresses the concentration quenching. As a consequence, the asymmetric D-A-A structured oTPAPO-DTPZ and pTPAPO-DTPZ exhibit relatively higher PL quantum yields and lower nonradiation rates, and thus better EL performance. In particular, device based on pTPAPO-DTPZ achieves the maximum luminance of 19360 cd m−2 and external quantum efficiency of 11.4 % at 632 nm, which are 2.3 and 1.5 times the values of pDTPA-DTPZ based device.

Microdroplet-Facilitated Assembly of Thermally Activated Delayed Fluorescence-Encoded Microparticles with Non-interfering Color Signals.

Encoded microparticles (EMPs) have shown demonstrative value for multiplexed high-throughput bioassays such as drug discovery and diagnostics. Herein, we propose for the first time the incorporation of thermally activated delayed fluorescence (TADF) dyes with low-cost, heavy metal-free, and long-lived luminescence properties into polymer matrices via a microfluidic droplet-facilitated assembly technique. Benefiting from the uniform droplet template sizes and polymer-encapsulated structures, the resulting composite EMPs are highly monodispersed, efficiently shield TADF dyes from singlet oxygen, well preserve TADF emission, and greatly increase the delayed fluorescence lifetime. Furthermore, by combining with phase separation of polymer blends in the drying droplets, TADF dyes with distinct luminescent colors can be spatially separated within each EMP. It eliminates optical signal interference and generates multiple fluorescence colors in a compact system. Additionally, in vitro studies reveal that the resulting EMPs show good biocompatibility and allow cells to adhere and grow on the surface, thereby making them promising optically EMPs for biolabeling.

Metal-Perturbed Multiresonance TADF Emitter Enables High-Efficiency and Ultralow Efficiency Roll-Off Nonsensitized OLEDs with Pure Green Gamut.

Multiresonance (MR)-induced thermally activated delayed fluorescence (TADF) emitters based on B- and N-embedded polycyclic aromatics are desirable for ultrahigh-definition organic light-emitting diodes (OLEDs) due to their high photoluminescence quantum yield (PLQY) and narrow bandwidth. But the reverse intersystem crossing (RISC) rates of MR-TADF emitters are usually small, resulting in severe device efficiency roll-off at high brightness. To solve this issue, a sensitizer for the MR-TADF emitter has been required. Herein, a new MR-TADF emitter is developed through coordination of Au with B/N-embedded polycyclic ligand. Benefitting from the Au perturbation, the RISC rate is dramatically accelerated to 2.3 × 107 s-1 , leading to delayed fluorescence lifetime as short as 4.3 µs. Meanwhile, the PLQY of 95% and full width at half maximum of 39nm (0.18eV) are essentially unchanged after metal coordination. Therefore, a high PLQY, short delayed fluorescence lifetime, and high color purity are concurrently realized in a single TADF emitter. Accordingly, vacuum-deposited OLEDs exhibit high-performance electroluminescence with a maximum external quantum efficiency (EQE) of 35.8% without sensitization. The EQE is maintained as high as 32.3% at 10000cd m-2 . Furthermore, solution-processed OLED based on the emitter also achieves excellent performance with a maximum EQE of 25.7% and a small efficiency roll-off.

Constructing high-efficiency orange-red thermally activated delayed fluorescence emitters by three-dimension molecular engineering

Preparing high-efficiency solution-processable orange-red thermally activated delayed fluorescence (TADF) emitters remains challenging. Herein, we design a series of emitters consisting of trinaphtho[3,3,3]propellane (TNP) core derivatized with different TADF units. Benefiting from the unique hexagonal stacking architecture of TNPs, TADF units are thus kept in the cavities between two TNPs, which decrease concentration quenching and annihilation of long-lived triplet excitons. According to the molecular engineering of TADF and host units, the excited states can further be regulated to effectively enhance spin-orbit coupling (SOC) processes. We observe a high-efficiency orange-red emission at 604 nm in one instance with high SOC value of 0.862 cm−1 and high photoluminescence quantum yield of 70.9%. Solution-processable organic light-emitting diodes exhibit a maximum external quantum efficiency of 24.74%. This study provides a universal strategy for designing high-performance TADF emitters through molecular packing and excited state regulation.