Blue organic light-emitting diodes realizing external quantum efficiency over 25% using thermally activated delayed fluorescence emitters.
ABSTRACT: Improving the performance of blue organic light-emitting diodes (OLEDs) is needed for full-colour flat-panel displays and solid-state lighting sources. The use of thermally activated delayed fluorescence (TADF) is a promising approach to efficient blue electroluminescence. However, the difficulty of developing efficient blue TADF emitters lies in finding a molecular structure that simultaneously incorporates (i) a small energy difference between the lowest excited singlet state (S1) and the lowest triplet state (T1), ?E ST, (ii) a large oscillator strength, f, between S1 and the ground state (S0), and (iii) S1 energy sufficiently high for blue emission. In this study, we develop TADF emitters named CCX-I and CCX-II satisfying the above requirements. They show blue photoluminescence and high triplet-to-singlet up-conversion yield. In addition, their transition dipole moments are horizontally oriented, resulting in further increase of their electroluminescence efficiency. Using CCX-II as an emitting dopant, we achieve a blue OLED showing a high external quantum efficiency of 25.9%, which is one of the highest EQEs in blue OLEDs reported previously.
Project description:Deep-blue emitters that can harvest both singlet and triplet excited states to give high electron-to-photon conversion efficiencies are highly desired for applications in full-color displays and white lighting devices based on organic light-emitting diodes (OLEDs). Thermally activated delayed fluorescence (TADF) molecules based on highly twisted donor-acceptor (D-A) configurations are promising emitting dopants for the construction of efficient deep-blue OLEDs. In this study, a simple and versatile D-A system combining acridan-based donors and pyrimidine-based acceptors has been developed as a new platform for high-efficiency deep-blue TADF emitters. The designed pre-twisted acridan-pyrimidine D-A molecules exhibit small singlet-triplet energy splitting and high photoluminescence quantum yields, functioning as efficient deep-blue TADF emitters. The OLEDs utilizing these TADF emitters display bright blue electroluminescence with external quantum efficiencies of up to 20.4%, maximum current efficiencies of 41.7 cd A-1, maximum power efficiencies of 37.2 lm W-1, and color coordinates of (0.16, 0.23). The design strategy featuring such acridan-pyrimidine D-A motifs can offer great prospects for further developing high-performance deep-blue TADF emitters and TADF-OLEDs.
Project description:The high driving voltage of blue organic light-emitting diodes (OLEDs) based on emitters with thermally activated delayed fluorescence (TADF) remains a constraint for their portable application. A major reason for this is that the high triplet (T1) of the host required to match the blue TADF emitters would always lead to inferiority in terms of carrier injection. Therefore, a suitable host should possess not only a high T1 but also a relatively low singlet (S1) for improved carrier injection, indicating that small singlet-triplet splittings (?ESTs) are highly desired. Here, four carbazolyl benzonitrile derivatives are facilely prepared in a one-step approach with restrained conjugate lengths to maintain high triplet energies while their highly twisted structures spatially separate the frontier orbital distribution to achieve relatively low ?ESTs. Meanwhile, the charge transporting mobilities of these hosts are effectively tuned by the different linker types of the host moieties. Consequently, high-triplet-energy hosts with favorable carrier injection/transporting abilities are realized, endowing blue TADF devices with a maximum external quantum efficiency of 21.5%, a maximum power efficiency of 42.0 lm W-1 and an ultra-low onset voltage of 2.8 V. It is noteworthy that a driving voltage of 4.9 V is achieved at a practical luminance of 1000 cd m-2, which is the lowest among the doped blue TADF OLEDs reported until now. This work suggests that manipulation of the molecular topologies not only leads to the flexible and feasible design of novel bipolar host materials, but also affords a promising method for fine-tuning physical properties and thus obtaining state-of-the-art device performances.
Project description:Recently, triplet harvesting via a thermally activated delayed fluorescence (TADF) process has been established as a realistic route for obtaining ultimate internal electroluminescence (EL) quantum efficiency in organic light-emitting diodes (OLEDs). However, the possibility that the rather long transient lifetime of the triplet excited states would reduce operational stability due to an increased chance for unwarranted chemical reactions has been a concern. Herein, we demonstrate dual enhancement of EL efficiency and operational stability in OLEDs by employing a TADF molecule as an assistant dopant and a fluorescent molecule as an end emitter. The proper combination of assistant dopant and emitter molecules realized a "one-way" rapid Förster energy transfer of singlet excitons from TADF molecules to fluorescent emitters, reducing the number of cycles of intersystem crossing (ISC) and reverse ISC in the TADF molecules and resulting in a significant enhancement of operational stability compared to OLEDs with a TADF molecule as the end emitter. In addition, we found that the presence of this rapid energy transfer significantly suppresses singlet-triplet annihilation. Using this finely-tuned rapid triplet-exciton upconversion scheme, OLED performance and lifetime was greatly improved.
Project description:Issues concerning excited state lifetime (?TADF) tuning of thermally activated delayed fluorescence (TADF) materials are critical for organic light emitting diode (OLED) applications and other specific fields. For TADF-OLEDs, employing emitters with a short ?TADF gives rise to suppressed singlet-triplet annihilation (STA) and triplet-triplet annihilation (TTA), leading to reduced efficiency roll-off at practical relevant brightness (100 and 1000 cd m-2 for display and illumination applications, respectively). Through molecular design, exciton dynamic process rate constants including fluorescence (kF), intersystem crossing (kISC), internal conversion (kIC) and reverse intersystem crossing (kRISC) are selectively altered, affording four representative TADF emitters. Based on lifetime and quantum yield measurements, kF, kISC, kIC and kRISC are calculated for four emitters and their interrelationship matches corrected time-dependent density functional theory simulation. Among them, even with a small kF, low photoluminescence quantum efficiency (?) and large kISC, molecules with a small singlet-triplet splitting energy (?EST) and lowest charge transfer triplet excited state (3CT) eventuate in shortening the ?TADF. Herein, kRISC, which is inversely proportional to ?EST, turns out to be the rate-limited factor in tuning the ?TADF ("rate limited effect" of the RISC process). As revealed by flexible potential surface scanning, PyCN-ACR exhibited a moderate kF, reduced kIC and enlarged kRISC, resulting in a short ?TADF and a moderate ? with orange-red emission. OLEDs containing PyCN-ACR as the emitting guest achieved orange-red TADF-OLEDs with an emission peak at 590 nm and the best external quantum efficiencies (EQEs) of 12.4%/9.9%/5.1% at practical luminances of 100/1000/10?000 cd m-2.
Project description:Organic light-emitting diodes (OLEDs) are attractive for next-generation displays and lighting applications because of their potential for high electroluminescence (EL) efficiency, flexibility and low-cost manufacture. Although phosphorescent emitters containing rare metals such as iridium or platinum produce devices with high EL efficiency, these metals are expensive and their blue emission remains unreliable for practical applications. Recently, a new route to high EL efficiency using materials that emit through thermally activated delayed fluorescence (TADF) was demonstrated. However, it is unclear whether devices that emit through TADF, which originates from the contributions of triplet excitons, are reliable. Here we demonstrate highly efficient, stable OLEDs that emit via TADF by controlling the position of the carrier recombination zone, resulting in projected lifetimes comparable to those of tris(2-phenylpyridinato)iridium(III)-based reference OLEDs. Our results indicate that TADF is intrinsically stable under electrical excitation and optimization of the surrounding materials will enhance device reliability.
Project description:The design of orange-light emitting, thermally activated, delayed ?uorescence (TADF) materials is necessary and important for the development and application of organic light-emitting diodes (OLEDs). Herein, two donor-acceptor-donor (D-A-D)-type orange TADF materials based on fluorenone and acridine, namely 2,7-bis(9,9-dimethylacridin-10(9H)-yl)-9H-fluoren-9-one (27DACRFT, 1) and 3,6-bis(9,9-dimethylacridin-10(9H)-yl)-9H-fluoren-9-one (36DACRFT, 2), were successfully synthetized and characterized. The studies on their structure-property relationship show that the different configurations have a serious effect on the photoluminescence and electroluminescence performance according to the change in singlet-triplet splitting energy (?EST) and excited state geometry. This indicates that a better configuration design can reduce internal conversion and improve triplet exciton utilization of TADF materials. Importantly, OLEDs based on 2 exhibited a maximum external quantum efficiency of 8.9%, which is higher than the theoretical efficiency of the OLEDs based on conventional fluorescent materials.
Project description:Deep-blue thermally activated delayed fluorescence (TADF) emitters are promising alternatives for conventional fluorescence and phosphorescence materials for practical application in organic light-emitting diodes (OLEDs). However, as appropriate bipolar hosts for deep-blue TADF-OLEDs are scarce, the development of efficient deep-blue TADF emitters that are applicable to both doped and non-doped systems is an urgent task. In this study, we developed a new family of blue TADF emitters that demonstrated high photoluminescence (PL) and electroluminescence (EL) quantum efficiencies in both doped and non-doped (neat) systems. Four new donor-acceptor (D-A)-type TADF molecules incorporating phenazasiline, phenazagermine, and tetramethylcarbazole as weak D units and phenothiaborin as a weak A unit were designed and synthesized. By varying the structural rigidity/flexibility as well as the electron-donating ability of the D units, the resulting photophysical and TADF properties of the D-A molecules could be systematically regulated. A comprehensive photophysical investigation revealed that phenazasiline and phenazagermine-based emitters concurrently exhibit blue TADF emissions (464-483 nm), high PL quantum efficiencies (?100%), extremely fast spin-converting reverse intersystem crossing rates (>107 s-1), and suppressed concentration quenching. These fascinating features in conjunction produced high-performance doped and non-doped blue TADF-OLEDs. The doped and non-doped TADF-OLEDs using the phenazasiline-based emitter demonstrated extremely high maximum external EL quantum efficiencies (? ext) of 27.6% and 20.9%, with CIE chromaticity coordinates of (0.14, 0.26) and (0.14, 0.20), respectively. Further, ultra-low efficiency roll-off behavior for both the doped and non-doped devices was demonstrated by their ? ext as high as 26.1% and 18.2%, respectively, measured at a practically high luminance of 1000 cd m-2.
Project description:We expose significant changes in the emission color of carbazole-based thermally activated delayed fluorescence (TADF) emitters that arise from the presence of persistent dimer states in thin films and organic light-emitting diodes (OLEDs). Direct photoexcitation of this dimer state in 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) reveals the significant influence of dimer species on the color purity of its photoluminescence and electroluminescence. The dimer species is sensitive to the sample preparation method, and its enduring presence contributes to the widely reported concentration-mediated red shift in the photoluminescence and electroluminescence of evaporated thin films. This discovery has implications on the usability of these, and similar, molecules for OLEDs and explains disparate electroluminescence spectra presented in the literature for these compounds. The dimerization-controlled changes observed in the TADF process and photoluminescence efficiency mean that careful consideration of dimer states is imperative in the design of future TADF emitters and the interpretation of previously reported studies of carbazole-based TADF materials.
Project description:The design of organic compounds with nearly no gap between the first excited singlet (S1) and triplet (T1) states has been demonstrated to result in an efficient spin-flip transition from the T1 to S1 state, that is, reverse intersystem crossing (RISC), and facilitate light emission as thermally activated delayed fluorescence (TADF). However, many TADF molecules have shown that a relatively appreciable energy difference between the S1 and T1 states (~0.2 eV) could also result in a high RISC rate. We revealed from a comprehensive study of optical properties of TADF molecules that the formation of delocalized states is the key to efficient RISC and identified a chemical template for these materials. In addition, simple structural confinement further enhances RISC by suppressing structural relaxation in the triplet states. Our findings aid in designing advanced organic molecules with a high rate of RISC and, thus, achieving the maximum theoretical electroluminescence efficiency in organic light-emitting diodes.
Project description:Aromatic organic deep-blue emitters that exhibit thermally activated delayed fluorescence (TADF) can harvest all excitons in electrically generated singlets and triplets as light emission. However, blue TADF emitters generally have long exciton lifetimes, leading to severe efficiency decrease, i.e., rolloff, at high current density and luminance by exciton annihilations in organic light-emitting diodes (OLEDs). Here, we report a deep-blue TADF emitter employing simple molecular design, in which an activation energy as well as spin-orbit coupling between excited states with different spin multiplicities, were simultaneously controlled. An extremely fast exciton lifetime of 750?ns was realized in a donor-acceptor-type molecular structure without heavy metal elements. An OLED utilizing this TADF emitter displayed deep-blue electroluminescence (EL) with CIE chromaticity coordinates of (0.14, 0.18) and a high maximum EL quantum efficiency of 20.7%. Further, the high maximum efficiency were retained to be 20.2% and 17.4% even at high luminance.