Red/Near‐Infrared Thermally Activated Delayed Fluorescence OLEDs with Near 100 % Internal Quantum Efficiency

Developing red thermally activated delayed fluorescence (TADF) emitters, attainable for both high‐efficient red organic light‐emitting diodes (OLEDs) and non‐doped deep red/near‐infrared (NIR) OLEDs, is challenging. Now, two red emitters, BPPZ‐PXZ and mDPBPZ‐PXZ, with twisted donor–acceptor structures were designed and synthesized to study molecular design strategies of high‐efficiency red TADF emitters. BPPZ‐PXZ employs the strictest molecular restrictions to suppress energy loss and realizes red emission with a photoluminescence quantum yield (Φ_PL) of 100±0.8 % and external quantum efficiency (EQE) of 25.2 % in a doped OLED. Its non‐doped OLED has an EQE of 2.5 % owing to unavoidable intermolecular π–π interactions. mDPBPZ‐PXZ releases two pyridine substituents from its fused acceptor moiety. Although mDPBPZ‐PXZ realizes a lower EQE of 21.7 % in the doped OLED, its non‐doped device shows a superior EQE of 5.2 % with a deep red/NIR emission at peak of 680 nm.     

Dicyano-Imidazole: A Facile Generation of Pure Blue TADF Materials for OLEDs

A series of dicyano-imidazole-based molecules with thermally activated delayed fluorescence (TADF) properties were synthesized to obtain pure blue-emitting organic light-emitting diodes (OLEDs). The targeted molecules used dicyano-imidazole with a short-conjugated system as the electron acceptor to strong intermolecular π-π interactions, and provide a relatively shallow energy level of the lowest unoccupied molecular orbital (LUMO). The cyano group was selected to improve imidazole as an electron acceptor due to its prominent electron-transporting characteristics. Four different electron donors, that is, 9,9-dimethyl-9,10-dihydroacridine (DMAC), 10H-spiro(acridine-9,9’-fluoren) (SPAC), and 9,9-diphenyl-9,10-dihydroacridine (DPAC), were used to alternate the highest occupied molecular orbital (HOMO) energy level to tune the emission color further. The crowded molecular structure in space makes the electron donor and acceptor almost orthogonal, reducing the energy gap (ΔE_ST) between the first excited singlet (S₁) and the triplet (T₁) states and introducing significant TADF property. The efficiencies of the blue-emissive devices with imM-SPAC and imM-DMAC obtained in this work are the highest among the reported imidazole-based TADF-OLEDs, which are 13.8 % and 13.4 %, respectively. Both of Commission Internationale de l′Eclairage (CIE) coordinates are close to the saturated blue region at (0.17, 0.18) and (0.16, 0.19), respectively. Combining these tailor-made TADF compounds with specific device architectures, electroluminescent (EL) emission from sky-blue to deep-blue could be achieved, proving their great potential in EL applications.     

Quinoxaline and Pyrido[x,y-b]pyrazine-Based Emitters: Tuning Normal Fluorescence to Thermally Activated Delayed Fluorescence and Emitting Color over the Entire Visible-Light Range

Quinoxaline (Q), pyrido[2,3-b]pyrazine (PP) and pyrido[3,4-b]pyrazine (iPP) are used as electron acceptors (A) to design a series of D–π–A-type light-emitting materials with different donor (D) groups. By adjusting the molecular torsion angles through changing D from carbazole (Cz) to 10-dimethylacridine (DMAC) or 10H-phenoxazine (PXZ) for a fixed A, the luminescence is tuned from normal fluorescence to thermally activated delayed fluorescence (TADF). By gradually enhancing the intramolecular charge-transfer extent through combining different D and A, the emission color is continuously and regularly tuned from pure blue to orange–red. Organic light-emitting diodes (OLEDs) containing these compounds as doped emitters exhibit bright electroluminescence with emission colors covering the entire visible-light range. An external quantum efficiency (η_ext) of 1.2 % with excellent color coordinates of (0.16, 0.07) is obtained for the pure-blue OLED of Q-Cz. High η_ext values of 12.9 (35.9) to 16.7 % (51.9 cd A⁻¹) are realized in the green, yellow, and orange–red TADF OLEDs. All PP- and iPP-based TADF emitters exhibit superior efficiency stabilities to that of analogues of Q. This provides a practical strategy to tune the emission color of Q, PP, and iPP derivatives with the same molecular skeletons over the entire visible-light range.     

Bright Solid‐State Emission of Disilane‐Bridged Donor–Acceptor–Donor and Acceptor–Donor–Acceptor Chromophores

The development of disilane‐bridged donor–acceptor–donor (D‐Si‐Si‐A‐Si‐Si‐D) and acceptor–donor–acceptor (A‐Si‐Si‐D‐Si‐Si‐A) compounds is described. Both types of compound showed strong emission (λ_em=ca. 500 and ca. 400 nm, respectively) in the solid state with high quantum yields (Φ: up to 0.85). Compound 4 exhibited aggregation‐induced emission enhancement in solution. X‐ray diffraction revealed that the crystal structures of 2 , 4 , and 12 had no intermolecular π–π interactions to suppress the nonradiative transition in the solid state.     

Effects of Electron Affinity and Steric Hindrance of the Trifluoromethyl Group on the π-Bridge in Designing Blue Thermally Activated Delayed Fluorescence Emitters

To explore the correlation of the acceptor electron affinity and the molecular conformation to the thermally activated delayed fluorescence (TADF) feature, a series of d -π-A molecules were designed and synthesized with triazine (Trz) as the acceptor (A) and carbazole (Cz) or tert-butylcarbazole (BuCz) as the donor (D). On the phenylene bridge between D and A, methyl or trifluoromethyl was incorporated close either to D or to A to tune the molecular conformation and the electron-withdrawing ability of acceptor. Both the twist angles and the singlet and triplet energy difference (ΔE_ST) were observed strongly dependent on the type and position of the substituent on the π-bridge. Only those molecules with trifluoromethyl locating close to the D side, namely TrzCz-CF₃ and TrzBuCz-CF₃, exhibit TADF feature, verifying that both sufficient electron affinity of the A unit and large dihedral angle between D and the π-bridge are necessary to ensure the occurrence of TADF. The blue organic light-emitting diodes fabricated with TrzCz-CF₃ and TrzBuCz-CF₃ achieved external quantum efficiencies of 9.40 % and 14.22 % with CIE coordinates of (0.19, 0.23) and (0.18, 0.29) respectively. This study provides practical design strategy for blue TADF materials particularly when planar and less crowded group is used as donor.     

Meta Junction Promoting Efficient Thermally Activated Delayed Fluorescence in Donor‐Acceptor Conjugated Polymers

The meta junction is proposed to realize efficient thermally activated delayed fluorescence (TADF) in donor–acceptor (D‐A) conjugated polymers. Based on triphenylamine as D and dicyanobenzene as A, as a proof of concept, a series of D‐A conjugated polymers has been developed by changing their connection sites. When the junction between D and A is tuned from para to meta, the singlet–triplet energy splitting (ΔE_ST) is found to be significantly decreased from 0.44 to 0.10 eV because of the increasing hole–electron separation. Unlike the para‐linked analogue with no TADF, consequently, the meta‐linked polymer shows a strong delayed fluorescence. Its corresponding solution‐processed organic light‐emitting diodes (OLEDs) achieve a promising external quantum efficiency (EQE) of 15.4 % (51.9 cd A^?1, 50.9 lm W^?1) and CIE coordinates of (0.34, 0.57). The results highlight the bright future of D‐A conjugated polymers used for TADF OLEDs.     

A Simple and Strong Electron‐Deficient 5,6‐Dicyano[2,1,3]benzothiadiazole‐Cored Donor‐Acceptor‐Donor Compound for Efficient Near Infrared Thermally Activated Delayed Fluorescence

Despite the success of thermally activated delayed fluorescent (TADF) materials in steering the next generation of organic light‐emitting diodes (OLEDs), effective near infrared (NIR) TADF emitters are still very rare. Here, we present a simple and extremely high electron‐deficient compound, 5,6‐dicyano[2,1,3]benzothiadiazole (CNBz), as a strong electron‐accepting unit to develop a sufficiently strong donor‐acceptor (D?A) interaction for NIR emission. End‐capping with the electron‐donating triphenylamine (TPA) unit created an effective D?A?D type system, giving rise to an efficient NIR TADF emissive molecule (λ_em=750 nm) with a very small ΔE_ST of 0.06 eV. The electroluminescent device using this NIR TADF emitter exhibited an excellent performance with a high maximum radiance of 10020 mW Sr^?1 m^?2, a maximum EQE of 6.57% and a peak wavelength of 712 nm.     

Meta Junction Promoting Efficient Thermally Activated Delayed Fluorescence in Donor-Acceptor Conjugated Polymers

The meta junction is proposed to realize efficient thermally activated delayed fluorescence (TADF) in donor–acceptor (D-A) conjugated polymers. Based on triphenylamine as D and dicyanobenzene as A, as a proof of concept, a series of D-A conjugated polymers has been developed by changing their connection sites. When the junction between D and A is tuned from para to meta, the singlet–triplet energy splitting (ΔE_ST) is found to be significantly decreased from 0.44 to 0.10 eV because of the increasing hole–electron separation. Unlike the para-linked analogue with no TADF, consequently, the meta-linked polymer shows a strong delayed fluorescence. Its corresponding solution-processed organic light-emitting diodes (OLEDs) achieve a promising external quantum efficiency (EQE) of 15.4 % (51.9 cd A⁻¹, 50.9 lm W⁻¹) and CIE coordinates of (0.34, 0.57). The results highlight the bright future of D-A conjugated polymers used for TADF OLEDs.     

Purely Organic Crystals Exhibit Bright Thermally Activated Delayed Fluorescence

Thermally activated delayed fluorescent (TADF) materials generally suffer from severe concentration quenching. Efficient non‐doped TADF emitters are generally highly twisted aromatic amine‐based compounds with isolated chemical moieties. Herein we demonstrate that co‐facial packing and strong π–π intermolecular interactions give rise to bright TADF emissions in non‐doped film and crystalline states within the compound 2,4‐diphenyl‐6‐(thianthren‐1‐yl)‐1,3,5‐triazine (oTE‐DRZ). Quantum chemistry simulations indicate that a disperse outer orbital of sulfur atoms, a folded thianthrene plane (for a reduced donor–acceptor distance), and a triazine acceptor with n–π* character, generate a spatially conjugated transition with a small singlet–triplet splitting energy. In company with a highly emissive non‐doped film, the corresponding organic light‐emitting diode achieved a 20.6 % external quantum efficiency, verifying its potential for high‐performance optoelectronic applications. In a crystalline state, it was verified that intra‐ and intermolecular dual TADF assisted by a hidden room‐temperature phosphorescent state. This state could preserve the long‐lived excitons while suppressing non‐radiation, and it could serve as a “spring‐board” for cascade up‐conversion processes. The oTE‐DRZ crystal showed greenish‐blue emission with a very high photoluminescent quantum yield of approximately 87 %, which is the highest among all TADF crystals reported to date.     

Molecular Design Strategy of Thermally Activated Delayed Fluorescent Emitters Using CN‐Substituted Imidazopyrazine as a New Electron‐Accepting Unit

Thermally activated delayed fluorescence (TADF)‐based organic light‐emitting diodes (OLEDs) have attracted enormous attention recently due to their capability to replace conventional phosphorescent organic light‐emitting diodes for practical applications. In this work, a newly designed CN‐substituted imidazopyrazine moiety was utilized as an electron‐accepting unit in a TADF emitter. Two TADF emitters, 8‐(3‐cyano‐4‐(9,9‐dimethylacridin‐10(9H)‐yl)phenyl)‐2‐phenylimidazo[1,2‐a]pyrazine‐3‐carbonitrile (Ac‐CNImPyr) and 8‐(3‐cyano‐4‐(10H‐phenoxazin‐10‐yl)phenyl)‐2‐phenylimidazo[1,2‐a]pyrazine‐3‐carbonitrile (PXZ‐CNImPyr), were developed based on the CN‐substituted imidazopyrazine acceptor combined with acridine and phenoxazine donor, respectively. A CN‐substituted phenyl spacer was introduced between the donor and acceptor for a sufficiently small singlet‐triplet energy gap (ΔE_ST) and molecular orbital management. Small ΔE_ST of 0.07 eV was achieved for the phenoxazine donor‐based PXZ‐CNImPyr emitter. As a result, an organic light‐emitting diode based on the PXZ‐CNImPyr emitter exhibited a high external quantum efficiency of up to 12.7 %, which surpassed the EQE limit of common fluorescent emitters. Hence, the CN‐modified imidazopyrazine unit can be introduced as a new acceptor for further modifications to develop efficient TADF‐based OLEDs.     

Design,synthesis, and properties of polystyrene-based through-space charge transfer polymers: Effect of triplet energy level of electron donor moiety on delayed fluorescence and electroluminescence performance

Two kinds of polystyrene-based through-space charge transfer (TSCT) polymers consisting of spatially-separated acridan donor moieties bearing phenyl or naphthyl substituents and triazine acceptor moieties are designed and synthesized. It is found that TSCT polymers containing phenyl-substituted acridan donors exhibit high-lying singlet (S₁) and triplet (T₁) states with small singlet-triplet energy splitting (∆E_ST) of 0.04–0.05 eV, resulting in thermally activated delayed fluorescence (TADF) with reverse intersystem crossing rate constants of 1.1–1.2 × 10⁶ s⁻¹. In contrast, polymers bearing naphthyl-substituted acridan donors, although still having TSCT emission, exhibit no TADF effect because of the large ∆E_ST of 0.30–0.33 eV induced by low-lying locally excited T₁ state of naphthyl donor moiety. Solution-processed organic light-emitting diodes using TSCT polymers containing phenyl-substituted acridan donors reveal sky-blue emission at 483 nm together with maximum external quantum efficiency (EQE) of 11.3%, which is about 30 times that of naphthyl-substituted counterpart with maximum EQE of 0.38%, shedding light on the importance of high triplet energy level of donor moiety on realizing TADF effect and high device efficiency for through-space charge transfer polymer.     

Quinoline-based aggregation-induced delayed fluorescence materials for highly efficient non-doped organic light-emitting diodes

Three new emitters,namely 10,10'-(quinoline-2,8-diyl)bis(10 H-phenoxazine)(Fene),10,10'-(quinoline-2,8-diyl)bis(10 H-phenothiazine)(Fens) and 10,10'-(quinoline-2,8-diyl)bis(9,9-dimethyl-9,10-dihydroacridine)(Yad),featuring quinoline as a new electron acceptor have been designed and conveniently synthesized.These emitters possessed small singlet-triplet splitting energy(ΔEst) and twisted structures,which not only endowed them show thermally activated delayed fluorescence(TADF)properties but also afforded a remarkable aggregation-induced emission(AIE) feature.Moreover,they also showed aggregation-induced delayed fluorescence(AIDF) property and good photoluminescence(PL) property,which are the ideal emitters for non-doped organic light-emitting diodes(OLEDs).Furthermore,high-performance non-doped OLEDs based on Fene,Fens and Yad were achieved,and excelle nt maximum external quantum efficiencies(EQE_(max)) of 14,9%,13.1% and 17,4%,respectively,were obtained.It was also found that all devices exhibited relatively low turn-on voltages ranging from 3.0 V to3.2 V probably due to their twisted conformation and the AIDF properties.These results demonstrated the quinoline-based emitters could have a promising application in non-doped OLEDs.     

Controlling Singlet–Triplet Energy Splitting for Deep‐Blue Thermally Activated Delayed Fluorescence Emitters

The development of efficient metal‐free organic emitters with thermally activated delayed fluorescence (TADF) properties for deep‐blue emission is still challenging. A new family of deep‐blue TADF emitters based on a donor–acceptor architecture has been developed. The electronic interaction between donor and acceptor plays a key role in the TADF mechanism. Deep‐blue OLEDs fabricated with these TADF emitters achieved high external quantum efficiencies over 19.2 % with CIE coordinates of (0.148, 0.098).     

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.

Two TADF emitters were developed by modifying a reported less successful emitter BP-DPAC with fluorene to suppress concentration quenching. Their non-doped OLEDs displayed excellent EQEs of 22.8% and 21.3% with well-suppressed roll-off.     

Molecular Design of Non-doped OLEDs Based on a Twisted Heptagonal Acceptor: A Delicate Balance between Rigidity and Rotatability

The development of efficient non-doped organic light-emitting diodes (OLEDs) is highly desired but very challenging because of a severe aggregation-caused quenching effect. Herein, we present a heptagonal diimide acceptor (BPI), which can restrict excessive intramolecular rotation and inhibit close intermolecular π–π stacking due to well-balanced rigidity and rotatability of heptagonal structure. The BPI-based luminogen ( DMAC-BPI ) shows significant aggregation-induced delayed florescence with an extremely high photoluminescence quantum yield (95.8 %) of the neat film, and the corresponding non-doped OLEDs exhibit outstanding electroluminescence performance with maximum external quantum efficiency as high as 24.7 % and remarkably low efficiency roll-off as low as 1.0 % at 1000 cd m⁻², which represents the state-of-the-art performance for non-doped OLEDs. In addition, the synthetic route to DMAC-BPI is greatly streamlined and simplified through oxidative Ar−H/Ar−H homo-coupling reaction.     

Dibenzo[a,j]phenazine‐Cored Donor–Acceptor–Donor Compounds as Green‐to‐Red/NIR Thermally Activated Delayed Fluorescence Organic Light Emitters

A new family of thermally activated delayed fluorescence (TADF) emitters based on U‐shaped D‐A‐D architecture with a novel accepting unit has been developed. All investigated compounds have small singlet‐triplet energy splitting (ΔE_ST) ranging from 0.02 to 0.20 eV and showed efficient TADF properties. The lowest triplet state of the acceptor unit plays the key role in the TADF mechanism. OLEDs fabricated with these TADF emitters achieved excellent efficiencies up to 16 % external quantum efficiency (EQE).     

甲基修饰的咔唑/二苯砜基AIE-TADF蓝光材料及其OLED器件

以四甲基咔唑为电子给体(D)、 二苯砜为电子受体(A)构建了具有D-A-D结构的纯有机咔唑/二苯砜衍生物——9,9'-[磺酰基双(3,1-亚苯基)]双(1,3,6,8-四甲基-9H-咔唑)(TMe-mSOCz). 对所合成材料的光物理性能研究表明, TMe-mSOCz表现出明显的聚集诱导发射(AIE)和热激活延迟荧光(TADF), 延迟寿命和延迟荧光占比分别为2.26 μs和47.7%, 并具有良好的电化学稳定性和热稳定性. 基于TMe-mSOCz作为非掺杂发光层制备了有机发光二极管(OLED)器件, 其启亮电压(V_on)为3.5 V, 最大外量子效率为5.63%, 国际照明委员会(CIE)坐标为(0.18, 0.26). 在1000 cd/m²亮度下, 非掺杂器件的效率滚降非常小(7.1%), 色彩稳定性较好, 其具有窄的半峰宽(FWHM=72 nm). 研究结果表明, 在传统TADF分子给受体间引入甲基修饰有利于开发具有AIE特性与更高效的D-A-D型TADF分子, 这为基于AIE-TADF分子开发新型OLED器件提供了新途径.     

Through-Space Charge-Transfer Polynorbornenes with Fixed and Controllable Spatial Alignment of Donor and Acceptor for High-Efficiency Blue Thermally Activated Delayed Fluorescence

Through-space charge transfer polynorbornenes with fixed and controllable spatial alignment of donor and acceptor in edge-to-face/face-to-face stacking patterns are developed for achieving high-efficiency blue thermally activated delayed fluorescence (TADF). The alignment is realized by using the cis, exo-configuration of norbornene to confine donor and acceptor in close proximity, and utilizing orthogonal and dendritic structures of donors to provide either perpendicular or parallel stacking motif relative to acceptors. Compared to edge-to-face counterparts, polynorbornenes with face-to-face aligned donor and acceptor exhibit much larger oscillator strength and higher photoluminescence quantum yield. The resulting polymers exhibit deep blue (422 nm) to sky blue (482 nm) emission and TADF effect with reverse intersystem crossing rates of 0.4–5.9×10⁶ s⁻¹, giving the maximum external quantum efficiency of 18.8 % for non-doped blue organic light-emitting diodes by solution process.     

Narrowband blue emission with insensitivity to the doping concentration from an oxygen-bridged triarylboron-based TADF emitter: nondoped OLEDs with a high external quantum efficiency up to 21.4%

Blue thermally activated delayed fluorescence (TADF) emitters that can simultaneously achieve narrowband emission and high efficiency in nondoped organic light-emitting diodes (OLEDs) remain a big challenge. Herein, we successfully design and synthesize two blue TADF emitters by directly incorporating carbazole fragments into an oxygen-bridged triarylboron acceptor. Depending on the linking mode, the two emitters show significantly different photophysical properties. Benefitting from the bulky steric hindrance between the acceptor and terminal pendants, the blue emitter TDBA-Cz exhibited a high photoluminescence quantum yield (PLQY) of 88% in neat films and narrowband emission. The corresponding non-doped blue device exhibited a maximum external quantum efficiency (EQE) of 21.4%, with a full width at half maximum (FWHM) of only 45 nm. This compound is the first blue TADF emitter that can concurrently achieve narrow bandwidth and high electroluminescence (EL) efficiency in nondoped blue TADF-OLEDs.

A donor–acceptor TADF emitter showed narrowband high-efficiency blue emission by fine molecular modulation. The corresponding OLEDs exhibited a maximum EQE of 21.4% and a small FWHM of 45 nm, representing the most efficient nondoped blue TADF-OLEDs.     

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.