First-Principles Investigation on Triazine Based Thermally Activated Delayed Fluorescence Emitters

Three kinds of triazine based organic molecules designed for thermally activated delayed fluorescence （TADF） emitters are investigated by first-principles calculations. An optimal Hartree-Fork （HF） method is adopted for the calculation of energy gap between the first singlet state （S1） and the first triplet state （T1）. The natural transition orbital, the electron- hole （e-h） distribution and the e-h overlap diagram indicate that the S1 states for the three systems include both charge-transfer and some localized excitation component. Further quantitative analysis of the excitation property is performed by introducing the index Ar and the integral of e-h overlap S. It is found that symmetric geometry is a necessary condition for TADF emitters, which can provide more delocalized transition orbitals and consequently a small S1-T1 energy gap. Artful inserting aromatic groups between donors and acceptors can significantly enhance the oscillator strength. Finally, the energy state structures calculated with the optimal HF method is presented, which can provide basis for the study of the dynamics of excited states.

Inuence of Electron Donating Ability on Reverse Intersystem Crossing Rate for One Kind of Thermally Activated Delayed Fluorescence Molecules

First-principles calculations are applied for investigating influence of electron donating ability of donor groups in eight thermally activated delayed fluorescence（TADF） molecules on their geometrical structures and transition properties as well as reverse intersystem crossing（RISC） processes. Results show that the diphenylamine substitution in the donor part can slightly change the bond angle but decrease bond length between donor and acceptor unit except for the lowest triplet state（Ti） of carbazole-xanthone molecule. As the electron donating ability of donor groups is increased, the overlap between the highest occupied molecular orbital（HOMO） and the lowest unoccupied molecular orbital（LUMO） is decreased. As the diphenylamine groups are added in donor part, the delocalization of HOMO is enlarged,which brings a decreased energy gap(△ES1-T1) between the lowest singlet excited state（S1）and T1 state. Furthermore, with the calculated spin-orbit coupling coefficient(HSO), one finds that the larger value of ■ is, the faster the RISC is. The results show that all investigated molecules are promising candidates as TADF molecules. Overall, a wise molecular design strategy for TADF molecules,in which a small △ES1-T1 can be achieved by enlarging the delocalization of frontier molecular orbitals with large separation between HOMO and LUMO, is proposed.

High Efficiency and Stable Organic Light-Emitting Diodes Based on Thermally Activated Delayed Fluorescence Emitter

High efficiency, stable organic light-emitting diodes （OLEDs） based on 2-pheyl-4＇-carbazole-9-H-Thioxanthen-9- one-10, 10-dioxide （TXO-PhCz） with different doping concentration are constructed. The stability of the encap- sulated devices are investigated in detail. The devices with the 10 wt% doped TXO-PhCz emitter layer （EML） show the best performance with a current efficiency of 52.1 cd/A, a power efficiency of 32.71re^W, and an external quantum efficiency （EQE） of 17.7%. The devices based on the lOwt%-doped TXO-PhCz EML show the best operational stability with a half-life time （LTSO） of 8Oh, which is 8 h longer than that of the reference devices based on fac-tris（2-phenylpyridinato）iridium（ Ⅲ） （Ir（ppy）a）. These indicate excellent stability of TXO-PhCz for redox and oxidation processes under electrical excitation and TXO-PhCz can be potentially used as the emitters for OLEDs with high efficiency and excellent stability. The high-performance device based on TXO-PhCz with high stability can be further improved by the optimization of the encapsulation technology and the development of a new host for TXO-PhCz.

Theoretical verification of intermolecular hydrogen bond induced thermally activated delayed fluorescence in SOBF-OMe

Thermally activated delayed fluorescence(TADF)molecules have attracted great attention as high efficient luminescent materials.Most of TADF molecules possess small energy gap between the first singlet excited state(S_(1))and the first triplet excited state(T_(1))to favor the up-conversion from T_(1)to S_(1).In this paper,a new TADF generation mechanism is revealed based on theoretical simulation.By systematic study of the light-emitting properties of SOBF-OMe in both toluene and in aggregation state,we find that the single SOBF-OMe could not realize TADF emission due to large energy gap as well as small up-conversion rates between S_(1)and T_(1).Through analysis of dimers,we find that dimers with intermolecular hydrogen bond(H-bond)are responsible for the generation of TADF,since smaller energy gap between S_(1)and T_(1)is found and the emission wavelength is in good agreement with experimental counterpart.The emission properties of SOBF-H are also studied for comparison,which reflect the important role of H-bond.Our theoretical results agree ith experimental results well and confirm the mechanism of H-bond induced TADF.

Effect of aggregation on thermally activated delayed fluorescence and ultralong organic phosphorescence:QM/MM study

Aggregation-induced thermally activated delayed fluorescence(TADF)phenomena have attracted extensive attention recently.In this paper,several theoretical models including monomer,dimer,and complex are used for the explanation of the luminescent properties of(R)-5-(9H-carbazol-9-yl)-2-(1,2,3,4-tetrahydronaphthalen-1-yl)isoindoline-1,3-dione((R)-ImNCz),which was recently reported[Chemical Engineering Journal 418129167(2021)].The polarizable continuum model(PCM)and the combined quantum mechanics and molecular mechanics(QM/MM)method are adopted in simulation of the property of the molecule in the gas phase,solvated in acetonitrile and in aggregation states.It is found that large spin–orbit coupling(SOC)constants and a smaller energy gap between the first singlet excited state and the first triplet excited state(△E_(st))in prism-like single crystals(SC_(p)-form)are responsible for the TADF of(R)-lmNCz,while no TADF is found in block-like single crystals(SC_(b)-form)with a larger △E_(st).The multiple ultralong phosphorescence(UOP)peaks in the spectrum are of complex origins,and they are related not only to ImNCz but also to a minor amount of impurities(ImNBd)in the crystal prepared in the laboratory.The dimer has similar phosphorescence emission wavelengths to the(R)-lmNCz-SC_(p) monomers.The complex composed of(R)-lmNCz and(R)-lmNBd contributes to the phosphorescent emission peak at about 600 nm,and the phosphorescent emission peak at about 650 nm is generated by(R)-lmNBd.This indicates that the impurity could also contribute to emission in molecular crystals.The present calculations clarify the relationship between the molecular aggregation and the light-emitting properties of the TADF emitters and will therefore be helpful for the design of potentially more useful TADF emitters.

Luminescent properties of thermally activated delayed fluorescence molecule with intramolecular π-π interaction between donor and acceptor

Influence of intramolecular π-π interaction on the luminescent properties of thermally activated delayed fluorescence（TADF） molecule（3, 5-bis（3,6-di-tert-butyl-9 H-carbazol-9-yl）-phenyl）（pyridin-4-yl） methanone（DTCBPY） is theoretically studied by using the density functional theory（DFT） and time-dependent density functional theory（TD-DFT）.Four conformations（named as A, B, C, and D） of the DTCBPY can be found by relax scanning, and the configuration C corresponds to the luminescent molecule detected experimentally. Besides, we calculate the proportion of each conformation by Boltzmann distribution, high configuration ratios（44% and 52%） can be found for C and D. Moreover, C and D are found to exist with an intramolecular π-π interaction between one donor and the acceptor; the intramolecular interaction brings a smaller Huang-Rhys factor and reduced reorganization energy. Our work presents a rational explanation for the experimental results and demonstrates the importance of the intramolecular π-π interaction to the photophysical properties of TADF molecules.

TADF敏化荧光策略构建高效、窄光谱发光电化学池器件

基于新一代热活化延迟荧光(Thermally activated delayed fluorescence,TADF)发光材料的发光电化学池(Light-emitting electrochemical cells,LECs)成为新兴的研究方向而受到关注。由于TADF发光材料电荷分离态的激子属性,该类LECs器件发光光谱半峰宽往往达到100 nm以上,难以满足LEC高色纯度的需求。鉴于此,本文尝试将TADF敏化荧光(TADF-sensitized fluorescence,TSF)的激子管控策略应用到LECs领域当中。通过筛选合适的传输主体、TADF敏化剂、高吸光系数荧光染料和离子液体固态电解质为LEC的发光层,我们成功构建了高效TSF型的LECs器件。最终获得的TSF-LECs器件峰值外量子效率(The highest external quantum ef-ficiency,EQEmax)达到3.7%,峰值亮度(The peak luminance,Lmax)达到2285 cd·m^(-2)。与TADF-LECs的参比器件相比,TSF-LECs器件的光谱半峰宽(Full width at half maximum,FWHM)从106 nm降低至38 nm。本文还详细讨论了所制备TSF-LECs器件中的能量转移和激子损失途径。该工作为进一步优化设计TSF-LECs材料和器件奠定了基础。

Chiral thermally activated delayed fluorescence materials for circularly polarized organic light-emitting diodes

Chirality is an important natural characteristic of organic molecules,and chiral organic molecules have shown extensive application in areas such as pharmaceutical development and material science.Benefiting from the ability to achieve circularly polarized luminescence(CPL),chiral luminescent materials have shown potential applications in anti-glare display,optical communication and,3D display,etc.Due to the ability to harvest both singlet and triplet excitons by a fast reverse intersystem crossing process without involving noble metals,chiral thermally activated delayed fluorescence(TADF)materials with point chirality,axial chirality,planar chirality and helical chirality are regarded as the state-of-the-art materials for circularly polarized organic light-emitting diodes(CP-OLEDs).In recent years,the chiral TADF materials and CP-OLEDs have rapidly developed,but unfortunately,the dissymmetry factors(g)are far from the requirement of practical applications.The ideal emitters and devices should have both high efficiency and a g factor,or at least a balance between these two elements.This review gives an overview of recent progress in chiral TADF materials,with a particular focus on the chiral skeleton,CPL property and device performance.Furthermore,the molecular design concept,device structure and methods to improve the g factors of chiral materials and CP-OLEDs are also discussed.

Chiral multiple-resonance thermally activated delayed fluorescence materials based on chiral spiro-axis skeleton for efficient circularly polarized electroluminescence

Chiral luminescence materials have potential applications in the field of three-dimensional displays due to their circularly polarized luminescence(CPL)characteristics.However,the further development of circularly polarized organic light-emitting diodes(CP-OLEDs)needs to meet the requirements of high efficiency,high color purity,low cost,and high dissymmetry factor(gPLor gEL),chiral multiple resonance thermally activated delayed fluorescence(MR-TADF)materials are considered as candidates in these aspects.Herein,based on a pair of chiral spirofluorene precursors,two pairs of high-performance chiral MR-TADF emitters((R/S)-p-Spiro-DtBuCzB and(R/S)-m-Spiro-DtBuCzB)are developed,which exhibit strong emissions peaking at 491 and 502 nm in toluene with full-width at half-maximum values of 25 and 33 nm,respectively.In addition,small singlet–triplet energy gaps of 0.15 and 0.10 eV with high absolute photoluminescence efficiencies of 95.0%and 96.7%are observed for p-Spiro-DtBuCzB and m-Spiro-DtBuCzB molecules,respectively.OLEDs based on p-Spiro-DtBuCzB and m-Spiro-DtBuCzB display high maximum external quantum efficiencies of 29.6%and 33.8%,respectively.Most importantly,CP-OLEDs present symmetric circularly polarized electroluminescence spectra with|gEL|factors of 3.36×10^(-4)and 7.66×10^(-4)for devices based on(R/S)-p-Spiro-DtBuCzB and(R/S)-m-Spiro-DtBuCzB enantiomers,respectively.

器件结构对蓝光TADF-OLED光电性能的影响

采用真空热蒸镀法,以热活化延迟荧光(TADF)材料为主体材料、发光材料为客体材料制备混合薄膜发光层,以提高蓝色荧光材料的OLED发光效率。当OLED器件结构为ITO/HAT-CN(5 nm)/TAPC(30 nm)/TCTA(10 nm)/Blue-Or:DMAC-DPS(30%,30 nm)/DPEPO(10 nm)/Bphen(30 nm)/LiF(1 nm)/Al(70 nm)时,器件的光电性能最佳。此蓝光TADF-OLED器件的外量子效率为12.39%,电流效率为21.68 cd/A,功率效率为19.44 lm/W。研究发现改变TADF-OLED的掺杂主体材料和添加空穴注入层均可有效地提高器件的光电特性。实验内容与该领域的前沿科学研究相结合,OLED器件的光电性能稳定、实验现象显著,适于引入本科实验课程。通过该综合实验学生可以夯实实验基础、了解研究热点、掌握最新的科研动态。

A modular approach to efficient thermally activated delayed fluorescence from metal-perturbed intraligand charge-transfer excited state of Au(Ⅰ)complexes

The efficient harvesting of triplet excitons is crucial to the realization of high-performance organic light-emitting diodes(OLEDs).Herein,we show that coordination of donor-acceptor(D-A)type molecules to a metal atom in a monodentate fashion can lead to thermally activated delayed fluorescence(TADF)emissions with wide color tunability only through varying the noncoordinating acceptor moiety.A panel of TADF gold(Ⅰ)complexes with emission maxima(λmax)of 545–645 nm from metal perturbed intraligand charge-transfer(MPICT)excited states have been developed.Synergetic effects of heavy atom-induced spin-orbit coupling(SOC),steric-induced donor-acceptor twisting and suppressed intramolecular motions lead to high emission efficiencies of 65%-85%in doped films with delayed fluorescence lifetime of as short as 2.0μs.Transient absorption spectroscopic studies on selected complexes determined the kISCto be 6.5×10^(9)s^(-1).Theoretical calculations confirmed the participation of minor d orbital into the lowest excited state,which led to an SOC value of 5.19 cm^(-1)between the lowest-lying singlet and triplet excited states.The yellow to deep red solution-processed OLEDs based on the new gold(Ⅰ)complexes incorporated with various D-A ligands demonstrated promising performances.This study validates a modular design for TADF metal complexes,which will broaden the choices of metal centers and allow for facile color tuning via simple ligand synthesis.

Thermally activated delayed fluorescence carbazole-triazine dendrimer with bulky substituents

Carbazole-triazine dendrimers with a bulky terminal substituent were synthesized,and the thermally activated delayed fluorescence(TADF)property was investigated.Compared to unsubstituted carbazole dendrimers,dendrimers with bulky terminal substituents showed comparable to better photoluminescence quantum yields(PLQY)in neat films.Phenylfluorene(PF)-substituted dendrimers showed the highest PLQY of 81%,a smallΔEst of 0.06 eV,and the fastest reverse intersystem crossing(RISC)rate of∼1×10^(5 )s^(−1) compared to other dendrimers.Phosphorescence measurements of dendrimers and dendrons(fragments)indicate that the close proximity of the triplet energy of phenylfluorene-substituted carbazole dendrons(^(3)LE)to that of phenylfluorene-substituted dendrimers(^(1)CT,^(3)CT)contributes to RISC promotion and improves TADF efficiency.Terminal modification fine-tunes the energy level and suppresses intermolecular interactions,and this study provides a guideline for designing efficient solution-processable and non-doped TADF materials.

基于器件结构提高TADF-OLED器件的发光性能

为了提高以TADF材料作为主体、天蓝色荧光材料作为客体的混合薄膜的OLED器件光电性能,我们调整了器件结构,使主体材料发挥其优势。制备了基本结构为ITO/NPB(40 nm)/DMAC-DPS∶x%BUBD-1(40 nm)/Bphen(30 nm)/LiF(0.5 nm)/Al的OLED器件。研究了主-客体材料在不同掺杂浓度下的OLED器件的光电特性。为了提高主体材料的利用率,在空穴传输层和发光层之间加入10 nm的DMAC-DPS作为间隔层;然后,在阳极和空穴传输层之间加入HAT-CN作为空穴注入层,形成HAT-CN/NPB结构的PN结,有效降低了器件的启亮电压(2.7 V)。测量了有无HAT-CN的单空穴器件的阻抗谱。结果表明,在最佳掺杂比例(2%)下,器件的外量子效率(EQE)达到4.92%,接近荧光OLED的EQE理论极限值;加入10 nm的DMAC-DPS作为间隔层,使得器件的EQE达到5.37%;HAT-CN/NPB结构的PN结有效地降低了器件的启亮电压(2.7 V),将OLED器件的EQE提高到5.76%;HAT-CN的加入提高了器件的空穴迁移率,降低了单空穴器件的阻抗。TADF材料作为主体材料在提高OLED器件的光电性能方面具有很大的潜力。

Heptagonal intramolecular-lock strategy enables high-performance thermally activated delayed fluorescence emitters

The development of highly efficient thermally activated delayed fluorescence(TADF)emitters is persistently pursued for the application of organic light-emitting diodes(OLED)in full-colour display and solid-state lighting.Herein,we present a heptagonal intramolecular-lock strategy to design high-performance TADF emitters.As a proof-of-concept,a new type of tribenzotropone(TBP)acceptor has been designed and synthesized by a cascade decarboxylative cyclization of aryl oxoacetic acid derivative with biphenyl boronic acid.Compared with the unlocked benzophenone(BP)acceptor,the TBP acceptor has a highly twisted heptagonal geometry with moderate rigidity and flexibility,which enables a high-performance TADF emitter with a small single-triplet energy gap(ΔE_(ST))of 0.04 e V,a high photoluminescence quantum yield(Φ_(PL))of 99% and a large horizontal orientation factor(Θ_(//))of 84.0%.Consequently,highly efficient OLEDs with an external quantum efficiency as high as 33.8% are assembled,which is significantly higher than those of DPAC-BP with a highly rotatable BP acceptor(23.8%)as well as DPACFO with a rigid fluorenone(FO)acceptor(6.9%).

Supramolecular Thermally Activated Delayed Fluorescence Materials via Through-Space Charge Transfer

Thermally activated delayed fluorescence(TADF)polymeric materials based on through-space charge transfer(TSCT)have emerged as a highly studied topic in recent years.However,the construction of TSCT TADF materials via a supramolecular approach is still a big challenge.In this work,we report the noncovalent synthesis of TSCT TADF materials using a cyclic peptide-based bottle-brushed supramolecular polymer as a scaffold.By bringing the TSCT donor and acceptor in close proximity in space using the supramolecular scaffold,distinctive TADF emission in both solution and solid states could be achieved.Furthermore,the TADF system could be utilized as a sensitizer to coassemble with fluorescence acceptors to build thermally assisted fluorescence systems,resulting in color-tunable delayed fluorescence with high efficiency and color purity.Our findings provide a facile yet effective approach to designing and fabricating TSCT TADF materials,which might hold great potential for applications in the fields of organic light-emitting diode,bioimaging,and sensing.

One-shot synthesis of heavy-atom-modified carbazole-fused multi-resonance thermally activated delayed fluorescence materials

Efficient multi-resonance thermally activated delayed fluorescence(MR-TADF)materials hold significant potential for applications in organic light-emitting diodes(OLEDs)and ultra-high-definition displays.However,the stringent synthesis conditions and low yields typically associated with these materials pose substantial challenges for their practical applications.In this study,we introduce an innovative strategy that involves peripheral modification with sulfur and selenium atoms for two materials,CFDBNS and CFDBNSe.This approach enables a directed one-shot borylation process,achieving synthesis yields of 66%and 25%,respectively,while also enhancing reverse intersystem crossing rates.Both emitters exhibit ultra-narrowband sky-blue emissions centered around 474 nm,with full width at half maximum(FWHM)values as narrow as 19 nm in dilute toluene solutions,along with high photoluminescence quantum yields of 98%and 99%in doped films,respectively.The OLEDs based on CFDBNS and CFDBNSe display sky-blue emissions with peaks at 476 and 477 nm and exceptionally slender FWHM values of 23 nm.Furthermore,the devices demonstrate remarkable performances,achieving maximum external quantum efficiencies of 24.1%and 27.2%.This work presents a novel and straightforward approach for the incorporation of heavy atoms,facilitating the rapid construction of efficient MR-TADF materials for OLEDs.

Bipolar Thermally Activated Delayed Fluorescence Emitter with Balanced Carrier Transport for High-Efficiency Nondoped Green Electroluminescent Devices

High-efficiency electroluminescent devices featuring simplified architecture have received considerable attention due to significant advantages in construction procedures and commercialized applications.However,there still remains a critical challenge with regard to the lack of organic semiconductors that simultaneously possess high luminescent efficiency and balanced carrier-transporting abilities.Herein,we design a thermally activated delayed fluorescence(TADF)emitter 4-(9,9-dimethyl-9,10-dihydroacridine)-4′-triphenylphosphineoxide-benzophenone(DMAC-BPTPO)by incorporating triphenylphosphine oxide into the donor–acceptor skeleton.The accessional electrontransporting moiety,rod-like dimer,and horizontally packing model synergistically enable DMAC-BP-TPO which possesses an excellent photoluminescence quantum yield of nearly 90%with a reverse intersystem crossing rate constant of 2.0×106 s−1,horizontal dipole ratio of 89%,and a balanced electron and hole mobilities with a small constrast ratio of 1.08.Eventually,simplified electroluminescent devices including organic lightemitting diodes(OLEDs)and organic light-emitting transistors(OLETs)incorporating DMAC-BP-TPO-based nondoped film are demonstrated due to their superior integrated optoelectronic properties along with preferable horizontal dipole orientation.A record-high external quantum efficiency value of 21.7%and 4.4%are finally achieved in the simplified nondoped OLED and OLET devices,which are among the highest values in the related research fields.This work provides a new avenue to develop a high-efficiency bipolar TADF emitter to advance the simplified electroluminescent devices.

Red phosphorescent organic light-emitting diodes based on a novel host material with thermally activated delayed fluorescent properties

High cost of phosphors and significant efficiency roll-off at high brightness are the two main factors that limit the wide application of phosphorescent organic light-emitting diodes （PHOLEDs）. Efforts have been paid to find ways to reduce the phosphors＇ concentration and efficiency roll-off of PHOLEDs. In this work, we reported red emission PHOLEDs with low dopant concentration and low efficiency roll-off based on a novel host material 2,4-biscyanophenyl-6-（12-phenylindole[2,3-a]carbazole-ll-yl）-1,3,5-triazine （BCPICT）, with thermally activated delayed fluorescent （TADF） properties. The device with 1.0% dopant concentration displayed a maximum external quantum efficiency of 10.7%. When the dopant concentration was increased to 2.0%, the device displayed a maximum external quantum efficiency of 10.5% and a low efficiency roll-off of 5.7% at 1000 cd/m^2.

High-Efficiency Narrow-Band Electro-Fluorescent Devices with Thermally Activated Delayed Fluorescence Sensitizers Combined Through-Bond and Through-Space Charge Transfers

Organic light-emitting diodes utilizing thermally activated delayed fluorescence sensitizers and multiple-resonance(MR)dopants may simultaneously offer high efficiencies and narrow-band emissions,but these devices still face intractable challenges with a lack of design rules for high-performance sensitizers.Here,sensitizers with ortho-arranged donor–acceptors on a(trifluoromethyl)benzene linker have been proposed,which not only facilitate relatively small molecular dipole moments but also combine through-bond and through-space charge transfers for fast reverse intersystem crossing(RISC).

Alkoxy encapsulation of carbazole-based thermally activated delayed fluorescent dendrimers for highly efficient solution-processed organic light-emitting diodes

Two n-butoxy-encapsulated dendritic thermally activated delayed fluorescent(TADF) emitters(namely O-D1 and O-D2) with the first-/second-generation carbazoledendrons are designed and synthesized via C—N coupling between carbazoledendrons and 2,4,6-tris(4-bromophenyl)-1,3,5-triazine core.It is found that,compa red with the commo nly-used tert-butyl groups,the use of n-butoxy encapsulation groups can lead to smallersinglet-triplet energy gap for the dendrimers,producing stronger TADF effect together with faster reverse intersystem crossing process.Solution-processed TADF organic light-emitting diodes(OLEDs) utilizingalkoxy-encapsulated dendrimers O-D1 and O-D2 as emitters exhibitstate-of-the-art device efficiency withthe maximum external quantum efficiency up to 16.8% and 20.6%,respectively,which are ~1.6 and~2.0 times that of the tert-butyl-encapsulated counterparts.These results suggest that alkoxy encapsulation of the carbazole-based TADF dendrimers can be a promising approach for developing highly efficient emitters for solution-processed OLEDs.