High Triplet Energy Research Articles

Versatile Host Materials for Both D-A-Type and Multi-Resonance TADF Emitters toward Solution-Processed OLEDs with Nearly 30% EQE.

Fabricating solution-processible host material for thermally activated delayed fluorescence (TADF) emitter remains a formidable challenge for organic light-emitting diodes (OLEDs). In this work, two new host materials, namely 3CzAcPy and 9CzAcPy, are found to exhibit high triplet energy levels, high thermal stability, and excellent film morphology from a solution process. An in-depth analysis on the photophysical data and device performance reveals the isomeric effect of the host materials has a significant impact not only on the host properties, but also on the host-dopant interactions and thus the performance of the resulting solution-processed TADF OLEDs. Impressively, the new hosts are proven to be suitable for both donor-acceptor type and multi-resonance TADF emitters, achieving state-of-the-art device performance. By using the new host 9CzAcPy, solution-processed OLED based on a donor-acceptor TADF emitter of DPAC-PCN, a maximum external quantum efficiency (EQE) of 29.5% is achieved, and solution-processed narrowband OLED based on a multiple-resonance TADF emitter of BN-CP1 acquires a maximum EQE of 26.6%. These efficiencies represent the highest values among the solution-processed TADF OLEDs. This study highlights the significance of host-dopant interactions in modulating the electroluminescence performance of TADF emitters, and provides an effective design principle for solution-processible host materials.

A symmetrical carbazole/benzonitrile-based high triplet energy bipolar host designed by a para-linkage strategy for efficient blue and green phosphorescent organic light-emitting diodes

Based on a para-linkage concept, a symmetrical carbazole-benzonitrile derivative of 4-(9H-carbazol-9-yl)-3,5-diphenyl-2,6-difluoronitrile (CzPhFBN) was designed and prepared as a host for phosphorescent organic light-emitting diodes (PhOLEDs). In the CzPhFBN molecular, a cyano (CN) unit and a carbazole (Cz) unit were attached to the central phenyl ring at the para positions. Simultaneously, the Cz group was surrounded by two phenyl units to increase structure distortion for high triplet energy and CN unit was surrounded by two F units to improve electron transporting behavior. The photophysical properties and carrier transport behavior of CzPhFBN were investigated. The results demonstrated that CzPhFBN offered a high triplet energy of exceeding 3.0 eV and bipolar carrier transporting property. By incorporating CzPhFBN as the host, the blue FIrpic- and green Ir(ppy)3-based PhOLEDs with a common device configuration delivered the maximum efficiencies of 11.1%/19.7 cd A−1/12.1 lm W−1 and/13.1%/43.6 cd A−1/28.6 lm W−1, respectively. These results indicate that this study provides a potential design strategy of high triplet energy bipolar host materials with a simple and elegant structure.

Metal-Organic Bichromophore Lowers the Upconversion Excitation Power Threshold and Promotes UV Photoreactions.

Sensitized triplet-triplet annihilation upconversion is a promising strategy to use visible light for chemical reactions requiring the energy input of UV photons. This strategy avoids unsafe ultraviolet light sources and can mitigate photo-damage and provide access to reactions, for which filter effects hamper direct UV excitation. Here, we report a new approach to make blue-to-UV upconversion more amenable to photochemical applications. The tethering of a naphthalene unit to a cyclometalated iridium(III) complex yields a bichromophore with a high triplet energy (2.68 eV) and a naphthalene-based triplet reservoir featuring a lifetime of 72.1 μs, roughly a factor of 20 longer than the photoactive excited state of the parent iridium(III) complex. In combination with three different annihilators, consistently lower thresholds for the blue-to-UV upconversion to crossover from a quadratic into a linear excitation power dependence regime were observed with the bichromophore compared to the parent iridium(III) complex. The upconversion system composed of the bichromophore and the 2,5-diphenyloxazole annihilator is sufficiently robust under long-term blue irradiation to continuously provide a high-energy singlet-excited state that can drive chemical reactions normally requiring UV light. Both photoredox and energy transfer catalyses were feasible using this concept, including the reductive N-O bond cleavage of Weinreb amides, a C-C coupling reaction based on reductive aryl debromination, and two Paternò-Büchi [2 + 2] cycloaddition reactions. Our work seems relevant in the context of developing new strategies for driving energetically demanding photochemistry with low-energy input light.

High‐Efficiency and Narrow‐Band Near‐Ultraviolet Emitters with Low CIEy of 0.03 by Incorporating Extra Weak Charge Transfer Channel into Multi‐Resonance Skeleton

AbstractHybridized local and charge‐transfer (HLCT) excited‐state emitters can effectively utilize non‐radiative triplet excitons through high‐lying reverse intersystem crossing (hRISC), but they are mostly limited to the donor‐π‐acceptor type molecules. It is a great challenge to develop high‐performance near‐ultraviolet (NUV) emitters with narrow‐band emission by HLCT due to the large carrier injection barriers and high triplet energy. In this work, by incorporating planar multi‐resonance (MR) skeleton of oxygen‐bridged triphenylborane (BO) and weak electron‐donating unit of tetraphenyl‐silane (TPS), two NUV emitters of tBOSi and tBOSiCz are developed, where an extra weak charge transfer (CT) channel between BO skeleton and peripheral phenyl in TPS is observed to increase CT component and activate hot exciton channel of hRISC. As a result, tBOSi and tBOSiCz show an outstanding narrow‐band NUV emission at 414 nm with a FWHM of about 32 nm in solution‐processed organic light‐emitting diodes (OLEDs), even at a heavy doping ratio. The best NUV electroluminescent properties are further achieved in the optimal tBOSi‐doped OLEDs with a record efficiency of 9.15% and a low CIEy of 0.034. This work provides a profound guidance for developing high‐performance narrow‐band NUV emitters by an extra weak CT channel into MR skeleton to activate HLCT emission.

Asymmetric Decoration of a meta-Linked Bitriazine-Based Host for Highly Efficient and Stable Blue Phosphorescent Organic Light-Emitting Diodes

High triplet energy hosts for blue phosphorescent organic light-emitting diodes were developed by decorating a meta-linked bitriazine core with carbazole and tetraphenylsilyl functional groups. A symmetric host with two carbazole units as the two triazine units of the core and an asymmetric host with one carbazole unit and one tetraphenylsilyl unit as the two triazine units were prepared. The triplet energy of these two hosts was 2.97 eV, suitable for triplet exciton harvesting of blue phosphors. Comparing the two host designs, the asymmetric decoration of the two triazine units with carbazole and tetraphenylsilyl units was superior to the symmetric decoration of the two triazine units with two carbazoles in terms of high external quantum efficiency (EQE) and long-term device stability. A high EQE of 19.7% and a long device lifetime of 2093.6 h at 100 cd m-2 were achieved using the asymmetrical host.

Benzimidazole-triazine based n-type hosts with twisted structure and high triplet energy level for efficient blue narrowband emitting OLEDs

Two benzimidazole-triazine based n-type hosts with twisted structure namely BIZ-2Me-TRZ and BIZ-6Me-TRZ were designed by combining two electron-transporting fragments of 1-phenyl-1H-benzo[d]imidazole and diphenyltriazine with a unit of 2′ or 6′ - position methyl substituted phenyl to achieve high triplet energy level over 3.0 eV. The BIZ-6Me-TRZ exhibits high electron mobility up to 1.27 × 10−4 cm2 V−1 s−1, which is two orders of magnitude higher than that of BIZ-2Me-TRZ (8.11 × 10−6 cm2 V−1 s−1), due to its moderate dihedral angle between the phenyl linker and triazine. The blue narrowband emitting device using BIZ-6Me-TRZ as the host shows low turn-on voltage of 2.8 V and high external quantum efficiency (EQE) of 29.2%. The device EQE could be further enhanced to 32.7% by using the n-type BIZ-6Me-TRZ as the acceptor to form exciplex host with a p-type material for improving the exciton utilization efficiency.

Sparkling Organic Phosphorescence from Fluorinated Tetrathia[7]helicenes: Synthesis and Photophysical, Electrochemical and Computational Studies.

Structure-property correlations in the thiahelicene family are often not trivial beacuse most of the functional groups present on the helical scaffold modify the conjugation size of the π-system. Selecting fluorine-containing groups to provide strong inductive effects without interacting with low-lying orbitals of the system could be the way to overcome the issue. Here we report a study on three fluorine-functionalized tetrathia[7]helicenes, highlighting interesting correlations between the position of the functional groups and the conjugated skeleton properties. Helicenes Heli-F2 and Heli-CF-F2 were prepared by photoinduced isomerization-electrocyclization (the Mallory photocyclization) of the corresponding fluorinated benzodithienyl-ethenes Alk-F2 and Alk-CF-F2, which were prepared in high yields through stereo-conservative Stille reaction. Notably these helicenes were found to display green phosphorescence around 530-550 nm, and the studies suggest an efficient spin-orbit coupling mechanism in these high-energy triplet nonplanar conjugated molecules. Both helicenes and their precursors were thoroughly characterized by means of optical and electrochemical measurements, while DFT calculations enable a rationale on their structure-property correlations to be defined.

Highly E-Selective Olefin Synthesis Catalysed by Novel Quinoxalinone Photocatalyst under Visible Light Conditions.

In photo-induced olefin synthesis, the photocatalysts with high triplet energy could cause the isomerization of olefins. This study demonstrates a new quinoxalinone photocatalytic system for highly stereoselective alkenes preparation from alkenyl sulfones and alkyl boronic acids. Our photocatalyst could not convert the thermodynamically favored E-olefin to Z-olefin, guaranteeing the high E-configuration selectivity of the reaction. There is weak interaction between boronic acids and quinoxalinone according to NMR experiments, probably decreasing the oxidation potential of boronic acids. This system can be further extended to the allyl and alkynyl sulfones to give corresponding alkenes and alkynes.

Steric modulation of thermally activated delayed fluorescence-type host for high quantum efficiency in blue phosphorescent organic light-emitting diodes

In organic light-emitting diodes (OLEDs), host engineering is important in improving the device performance. however, it remains as a big challenge in blue phosphorescent OLEDs because of the high triplet energy of blue phosphors. In this work, we develop a sterically modulated thermally activated delayed fluorescence-type host based on an ortho-linked carbazole–triazine backbone structure. An additional π-spacer spatially twisting the two moieties delivers a short delayed decay time of 5.0 μs without any loss of the photoluminescence quantum yield while realizing high triplet and small singlet-triplet energy splitting. The photophysical modulation enables a more efficient utilization of the triplet excitons of the two blue phosphorescent emitters in OLEDs. The fabricated blue phosphorescent OLEDs exhibit a significantly improved device performance in all efficiency parameters compared to reference devices with a maximum external quantum efficiency of 23.6%. This work demonstrates a simple and powerful thermally activated delayed fluorescence host design strategy to realize high efficiency blue-phosphorescence OLEDs.

Frontispiece: Spiroborate‐Based Host Materials with High Triplet Energies and Ambipolar Charge‐Transport Properties

Organic Electronics. Spiroborate-based host materials with high triplet energies and ambipolar charge-transport properties are reported by Takuji Hatakeyama et al. in their Communication (e202217512).

Frontispiz: Spiroborate‐Based Host Materials with High Triplet Energies and Ambipolar Charge‐Transport Properties

Organic Electronics. Spiroborate-based host materials with high triplet energies and ambipolar charge-transport properties are reported by Takuji Hatakeyama et al. in their Communication (e202217512).

In Search of Hosts for Blue OLEDs: Computational Design and Experimental Validation.

Considering the difficulties associated with the conventional 'trial and error' method for a complete analysis of a giant molecular space, we took the aid of computational pathway (DFT) in screening a large space search of 780 (12×13×5) molecules to search for a host for the blue emitter. The selection process was completed in three Tiers with the conditions of highest theoretical triplet energy (>2.81 eV), aligned HOMO/LUMO levels w.r.t blue dopant (FIrpic), and position of substituents to meet the optimal requirements as host materials. Tier 1 screened twelve different imidazole heterocycle derivatives as base space groups which resulted in the selection of 4,5-diphenyl-1H-imidazole. Tier 2 process converged the search to mCN-CZ having the highest triplet energy and appropriate HOMO/LUMO level relative to FIrpic and ETL. Further, the carbazole of mCN-CZ was replaced with different aromatic hydrocarbons to find the other best compound in terms of triplet energy and HOMO/LUMO. Tier 3 resulted in another promising candidate (mCN-FL) as possible host materials. The band alignment with guest predicted mCN-FL and mCN-CZ to have optimal device performances compared to CZ-CZ and the experimentally observed device performance was in accordance with virtual screening results when TAPC was utilized as the hole transporter. The device results of mCN-CZ and mCN-FL were better than the reference host TCTA. The obtained results thus proved that a virtual screening process will be a useful tool for synthetic chemists in designing task-specific materials.

Spiroborate-Based Host Materials with High Triplet Energies and Ambipolar Charge-Transport Properties.

Organic light-emitting diodes (OLEDs) receive considerable attention because of their commercial use in flat panel displays. Herein, highly efficient spiroborate-based host materials are reported for use in blue OLEDs. Our designed spiroborates (SBOX) were simple to synthesize and exhibited high triplet excitation energies, narrow S-T gaps, and balanced charge carrier mobilities. A blue OLED containing one of the designed spiroborates, SBON, as a host exhibited a high external quantum efficiency (27.6 %) and low turn-on voltage (3.7 V) compared to those observed using 3,3'-di(9H-carbazol-9-yl)-1,1'-biphenyl (17.6 % and 4.5 V, respectively), indicating their potential as host materials in OLEDs.

Spiroborate‐Based Host Materials with High Triplet Energies and Ambipolar Charge‐Transport Properties

AbstractOrganic light‐emitting diodes (OLEDs) receive considerable attention because of their commercial use in flat panel displays. Herein, highly efficient spiroborate‐based host materials are reported for use in blue OLEDs. Our designed spiroborates (SBOX) were simple to synthesize and exhibited high triplet excitation energies, narrow S‐T gaps, and balanced charge carrier mobilities. A blue OLED containing one of the designed spiroborates, SBON, as a host exhibited a high external quantum efficiency (27.6 %) and low turn‐on voltage (3.7 V) compared to those observed using 3,3′‐di(9H‐carbazol‐9‐yl)‐1,1′‐biphenyl (17.6 % and 4.5 V, respectively), indicating their potential as host materials in OLEDs.

Soluble Diphenylhexatriene Dimers for Intramolecular Singlet Fission with High Triplet Energy.

Intramolecular singlet fission (iSF) facilitates single-molecule exciton multiplication, converting an excited singlet state to a pair of triplet states within a single molecule. A critical parameter in determining the feasibility of SF-enhanced photovoltaic designs is the triplet energy; many existing iSF materials have triplet energies too low for efficient transfer to silicon via a photon multiplier scheme. In this work, a series of six novel dimers based upon the high-triplet-energy, SF-active chromophore, 1,6-diphenyl-1,3,5-hexatriene (DPH) [E(T1) ∼ 1.5 eV], were designed, synthesized, and characterized. Transient absorption spectroscopy and fluorescence lifetime studies reveal that five of the dimers display iSF activity, with time constants for singlet fission varying between 7 ± 2 ps and 2.2 ± 0.2 ns and a high triplet yield of 163 ± 63% in the best-performing dimer. A strong dependence of the rate of fission on the coupling geometry is demonstrated. For optimized iSF behavior, close spatial proximity and minimal through-bond communication are found to be crucial for balancing the rate of SF against the reverse recombination process.

Spiral donor-based host materials for highly efficient blue thermally activated delayed fluorescence OLEDs

Spiral donor units have attracted extensive research focuses in designing highly emissive thermally activated delayed fluorescence (TADF) emitters. Herein, to reveal the significance of spiral donor units for constructing highly efficient host materials, several spiral donor-based host materials are developed. With the incorporation of spiral donor, increased intermolecular distance is achieved to reduce the concentration quenching effect of dopant. Moreover, the high triplet energy level of spiral donor can provide an additional energy transfer channel to further improve the device performance. Noteworthy, by connecting spiral donors or conventional carbazole unit with different electron-withdrawing units phenoxathiine 10,10-dioxide (PX) or phenoxathiine (PA), these hosts are given different photophysical properties of TADF, room-temperature phosphorescence (RTP) and conventional fluorescence (CF). The strong electron-withdrawing ability of PX is beneficial to the TADF character of spiral donor-based molecules, while the weak electron-withdrawing ability of PA is beneficial to the RTP property. Consequently, the blue OLEDs with DspiroAc-TRZ as a dopant emitter based on the hosts with TADF characters exhibit higher performance than those with RTP and CF properties, and excellent external quantum efficiency (EQE) of 36.1 % and current efficiency of 84.6 cd/A are achieved in a simple device structure. Furthermore, peak EQEs of 34.0 % and 33.0 % are achieved, when DspiroS-PX and DspiroS-PA hosted DspiroAc-TRZ are used to sensitize blue multi-resonance TADF emitter v-DABNA. Our work may shed new light on designing highly efficient host materials for TADF emitters.

Rationally heteroarylated pyridines as hole transport materials for OLEDs.

The advancement in developing highly efficient hole transport materials for OLED devices has been a challenge over the past several years. For an efficient OLED device, there should be an efficient promotion of charge carriers from each electrode and effective confinement of triplet excitons in the emissive layer of the phosphorescent OLED (PhOLED). Thus, the development of stable and high triplet energy hole transport materials is in urgent demand for high-performing PhOLED devices. The present work demonstrates the development of two hetero-arylated pyridines as high triplet energy (2.74-2.92 eV) multifunctional hole transport materials to reduce the exciton quenching and to enhance the extent of charge carrier recombination in the emissive layer. In this regard, we report the design, synthesis, and theoretical modeling with electro-optical properties of two molecules, namely PrPzPy and MePzCzPy, with suitable HOMO/LUMO energy levels and high triplet energy, by incorporating phenothiazine as well as other donating units into a pyridine scaffold, and finally developing a hybrid phenothiazine-carbazole-pyridine based molecular architecture. The natural transition orbital (NTO) calculations were done to analyze the excited state sensation in these molecules. The long-range charge transfer characteristics between the higher singlet and triplet states were also analyzed. The reorganization energy of each molecule was calculated to examine their hole transportability. The theoretical calculations for PrPzPy and MePzCzPy revealed that these two molecular systems could be promising materials for the hole transport layer of OLED devices. As a proof of concept, a solution-processed hole-only device (HOD) of PrPzPy was fabricated. The increase in current density with an increase in operating voltage in the range of ∼3-10 V supported that the suitable HOMO energy of PrPzPy can facilitate the hole transportation from the hole injection layer (HIL) to the emissive layer (EML). These results indicated the promising hole transportability of the present molecular materials.

Alkyl fluorene-based cross-linkable hole transport materials with high triplet energy for high-efficiency solution-processed green PHOLEDs

Two alkyl fluorene-based cross-linkable hole transport materials with high triplet energies were designed and synthesized, providing a simple molecular design strategy for constructing efficient solution-processed PHOLEDs.

3,5-Dicyanopyridine motifs for electron-transporting semiconductors: from design and synthesis to efficient organic light-emitting diodes

Proposing 3,5-dicyanopyridine motifs for the design of electroactive materials for optoelectronic devices, three electron-transporting semiconductors are synthesised. The best performance was observed for OLED containing FPDD as a host (EQE = 21.9%).

Highly efficient deep-blue organic light-emitting diodes (OLEDs) based on hot-exciton materials with multiple triplet exciton conversion channels

High-energy triplet exciton conversion, high exciton utilization efficiency and high device efficiency were achieved through multiple hot-exciton conversion channels.