Efficient Thermally Activated Delayed Fluorescence Emitters Research Articles

Efficient TADF from carbon−carbon bonded donor−acceptor molecules based on boron-carbonyl hybrid acceptor

We present a new type of thermally activated delayed fluorescence (TADF) emitters, namely, PCzBCO and BuPCzBCO, composed of the donor (D) and acceptor (A) units linked by a C–C bond. The two emitters have N-aryl carbazole as a donor and a planarized boron-carbonyl (BCO) unit as an acceptor. The crystal structure of BuPCzBCO reveals a moderate twist between the D and A units with a dihedral angle of 49.2°. Although both emitters exhibit the prompt fluorescence only in solution, they exhibit distinct TADF characteristics in the rigid state, with the high photoluminescence quantum yields of 81% and 93% in an mCBP host, respectively. Importantly, fast reverse intersystem crossing (RISC) with the rate constants of ∼106 s−1 is obtained in their host films. Along with the small singlet−triplet energy gap below 50 meV, theoretical studies demonstrate that RISC is facilitated by the strong spin-orbit coupling between the charge-transfer singlet excited state (1CT, S1) and the BCO-centered, local triplet excited state (3LE, T2) with a 3nπ* character. With the PCzBCO and BuPCzBCO molecules as emitters, efficient greenish blue TADF-OLEDs with similar maximum external quantum efficiency of 16.2% are realized. These findings highlight the potential of C–C bonded D−A molecules as efficient TADF emitters.

Modified Intramolecular‐Lock Strategy Enables Efficient Thermally Activated Delayed Fluorescence Emitters for Non‐Doped OLEDs

The development of intramolecular-lock strategy is an appealing task for designing efficient thermally activated delayed fluorescence (TADF) molecules, but only limited examples have been reported so far. Herein we present a "medium ring"-lock strategy to develop TADF emitters for improving the efficiency of organic light-emitting diodes (OLEDs). The installation of an electron-deficient heptagonal diimide lock onto a highly rotatable biphenyl-based emitter not only enhances electron-withdrawing ability of acceptor that decreases singlet-triplet energy gap (ΔEST ), but also endows the skeleton with modest rigidity and flexibility that increases photoluminescence quantum yield (PLQY) in neat film. In particular, the integration of the diimide lock also leads to an increase in horizontal orientation factor (Θ// ) from 69 % to 83 %. Consequently, this modified intramolecular-lock strategy enables an efficient TADF emitter to assemble high-performance non-doped OLEDs with a high external quantum efficiency of 26.2 % and a power efficiency of 76.6 lm W-1 .

Modified Intramolecular‐Lock Strategy Enables Efficient Thermally Activated Delayed Fluorescence Emitters for Non‐Doped OLEDs

AbstractThe development of intramolecular‐lock strategy is an appealing task for designing efficient thermally activated delayed fluorescence (TADF) molecules, but only limited examples have been reported so far. Herein we present a “medium ring”‐lock strategy to develop TADF emitters for improving the efficiency of organic light‐emitting diodes (OLEDs). The installation of an electron‐deficient heptagonal diimide lock onto a highly rotatable biphenyl‐based emitter not only enhances electron‐withdrawing ability of acceptor that decreases singlet‐triplet energy gap (ΔEST), but also endows the skeleton with modest rigidity and flexibility that increases photoluminescence quantum yield (PLQY) in neat film. In particular, the integration of the diimide lock also leads to an increase in horizontal orientation factor (Θ//) from 69 % to 83 %. Consequently, this modified intramolecular‐lock strategy enables an efficient TADF emitter to assemble high‐performance non‐doped OLEDs with a high external quantum efficiency of 26.2 % and a power efficiency of 76.6 lm W−1.

Phosphonium-Based Ionic Thermally Activated Delayed Fluorescence Emitters for High-Performance Partially Solution-Processed Organic Light-Emitting Diodes

Phosphonium-Based Ionic Thermally Activated Delayed Fluorescence Emitters for High-Performance Partially Solution-Processed Organic Light-Emitting Diodes

(Invited) Structural Analysis of Organic Semiconducting Materials By Solid State NMR

Recently, our group have successfully developed several blue and green thermally activated delayed fluorescence (TADF) emitters showing high external quantum efficiencies in OLEDs through high-throughput screening based on quantum chemical calculations. Although a number of highly efficient TADF emitters have been reported, the study about their conformation and aggregated structure in an amorphous states, which is expected to be the origin of high device performance, is still limited. Thus we have carried out multiscale simulations and solid-state NMR (ssNMR) analysis of organic amorphous thin films. The ssNMR is one of the powerful technique to acquire the structural information of amorphous aggregated materials, which has been difficult by diffraction techniques due to the lack of long range order for amorphous state. In this presentation, we demonstrate ssNMR analysis of amorphous organic semiconducting materials.Reference(1) “Analysis of Molecular Orientation in Organic Semiconducting Thin Films Using Static Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy”, Suzuki, K.; Kubo, S.; Aussenac, F.; Engelke, F.; Fukushima, T.; Kaji, H. Angew. Chem. Int. Ed. 2017, 56, 14842.(2) “Efficient blue thermally activated delayed fluorescence emitters showing very fast reverse intersystem crossing”, Ren, Y., Wada, Y., Suzuki, K., Kusakabe, Y., Geldsetzer, J. and Kaji, H. Appl. Phys. Express, 2021, 14, 071003.(3) “Solution-processable thermally activated delayed fluorescence emitters for application in organic light emitting diodes”, Suzuki, K.; Adachi, C.; Kaji, H. J. Soc. Inf. Disp. 2017, 25, 480.(4) “Combined Inter- and Intramolecular Charge-Transfer Processes for Highly Efficient Fluorescent Organic Light-Emitting Diodes with Reduced Triplet Exciton Quenching”, Moon, C.-K.; Suzuki, K.; Shizu, K.; Adachi, C.; Kaji, H.; Kim, J.-J. Adv. Mater. 2017, 131, 6614.(5) “Triarylboron-based Fluorescent Organic Light-emitting Diodes with External Quantum Efficiencies Exceeding 20%”, Suzuki, K.; Kubo, S.; Shizu, K.; Fukushima, T.; Wakamiya, A.; Murata, Y.; Adachi, C.; Kaji, H.; Angew. Chem. Int. Ed. 2015, 54, 15231.(5) “Purely organic electroluminescent material realizing 100% conversion from electricity to light”, Kaji, H.; Suzuki, H.; Fukushima, T.; Shizu, K.; Suzuki, K.; Kubo, S.; Komino, T.; Oiwa, H.; Suzuki, F.; Wakamiya, A.; Murata, Y.; Adachi, C. Nat. Commun. 2015, 6, 8476.

Multiplying the efficiency of red thermally activated delayed fluorescence emitter by introducing intramolecular hydrogen bond

As one of the three primary colors, red organic light-emitting diodes (OLEDs) are indispensable in practical applications. However, red emitters are generally subject to severe non-radiative exciton loss due to their narrow energy gap. In this work, three new thermally activated delayed fluorescence (TADF) emitters were developed, namely 4-(acenaphtho[1,2-b]quinoxalin-9-yl)-N,N-diphenylaniline (TPA-AP), 4-(acenaphtho[1,2-b]pyrido[2,3-e]pyrazin-10-yl)-N,N-diphenylaniline (TPA-APy), and 4-(acenaphtho[1,2-b]pyrazino[2,3-e]pyrazin-9-yl)-N,N-diphenylaniline (TPA-APm), employing a series of finely modified acenaphtho[1,2-b]quinoxaline (AP) derivatives as acceptor units. Among three TADF emitters, an intramolecular hydrogen bond is formed between the donor (D) and acceptor (A) units in TPA-APm. Consequently, the overlap of the frontier molecular orbitals (FMOs) of TPA-APm can increase appropriately, and the fluorescence radiative rate (kF) of TPA-APm is nearly twofold than that of TPA-AP and TPA-APy. Furthermore, the non-radiative decay rate (knr) of TPA-APm is less than that of TPA-AP and TPA-APy by an order of magnitude, which is attributed to the improved molecular rigidity caused by intramolecular hydrogen bond. As a result, TPA-APm-based OLEDs achieved a multiplied external quantum efficiency (EQE) of 21.1% with the electroluminescence peak at 590 nm, comparing to only 7.0% and 11.5% for the TPA-AP-based and TPA-APy-based devices, respectively. These results demonstrate appropriate intramolecular hydrogen bond can suppress the influence of non-radiative decay by simultaneously enhancing molecular rigidity and facilitating the fluorescence process, and have great potential in the design of efficient red TADF emitters.

A facile strategy for enhancing reverse intersystem crossing of red thermally activated delayed fluorescence emitters

By enhancing electron-withdrawing abilities of the secondary acceptor attachments into the main acceptor core, their charge transfer triplet ( 3 CT) energy levels are gradually reduced, while the locally excited triplet ( 3 LE A ) levels are well maintained. The well-aligned excited states, consequently, results in the enhancement of the rates of reverse intersystem crossing (RISC), and boosting the device efficiencies in red OLEDs. • A facile strategy to modulate CT states while maintaining LE state is proposed. • CT energy levels are gradually reduced, while the 3 LE A ones are well maintained. • Fast k RISC , small ΔE ST and high PLQY can be realized simultaneously. • mDPBPZ-DPXZ-based red OLED exhibits much higher EQE compared to its counterparts. Realizing highly efficient reverse intersystem crossing (RISC) process for red thermally activated delayed fluorescence (TADF) emitters remains a formidable challenge. Herein we demonstrate that charge transfer (CT) energy levels are gradually reduced with enhancing electron-withdrawing abilities of the secondary acceptor (A) attachments. Meanwhile, their local excited triplet ( 3 LE A ) state levels are well maintained due to the conjugations between the main framework and the attachments are all similar for these A segments. The optimized molecular energy level alignments are obtained in the case of mDPBPZ-DPXZ, in which 3 CT and the 3 LE A states are almost degenerate, and gives rise to a small singlet–triplet energy difference ( ΔE ST ) of 0.02 eV, a fast RISC rate of 1.54 × 10 6 s −1 and a high photoluminescence quantum yield of 93%, simultaneously. And the corresponding device achieves an external quantum efficiency of 21.6%, significantly higher than the other counterparts. This work demonstrates that the energy alignment between the CT and 3 LE A state can be easily managed by introducing secondary A attachments on original A framework, which shifts the 1 CT and 3 CT state to lower energies without affecting the 3 LE A energy. It provides a facile design strategy to promote the RISC process, which is particular useful in designing highly efficient red TADF emitters.

Controlling the conjugation extension inside acceptors for enhancing reverse intersystem crossing of red thermally activated delayed fluorescence emitters

Increasing the reverse intersystem crossing (RISC) rates remains a challenge for red thermally activated delayed fluorescence (TADF) emitters, and energy level alignments play an important role. In this work, we demonstrate that locally excited triplet energy levels from acceptor segments (3LEA) can be well modulated by changing the conjugation extension inside acceptors. Our newly designed compounds pDPAPQ-PXZ and pDPBPZ-PXZ show nearly identical charge-transfer (CT) properties because of similar donor and acceptor strengths. On the other hand, the 3LEA state of pDPBPZ-PXZ was significantly lower than that of pDPAPQ-PXZ only because of its greater π-delocalization. In the case of pDPBPZ-PXZ, ideal molecular energy level alignments are obtained with near-degenerate CT featuring singlet and triplet states (1CT, 3CT) and 3LEA. As a result, pDPBPZ-PXZ simultaneously achieves an approximately 10-fold improved kRISC and a dramatically improved photoluminescence quantum yield of 85.6% compared with pDPAPQ-PXZ. The corresponding OLED successfully doubles the external quantum efficiency to 20.3%. This work demonstrates that the conjugation extensions of acceptors play a fatal role in determining 3LEA levels and that they can be isolated from controlling the acceptor strengths. This provides a promising approach toward enhancing RISC efficiency and developing highly efficient red TADF emitters.

Polycyclic phenazine-derived rigid donors construct thermally activated delayed fluorescence emitters for highly efficient orange OLEDs with extremely low roll-off

Two new thermally activated delayed fluorescence (TADF) molecules, tBuInPz-BO and InPz-BO, are constructed via connecting novel rigid polycyclic phenazine-derived donors with oxygen-bridged boron acceptor. Both emitters exhibit fast reverse intersystem crossing rates and high photoluminescence quantum yields, owing to the high molecular structural rigidity. As a result, the orange organic light-emitting diode (OLED) fabricated with tBuInPz-BO shows a maximum external quantum efficiency (EQEmax) of 22.0% with the electroluminescence peak at 585 nm. Moreover, the device displays extremely low efficiency roll-off. At high luminance of 1000 and 10000 cd/m2, the EQE values still maintain a high level of 20.2% and 14.8%, respectively, achieving state-of-the-art electroluminescence performance among TADF-based orange OLEDs. This work reveals the great potential of the new phenazine-derived donors for constructing highly efficient TADF emitters.

A novel orange-red thermally activated delayed fluorescence emitter with high molecular rigidity and planarity realizing 32.5% external quantum efficiency in organic light-emitting diodes.

Simultaneous optimization of photoluminescence quantum yield (ΦPL) and horizontally oriented dipoles (Θ‖) is considerably challenging for orange and red thermally activated delayed fluorescence (TADF) emitters, due to the conflicts between enhancing molecular rigidity and improving molecular planarity. Herein, a novel orange-red TADF emitter 10-(dipyrido[3,2-a:2',3'-c]phenazin-11-yl)-10H-spiro[acridine-9,9'-fluorene] (SAF-2NP) was constructed with a donor-acceptor structure. The highly rigid donor and acceptor segments ensure the overall rigidity of the emitter. More importantly, the quasi-coplanar structure between the acceptor and the fluorene moiety in the donor unit enlarges the molecular plane without weakening rigidity. Consequently, SAF-2NP exhibited extremely high ΦPL and Θ‖ of 99% and 85%, respectively. The optimal organic light-emitting diode using SAF-2NP as the emitter and 4,4'-di(9H-carbazol-9-yl)-1,1'-biphenyl (CBP) as the host demonstrated an unparalleled external quantum efficiency of 32.5% and a power efficiency of 85.2 lm W-1 without any extra light extraction structure. This work provides a feasible strategy to establish efficient orange and red TADF emitters with both high rigidity and planarity.

Through-Space Charge-Transfer Emitters Developed by Fixing the Acceptor for High-Efficiency Thermally Activated Delayed Fluorescence.

Through-space charge-transfer (TSCT) emitters have been extensively explored for thermally activated delayed fluorescence (TADF), but arranging various donors and acceptors into rigid cofacial conformations for various efficient TSCT TADF emitters has remained challenging. Here, we report a "fixing acceptor" design to reach various efficient TSCT TADF emitters. By chemically fixing the acceptor (benzophenone) with a rigid spiro-structure and cofacially aligning various donors with the fixed acceptor, a series of efficient TSCT TADF emitters have been developed. Single-crystal structures and theoretical calculations have verified closely packed cofacial donor/acceptor conformations and favorable TSCT in the emitters. In doped films, the emitters afford sky blue to yellow TADF emission, with high photoluminescence efficiencies up to 0.92 and reverse intersystem crossing rates up to 1.0 × 106 s-1. Organic light-emitting diodes using the emitters afford sky blue to yellow electroluminescence with high external quantum efficiencies up to 20.9%. The work opens a new avenue toward a wide variety of efficient TSCT TADF emitters.

Novel D-D′-A structure thermally activated delayed fluorescence emitters realizing over 20% external quantum efficiencies in both evaporation- and solution-processed organic light-emitting diodes

Thermally activated delayed fluorescence (TADF) emitters have only realized limited performance in solution-processed organic light-emitting diodes (OLEDs) comparing to in evaporation-processed OLEDs. To address this issue, a novel D-D′-A structure, where A is the electron-accepting group, D is the primary electron-donating group and D′ is the secondary electron-donating group, was proposed to develop efficient solution-processable TADF emitters in this work. As the intermediate D′ spacer weakens the direct intramolecular interaction between D and A groups, D-D′-A structure molecules simultaneously possess intramolecular and intermolecular charge-transfer transition channels, suppressing the aggregation-caused quenching induced by solution process. Accordingly, a novel TADF emitter 2-(3,6-bis(9,9-dimethylacridin-10(9H)-yl)-9H-carbazol-9-yl)thianthrene 5,5,10,10-tetraoxide (DMAC-Cz-TTR) was designed and synthesized. In the optimized evaporation- and solution-processed OLEDs, DMAC-Cz-TTR successfully realized similar maximum external quantum efficiencies (EQEs) of 21.1% and 20.6%, respectively. To the best of our knowledge, this is the first TADF emitter realizing nearly equal performance in both evaporation- and solution-processed OLEDs with over 20% EQEs. The outstanding performance of DMAC-Cz-TTR successfully demonstrates the feasibility of the D-D′-A structure to develop efficient solution-processable TADF emitters. • A novel D-D′-A structure was proposed to develop efficient solution-processed TADF emitters. • A new TADF emitter DMAC-Cz-TTR was developed accordingly with intra- and inter-CT transition channels simultaneously. • In the evaporation- and solution-processed OLEDs, DMAC-Cz-TTR realized maximum EQEs of 21.1% and 20.6%, respectively.

Molecular engineering by σ-linkers enables delayed fluorescence emitters for high-efficiency sky-blue solution-processed OLEDs

Two novel thermally activated delayed fluorescence (TADF) emitters, namely Me2AcBO and F2AcBO, based on the 9,9-dimethrylacridine donor and a rigid oxygen-bridged cyclized boron acceptor, were designed and synthesized for highly efficient blue solution-processed organic light-emitting diodes (OLEDs). Me2AcBO and F2AcBO feature a twin structure derived by coupling two individual TADF monomers through non-conjugated linkers. The two new emitters exhibit 3D molecular structures, excellent thermal/morphological properties, high photoluminescence quantum yields over 97%, and high reverse intersystem crossing rates on the order of 106 s−1, which greatly benefit the high device efficiency. Solution-processed sky-blue TADF OLEDs based on Me2AcBO and F2AcBO achieved the maximum external quantum efficiency of 11.0% and 10.9%, respectively, with Commission Internationale de L’Eclairage (CIE) coordinates of (0.14, 0.25). Interestingly, relatively low efficiency roll-offs of 33% and 34% at the luminance of 1000 cd/m2 were demonstrated for Me2AcBO and F2AcBO based devices, respectively. This study presents a novel strategy to realize highly efficient sky-blue TADF emitters for solution-processed OLEDs.

A novel molecular design featuring the conversion of inefficient TADF emitters into efficient TADF emitters for deep-blue organic light emitting diodes

Abstract In this report, we unveiled a new molecular design featuring the transformation of inefficient thermally activated delayed fluorescence (TADF) emitters into the efficient TADF emitters by combing them with non-TADF type chromophore units to develop deep-blue TADF emitters for organic light-emitting diodes. The inefficient TADF emitter and non-TADF chromophore were connected directly through a phenyl linker in a sterically hindered configuration by selectively interlocking two donors in the backbone structure. The new TADF emitter demonstrated excellent device performances with maximum external quantum efficiency up to 22% and y color coordinate of 0.15. Based on these results, we believe that the proposed new design strategy is effective with regard to the conversion of inefficient deep-blue TADF emitters to efficient deep-blue TADF emitters and can be diversely applied for the development of efficient TADF emitters.

TD-DFT and Experimental Methods for Unraveling the Energy Distribution of Charge-Transfer Triplet/Singlet States of a TADF Molecule in a Frozen Matrix.

Reverse intersystem crossing (RISC) rate of a thermally activated delayed fluorescence (TADF) molecule is sensitive to the energy alignment of the singlet charge-transfer state (1CT), triplet charge-transfer state (3CT), and locally excited triplet state (3LE). However, the energy distribution of the charge-transfer states originating from the conformational distribution of TADF molecules in a solid matrix inevitably generated during the preparation of a solid sample due to the rotatable donor-acceptor linkage is rarely considered. Moreover, the investigation of the energy distribution of the 3CT state is both theoretically and experimentally difficult due to the triplet instabilities of time-dependent density functional (TD-DFT) calculations and difficulties in phosphorescence measurements, respectively. As a result, the relationships between conformational distribution, configurations of excited state transition orbitals, and excited state energies/dynamics have not been clearly explained. In this work, we determined the energy distribution of CT states of the TADF emitter TPSA in frozen toluene at 77 K by the measurement of time-resolved spectra in the full time range (1 ns to 30 s) of emission including prompt fluorescence, TADF, 3CT phosphorescence, and 3LE phosphorescence. We obtained the energy band of CT states where 1CT and 3CT states are distributed in the range of 2.85-3.00 and 2.64-2.96 eV, respectively. We tested various global hybrid and long-range corrected functionals for the TD-DFT calculation of 3CT energy of TPSA and found that only the M11 functional shows consistent results without triplet instability. We performed TD-DFT with the M11* functional optimized for a robust dihedral angle scan of 3CT states without triplet instability and reproduced the energy band structure obtained from the experiment. Through TD-DFT and experimental investigations, it is estimated that the dihedral angles of donor-acceptor (θD-A) and acceptor-linker (θA) of TPSA in frozen toluene lie within the range 70° ≤ θD-A ≤ 90° and 0° ≤ θA ≤ 30° respectively. Our results show that the dihedral angle distribution must be considered for further investigation of the photophysics of TADF molecules and the development of stable and efficient TADF emitters.

Highly efficient blue TADF emitters incorporating bulky acridine moieties and their application in solution-processed OLEDs

Two bulky acridine moieties, 9,9-diphenyl-9,10-dihydroacridine (DPAc) and 10H-spiro [acridine-9,9′-fluorene] (SpiroAc), were selected as electron donors. Compared with commonly used 9,9-dimethyl-9,10-dihydroacridine (DMAc), phenyl modified acridines exhibited low-lying highest occupied molecular orbital (HOMO) levels and relatively weak electron-donating abilities, which make them potential units to create blue TADF emitter. DPAc and SpiroAc were connected with a triarylboron group and constructed centrosymmetric 3D-A architectures, namely 3DPAc-TB and 3SpiroAc-TB, respectively. Density functional theory calculations showed that both molecules exhibited large dihedral angles between the triarylboron unit and acridine planes. The well-separated frontier molecular orbitals contributed to small energy gaps between S1 and T1 states of the designed molecules (0.12 and 0.07 eV, respectively). Both molecules exhibited distinct thermally activated delayed fluorescence (TADF) character. The bulky acridine donors endowed both molecules with rigid structures and realized high photoluminescent quantum yields (71.6% and 84.3%, respectively). Solution-processed organic light-emitting diodes (OLEDs) utilizing 3DPAc-TB and 3SpiroAc-TB as emitters exhibited blue emissions with emission peaks of 472 nm and 490 nm, respectively. The maximum external quantum efficiencies of 3DPAc-TB and 3SpiroAc-TB based devices were 12.8% and 17.3%, respectively.

Optimizing molecular rigidity and thermally activated delayed fluorescence (TADF) behavior of phosphoryl center π-conjugated heterocycles-based emitters by tuning chemical features of the tether groups

Four novel fluorescent molecules based on pentavalent phosphoryl center π-conjugated heterocycles (PCCH) as acceptor have been constructed by ether, sulfide, and sulfonyl groups as tethering groups and phenoxazine or phenothiazine as the donor. Their molecular configurations, photophysical, electrochemical behaviors and electroluminescent (EL) performances have been studied. The molecular configuration of these PCCH-based emitters look like bowls, due to the bowl-shape PCCH-based acceptors. According to their special molecular structure and photophysical results, it can be concluded that the PCCH-based emitters with phenoxazyl as donors have efficient thermally activated delayed fluorescence (TADF) behavior. Interestingly, their molecular rigidity, photoluminescent quantum yield (PLQY) and TADF behaviors are correlate with the depth of the bowl in the case of the same donor. The sulfone group as tethering group into the acceptor unit among of these PCCH-based emitters exhibit optimal PL and EL performances. It has a highest PLQY of ca. 0.83, measured in doped CBP film, and the highest kRISC of 106 s−1. Importantly, its doped OLEDs can achieve exceptional EL performances with a maximum ηext of 28.2%, ηL of 90.8 cd A−1 and ηP of 83.5 lm W−1. In addition, these bowl molecules of PCCH-based emitters will enrich the structural diversity of high efficient TADF emitters.

Deep-blue organic light-emitting diodes based on a doublet d\u2013f transition cerium(III) complex with 100% exciton utilization efficiency

Compared to red and green organic light-emitting diodes (OLEDs), blue OLEDs are still the bottleneck due to the lack of efficient emitters with simultaneous high exciton utilization efficiency (EUE) and short excited-state lifetime. Different from the fluorescence, phosphorescence, thermally activated delayed fluorescence (TADF), and organic radical materials traditionally used in OLEDs, we demonstrate herein a new type of emitter, cerium(III) complex Ce-1 with spin-allowed and parity-allowed d–f transition of the centre Ce3+ ion. The compound exhibits a high EUE up to 100% in OLEDs and a short excited-state lifetime of 42 ns, which is considerably faster than that achieved in efficient phosphorescence and TADF emitters. The optimized OLEDs show an average maximum external quantum efficiency (EQE) of 12.4% and Commission Internationale de L’Eclairage (CIE) coordinates of (0.146, 0.078).

In-Depth Ab Initio Study of Thermally Activated Delayed Fluorescence in 4,5-Di(9H-carbazol-9-yl)-phthalonitrile.

Molecules capable of thermally activated delayed fluorescence (TADF) are promising as emitters in organic light-emitting devices. Processes leading to and competing with TADF in 4,5-di(9H-carbazol-9-yl)-phthalonitrile are analyzed in detail. It is demonstrated that the key features of an efficient TADF emitter include the presence of two triplet states of different natures with potential energy surfaces crossing between the T1 and S1 minima and a noticeable dependence of the S1 → S0 oscillator strength on molecular deformations from low-frequency antisymmetric vibrational modes. These conclusions can be useful in the targeted design of efficient TADF emitters.

Improving the Efficiency of Red Thermally Activated Delayed Fluorescence Organic Light‐Emitting Diode by Rational Isomer Engineering

AbstractThe development of efficient red thermally activated delayed fluorescence (TADF) emitters with an emission wavelength beyond 600 nm remains a great challenge for organic light‐emitting diodes (OLEDs). Herein, two pairs of isomers are designed and synthesized by attaching electron‐donor 9,9‐diphenyl‐9,10‐dihydroacridine (DPAC) moiety to the different positions of two kinds of highly rigid planar acceptor cores (PDCN and PPDCN). Their TADF efficiencies and emission maxima (599–726 nm) are regulated by molecular isomer manipulation. Interestingly, the photoluminescence quantum yields (ΦPLs) of trans‐isomers T‐DA‐1 and T‐DA‐2 (78% and 89%) are remarkably higher than those of their corresponding cis‐isomers C‐DA‐1 and C‐DA‐2 (12% and 14%). Significantly increased ΦPL values can be explained by single crystal structures and theoretical simulation. As a result, a deep red TADF‐OLED based on T‐DA‐2 displays a maximum external quantum efficiency (EQE) of 26.26% at 640 nm. Notably, at a brightness of 100 cd m−2, the EQE value of T‐DA‐2‐based device still remains at an extremely high level of 23.95%, representing the highest value for reported red TADF‐OLEDs at the same brightness. These results provide a reasonable pathway to optimize optoelectronic properties and thereby construct efficient red TADF emitters through rational isomer engineering.