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.

Managing Locally Excited and Charge-Transfer Triplet States to Facilitate Up-Conversion in Red TADF Emitters That Are Available for Both Vacuum- and Solution-Processes.

Developing red thermally activated delayed fluorescence (TADF) emitters for high-performance OLEDs is still facing great challenge. Herein, three red TADF emitters, pDBBPZ-DPXZ, pDTBPZ-DPXZ, and oDTBPZ-DPXZ, are designed and synthesized with same donor-acceptor (D-A) backbone with different peripheral groups attaching on the A moieties. Their lowest triplet states change from locally excited to charge transfer character leading to significantly enhance reverse intersystem crossing process. In particular, oDTBPZ-DPXZ exhibits efficient TADF feature and exciton utilization. It not only achieves an external quantum efficiency (EQE) of 20.1 % in red vacuum-processed OLED, but also realize a high EQE of 18.5 % in a solution-processed OLED, which is among the best results in solution-processed red TADF OLEDs. This work provides an effective strategy for designing red TADF molecules by managing energy level alignments to facilitate the up-conversion process and thus enhance exciton harvesting.

Characterizing the Conformational Distribution in an Amorphous Film of an Organic Emitter and Its Application in a "Self-Doping" Organic Light-Emitting Diode.

The conformational distribution and mutual interconversion of thermally activated delayed fluorescence (TADF) emitters significantly affect the exciton utilization. However, their influence on the photophysics in amorphous film states is still not known due to the lack of a suitable quantitative analysis method. Herein, we used temperature-dependent time-resolved photoluminescence spectroscopy to quantitatively measure the relative populations of the conformations of a TADF emitter for the first time. We further propose a new concept of "self-doping" for realizing high-efficiency nondoped OLEDs. Interestingly, this "compositionally" pure film actually behaves as a film with a dopant (quasi-equatorial form) in a matrix (quasi-axial form). The concentration-induced quenching that may occur at high concentrations is thus expected to be effectively relieved. The "self-doping" OLED prepared with the newly developed TADF emitter TP2P-PXZ as a neat emitting layer realizes a high maximum external quantum efficiency of 25.4 % and neglectable efficiency roll-off.

Intermolecular Charge-Transfer Transition Emitter Showing Thermally Activated Delayed Fluorescence for Efficient Non-Doped OLEDs.

A novel molecular model of connecting electron-donating (D) and electron-withdrawing (A) moieties via a space-enough and conjugation-forbidden linkage (D-Spacer-A) is proposed to develop efficient non-doped thermally activated delayed fluorescence (TADF) emitters. 10-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl) phenoxy) phenyl)-9,9-dimethyl-9,10-dihydroacridine (DMAC-o-TRZ) was designed and synthesized accordingly. As expected, it exhibits local excited properties in single-molecule state as D-Spacer-A molecular backbone strongly suppress the intramolecular charge-transfer (CT) transition. And intermolecular CT transition acted as the vital radiation channel for neat DMAC-o-TRZ film. As in return, the non-doped device exhibits a remarkable maximum external quantum efficiency (EQE) of 14.7 %. These results prove the feasibility of D-Spacer-A molecules to develop intermolecular CT transition TADF emitters for efficient non-doped OLEDs.

Harnessing Heavy-Atom Effects in Multiple Resonance Thermally Activated Delayed Fluorescence (MR-TADF) Sensitizers: Unlocking High-Performance Visible-to-Ultraviolet (Vis-to-UV) Triplet Fusion Upconversion.

Ultraviolet (UV) light plays a crucial role in various applications, but currently, the efficiency of generating artificial UV light is low. The visible-to-ultraviolet (Vis-to-UV) system based on the triplet-triplet annihilation upconversion (TTA-UC) mechanism can be a viable solution. Metal-free multiple resonance thermally activated delayed fluorescence (MR-TADF) materials are ideal photosensitizers (PSs) apart from the drawback of high photoluminescence quantum yields (PLQYs). Herein, we systematically investigated the impact of the heavy-atom effect (HAE) on the MR-TADF sensitizers. BNCzBr was then synthesized by incorporating a bromine atom into the skeleton of the precursor BNCz. Impressively, the internal HAE (iHAE) leads to a significantly decreased PLQY and a remarkably increased intersystem crossing quantum yield (ΦISC). Consequently, a higher upconversion quantum efficiency of 12.5% was realized. While the external HAE (eHAE) harms the UC performance. This work guides the further development of MR-TADF sensitizers for high-performance Vis-to-UV TTA-UC systems.

Programmable multimode optical encryption of advanced printable security inks by integrating structural color with Down/Up- conversion photoluminescence.

Optical information encryption with high encoding capacities can significantly boost the security level of anti-counterfeiting in the scenario of guaranteeing the authenticity of a wide scope of common and luxury goods. In this work, a novel counterfeiting material with high-degree complexity is fabricated by microencapsulating cholesteric liquid crystals and triplet-triplet annihilation upconversion fluorophores to integrate structural coloration with fluorescence and upconversion photoluminescence. Moreover, the multimode security ink presents tailorable optical behaviors and programmable abilities on flexible substrates by various printing techniques, which offers distinct information encryption under different optical modes. The advanced strategy provides a practical versatile platform for high-secure-level multimode optical inks with largely enhanced encoding capacities, programmability, printability, and cost-effectiveness, which manifests enormous potentials for information encryption and anti-counterfeiting technology.

An A-D-A-Type Thermally Activated Delayed Fluorescence Emitter with Intrinsic Yellow Emission Realizing Record-High Red/NIR OLEDs upon Modulating Intermolecular Aggregations.

Realizing efficient red/near-infrared (NIR) electroluminescence (EL) by precisely modulating molecular aggregations of thermally activated delayed fluorescence (TADF) emitters is an attractive pathway, yet the molecular designs are elusive. Here, a new approach is proposed to manage molecular aggregation via a mild-twist acceptor-donor-acceptor (A-D-A)-type molecular design. A proof-of-concept TADF molecule, QCN-PhSAC-QCN, is developed that furnishes a fast radiative rate and obvious aggregation-induced emission feature. Its emission bands can be facilely shifted from intrinsic yellow to the red/NIR region via fine-tuning doping levels and molecular aggregates while maintaining elegant photoluminescence quantum yields benefiting from suppressed exciton annihilation processes. As a result, a QCN-PhSAC-QCN-based organic light-emitting diode (OLED) exhibits a record-setting external quantum efficiency (EQE) of 39.1% at a doping ratio of 10 wt.%, peaking at 620 nm. Moreover, its nondoped NIR OLED affords a champion EQE of 14.3% at 711 nm and retains outstanding EQEs of 5.40% and 2.35% at current densities of 10 and 100 mA cm-2 , respectively, which are the highest values among all NIR-TADF OLEDs at similar density levels. This work validates the feasibility of such mild-twist A-D-A-type molecular design for precisely controlling molecular aggregation while maintaining high efficiency, thus providing a promising pathway for high-performance red/NIR TADF OLEDs.

Photochemically deoxygenating micelles for protecting TTA-UC against oxygen quenching.

Pluronic F127, P123 and cross-linked F127 diacrylate micelles are photochemically deoxygenating nanocapsules in which oxygen could be removed by photochemical reaction with a surfactant and efficient triplet-triplet annihilation photon upconversion (TTA-UC) can be achieved in air. The efficiency of TTA-UC under air is comparable to that under deoxygenated conditions.

Recent progress in thermally activated delayed fluorescence emitters for nondoped organic light-emitting diodes.

Nondoped organic light-emitting diodes (OLEDs) have drawn immense attention due to their merits of process simplicity, reduced fabrication cost, etc. To realize high-performance nondoped OLEDs, all electrogenerated excitons should be fully utilized. The thermally activated delayed fluorescence (TADF) mechanism can theoretically realize 100% internal quantum efficiency (IQE) through an effective upconversion process from nonradiative triplet excitons to radiative singlet ones. Nevertheless, exciton quenching, especially related to triplet excitons, is generally very serious in TADF-based nondoped OLEDs, significantly hindering the pace of development. Enormous efforts have been devoted to alleviating the annoying exciton quenching process, and a number of TADF materials for highly efficient nondoped devices have been reported. In this review, we mainly discuss the mechanism, exciton leaking channels, and reported molecular design strategies of TADF emitters for nondoped devices. We further classify their molecular structures depending on the functional A groups and offer an outlook on their future prospects. It is anticipated that this review can entice researchers to recognize the importance of TADF-based nondoped OLEDs and provide a possible guide for their future development.

Distinguishing the respective determining factors for spectral broadening and concentration quenching in multiple resonance type TADF emitter systems.

Multiple resonance (MR) type thermally activated delayed fluorescence (TADF) emitters have attracted much recent attention due to their narrow emission spectra and high photoluminescence quantum yields (PLQYs). Spectral broadening and concentration quenching at high doping concentrations are two issues currently limiting the development of MR-TADF emitters. However, the origins of these have not been fully clarified so far. In this work, by investigating emitters with the same MR cores but peripheral groups of different steric types, we distinguished that the spectral broadening and concentration quenching are mainly caused by excimer formation and triplet exciton annihilation, respectively. This understanding on aggregated behaviors of MR emitters provides new insight for the further development of high-performance MR-TADF emitters with low concentration sensitivities.

Approaching Efficient and Narrow RGB Electroluminescence from D-A-Type TADF Emitters Containing an Identical Multiple Resonance Backbone as the Acceptor.

Highly twisted electron donor (D)-electron acceptor (A)-type thermally activated delayed fluorescence (TADF) emitters can achieve high efficiency while suffering from serious structural relaxations and broad emissions. Multiple resonance (MR)-type TADF emitters can realize narrow emission. However, until now, only a few efficient MR-emitting cores are reported and custom tunning of their emission color remains a major challenge in their wider applications. In this work, by combining the conventional TADF and MR-TADF designs, we demonstrate that color tuning and narrowing the spectral width of conventional TADF emission can be easily achieved simultaneously. We select a prototypical carbonyl (C═O)/N-based MR core as a backbone and attach it with D segments of different electron-donating abilities and numbers to obtain three different TADF emitters with emissions from sky blue to green and orange-red while maintaining the narrow emission of the original MR core. The corresponding sky blue, green, and orange-red organic light-emitting diodes achieve maximum external quantum efficiencies of 20.3, 27.3, and 26.3%, respectively, and narrow full widths at half-maximum all below 0.28 eV. These results provide a new molecular design strategy for developing narrowband TADF emitters with easily tunable emissions covering the full visible range.

Nonconjugated Triptycene-Spaced Donor-Acceptor-Type Emitters Showing Thermally Activated Delayed Fluorescence via Both Intra- and Intermolecular Charge-Transfer Transitions.

Thermally activated delayed fluorescence (TADF) emitters have aroused considerable attention, particularly for their great potential in organic light-emitting diodes (OLEDs). In typical TADF molecules, intramolecular charge transfer (CT) between electron-donor (D) and electron-acceptor (A) moieties is the dominant transition. Actually, CT transitions can possibly occur between different molecules as well. Herein, we used a nonconjugated triptycene (TPE) moiety to space D and A moieties and developed two novel emitters tBuDMAC-TPE-TRZ and tBuDMAC-TPE-TTR to explore the roles of intra- and intermolecular CT transitions. Along with weak intramolecular CT transitions, intermolecular CT transitions are dominant for tBuDMAC-TPE-TRZ and tBuDMAC-TPE-TTR neat films. Particularly, tBuDMAC-TPE-TRZ showed a high maximum external quantum efficiency of 10.0% in a nondoped solution-processed OLED, which was evidently higher than that of a corresponding 10 wt % tBuDMAC-TPE-TRZ-doped OLED with 4,4',4″-tris(carbazol-9-yl)triphenylamine (TCTA) as the host matrix. The results prove that intermolecular CT transitions indeed participate in the CT transition process in these systems and they are helpful to enhance the electroluminescence performance of emitting systems with weak intramolecular CT transitions.

Using fluorene to lock electronically active moieties in thermally activated delayed fluorescence emitters for high-performance non-doped organic light-emitting diodes with suppressed roll-off.

Thermally activated delayed fluorescence (TADF) emitters with aggregation-induced emission (AIE) features are hot candidates for non-doped organic light-emitting diodes (OLEDs), as they are highly emissive in solid states upon photoexcitation. Nevertheless, not every AIE-TADF emitter in the past had guaranteed decent efficiencies in non-doped devices, indicating that the AIE character alone does not necessarily afford ideal non-doped TADF emitters. As intermolecular electron-exchange interaction that involves long-lived triplet excitons plays a dominant role in the whole quenching process of TADF, we anticipate that it is the main reason for the different electroluminescence performances of AIE-TADF emitters. Therefore, in this work, we designed two TADF emitters SPBP-DPAC and SPBP-SPAC by modifying a reported less successful emitter BP-DPAC with extra fluorenes to increase intermolecular distances and attenuate this electron-exchange interaction. With the fluorene lock as steric hindrance, SPBP-DPAC and SPBP-SPAC exhibit significantly higher exciton utilization in non-doped films due to the suppressed concentration quenching. The non-doped OLEDs based on SPBP-DPAC and SPBP-SPAC show an excellent maximum external quantum efficiency (EQE) of 22.8% and 21.3% respectively, and what's even more promising is that ignorable roll-offs at practical brightness (e.g., 1000 and 5000 cd m-2) were realized. These results reveal that locking the phenyl rings as steric hindrance can not only enhance the molecular rigidity, but also cause immediate relief of concentration quenching, and result in significant performance improvement under non-doped conditions. Our approach proposes a feasible molecular modification strategy for AIE-TADF emitters, potentially increasing their applicability in OLEDs.

Highly Efficient Thermally Activated Delayed Fluorescence Emitter Developed by Replacing Carbazole With 1,3,6,8-Tetramethyl-Carbazole.

Carbazole (Cz) is the one of the most popular electron donors to develop thermally activated delayed fluorescence (TADF) emitters, but additional groups are generally required in the molecules to enhance the steric hindrance between Cz and electron acceptor segments. To address this issue, we replaced Cz with its derivative 1,3,6,8-tetramethyl-carbazole (tMCz) to develop TADF emitters. Two novel compounds, 6-(4-(carbazol-9-yl)phenyl)-2,4-diphenylnicotinonitrile (CzPN) and 2,4-diphenyl-6-(4- (1,3,6,8-tetramethyl-carbazol-9-yl)phenyl) nicotinonitrile (tMCzPN) were designed and synthesized accordingly. With the same and simple molecular framework, tMCzPN successfully exhibits TADF behavior, while CzPN is a non-TADF fluorophor, as the additional steric hindrance of methyl groups leads to a more twisted structure of tMCzPN. In the organic light-emitting diodes (OLEDs), tMCzPN exhibits extremely high forward-viewing maximum external quantum efficiency of 26.0%, without any light out-coupling enhancement, which is significantly higher than that of 5.3% for CzPN. These results indicate that tMCzPN is an excellent TADF emitter and proves that tMCz is a more appropriate candidate than Cz to develop TADF emitters.

Development of Red Exciplex for Efficient OLEDs by Employing a Phosphor as a Component.

Exciplexes are ideal candidates as effective thermally activated delayed fluorescence (TADF) emitters. However, efficient orange and red TADF exciplexes have been reported seldomly, because their significant non-radiative (NR) decay of excited states lead to unavoidable energy loss. Herein, we propose a novel strategy to construct efficient red TADF exciplexes by introducing phosphor as one component. Due to the strong spin-orbit coupling of heavy metal (e.g., Ir, Pt, et al.) ion cores, the NR decays will be evidently decreased for both singlet and triplet excitons, reducing the undesired exciton waste. Moreover, compared with the conventional exciplexes, phosphorescence plays an important role for such novel exciplexes, further improving the exciton utilization. Based on this strategy, we fabricated a red exciplex containing 1,3,5-triazine-2,4,6-triyl)tris(benzene-3,1-diyl)tris(diphenylphosphine oxide) (PO-T2T) and tris(2-phenylpyridine) iridium(III) (Ir(ppy)3) as components and realize a red emission with a peak at 604 nm, a CIE coordinate of (0.55, 0.44), and a high maximum external quantum efficiency of 5% in organic light-emitting device. This efficiency is 2.6 times higher than that of the device based on the conventional red exciplex emitter, proving the superiority of our novel strategy to construct TADF exciplexes with phosphors.

Tricomponent Exciplex Emitter Realizing over 20% External Quantum Efficiency in Organic Light-Emitting Diode with Multiple Reverse Intersystem Crossing Channels.

With the naturally separated frontier molecular orbitals, exciplexes are capable of thermally activated delayed fluorescence emitters for organic light-emitting diodes (OLEDs). And, the current key issue for exciplex emitters is improving their exciton utilization. In this work, a strategy of building exciplex emitters with three components is proposed to realize multiple reverse intersystem crossing (RISC) channels, improving their exciton utilization by enhancing upconversion of nonradiative triplet excitons. Accordingly, a tricomponent exciplex DBT-SADF:PO-T2T:CDBP is constructed with three RISC channels respectively on DBT-SADF, DBT-SADF:PO-T2T, and CDBP:PO-T2T. Furthermore, its photoluminescence quantum yield and rate constant of the RISC process are successfully improved. In the OLED, DBT-SADF:PO-T2T:CDBP exhibits a remarkably high maximum external quantum efficiency (EQE) of 20.5%, which is the first report with an EQE over 20% for the OLEDs based on exciplex emitters to the best of our knowledge. This work not only demonstrates that introducing multiple RISC channels can effectively improve the exciton utilization of exciplex emitters, but also proves the superiority of the tricomponent exciplex strategy for further development of exciplex emitters.

Thermally Activated Delayed Fluorescence Carbonyl Derivatives for Organic Light-Emitting Diodes with Extremely Narrow Full Width at Half-Maximum.

Two novel thermally activated delayed fluorescence (TADF) emitters, 3-phenylquinolino[3,2,1- de]acridine-5,9-dione (3-PhQAD) and 7-phenylquinolino[3,2,1- de]acridine-5,9-dione (7-PhQAD), were designed and synthesized based on a rigid quinolino[3,2,1- de]acridine-5,9-dione (QAD) framework. With the effective superimposed resonance effect from electron-deficient carbonyls and electron-rich nitrogen atom, both emitters realize significant TADF characteristics with small Δ ESTs of 0.18 and 0.19 eV, respectively. And, molecular relaxations were dramatically suppressed for both emitters because of their conjugated structure. In the devices, 3-PhQAD realizes superior performance with a maximum external quantum efficiency (EQE) of 19.1% and a narrow full width at half-maximum (FWHM) of 44 nm, whereas a maximum EQE of 18.7% and an extremely narrow FWHM of 34 nm are realized for 7-PhQAD. These superior results reveal that apart from nitrogen and boron-aromatic systems, QAD framework can also act as a TADF matrix with effective resonance effect, and QAD derivatives are ideal candidates to develop TADF emitters with narrow FWHMs for practical applications.

Control of Dual Conformations: Developing Thermally Activated Delayed Fluorescence Emitters for Highly Efficient Single-Emitter White Organic Light-Emitting Diodes.

In this work, we propose a novel concept to develop two fluorophores 2-(10 H-phenothiazin-10-yl)thianthrene 5,5,10,10-tetraoxide (PTZ-TTR) and 2-(4-(10 H-phenothiazin-10-yl)phenyl)thianthrene 5,5,10,10-tetraoxide (PTZ-Ph-TTR) showing dual conformations for highly efficient single-emitter white organic light-emitting diodes (WOLEDs). Both molecules exist in two stable conformations. Their nearly orthogonal forms own lower energy levels and show thermally activated delayed fluorescence (TADF) characteristics, whereas their nearly planar conformers possess higher energy levels and show only prompt fluorescence. These dual conformers were exploited for fabricating WOLEDs with complementary emission colors contributed by the two conformations. Moreover, the originally wasted triplet energy on the nearly planar conformation can be transferred to the nearly orthogonal one and then harvested via the TADF channel, realizing full exciton utilization. A PTZ-TTR-based single-emitter device exhibits standard white emission with a CIE coordinate of (0.33, 0.33) and a high color rendering index value of 92. On the other hand, the PTZ-Ph-TTR-based single-emitter device realizes an emission approaching warm white light and a high maximum external quantum efficiency of 16.34%. These results demonstrate an alternative approach for designing high-performance WOLEDs based on single TADF emitters.

Red Organic Light-Emitting Diode with External Quantum Efficiency beyond 20% Based on a Novel Thermally Activated Delayed Fluorescence Emitter.

A novel thermally activated delayed fluorescence (TADF) emitter 12,15-di(10H-phenoxazin-10-yl)dibenzo[a,c]dipyrido[3,2-h:2',3'-j]phenazine (DPXZ-BPPZ) is developed for a highly efficient red organic light-emitting diode (OLED). With rigid and planar constituent groups and evident steric hindrance between electron-donor (D) and electron-acceptor (A) segments, DPXZ-BPPZ realizes extremely high rigidity to suppress the internal conversion process. Meanwhile, the highly twisted structure between D and A segments will also lead to an extremely small singlet-triplet energy split to DPXZ-BPPZ. Therefore, DPXZ-BPPZ successfully realizes an efficient fluorescent radiation transition and reverse intersystem crossing process, and possesses an extremely high photoluminescence quantum efficiency of 97.1 ± 1.1% under oxygen-free conditions. The OLED based on DPXZ-BPPZ shows red emission with a peak at 612 nm and a Commission Internationale de L'Eclairage (CIE) coordinate of (0.60, 0.40), and it achieves high maximum forward-viewing efficiencies of 20.1 ± 0.2% (external quantum efficiency), 30.2 ± 0.6 cd A-1 (current efficiency), and 30.9 ± 1.3 lm W-1 (power efficiency). The prepared OLED has the best performance among the reported red TADF OLEDs. These results prove that DPXZ-BPPZ is an ideal candidate for red TADF emitters, and the designing approach is valuable for highly efficient red TADF emitters.