Organic Light-Emitting Diodes Based on Conjugation-Induced Thermally Activated Delayed Fluorescence Polymers: Interplay Between Intra- and Intermolecular Charge Transfer States.
ABSTRACT: In this work, interactions between different host materials and a blue TADF polymer named P1 are systematically investigated. In photoluminescence, the host can have substantial impact on the photoluminescence quantum yield (PLQY) and the intensity of delayed fluorescence (? DF), where more than three orders of magnitude difference of ? DF in various hosts is observed, resulting from a polarity effect of the host material and energy transfer. Additionally, an intermolecular charge-transfer (CT) emission with pronounced TADF characteristics is observed between P1 and 2,4,6-tris[3-(diphenylphosphinyl)phenyl]-1,3,5-triazine (PO-T2T), with a singlet-triplet splitting of 7 meV. It is noted that the contribution of harvested triplets in monochrome organic light-emitting diodes (OLEDs) correlates with ? DF. For devices based on intermolecular CT-emission, the harvested triplets contribute ~90% to the internal quantum efficiency. The results demonstrate the vital importance of host materials on improving the PLQY and sensitizing ? DF of TADF polymers for efficient devices. Solution-processed polychrome OLEDs with a color close to a white emission are presented, with the emission of intramolecular (P1) and intermolecular TADF (PO-T2T:P1).
Project description:Although numerous thermally activated delayed fluorescence (TADF) organic light-emitting diodes (OLEDs) have been demonstrated, efficient blue or even sky-blue TADF-based nondoped solution-processed devices are still very rare. Herein, through-space charge transfer (TSCT) and through-bond charge transfer (TBCT) effects are skillfully incorporated, as well as the multi-(donor/acceptor) characteristic, into one molecule. The former allows this material to show small singlet-triplet energy splitting (?E ST) and a high transition dipole moment. The latter, on the one hand, further lights up multichannel reverse intersystem crossing (RISC) to increase triplet exciton utilization via degenerating molecular orbitals. On the other hand, the nature of the molecular twisted structure effectively suppresses intermolecular packing to obtain high photoluminescence quantum yield (PLQY) in neat flims. Consequently, using this design strategy, T-CNDF-T-tCz containing three donor and three acceptor units, successfully realizes a small ?E ST (?0.03 eV) and a high PLQY (?0.76) at the same time; hence the nondoped solution-processed sky-blue TADF-OLED displays record-breaking efficiency among the solution process-based nondoped sky-blue OLEDs, with high brightness over 5200 cd m-2 and external quantum efficiency up to 21.0%.
Project description:A surprising yet highly practical approach to improve the performance of a TADF exciplex blend is reported. Using the TSBPA donor and PO-T2T acceptor to form an exciplex, we are able to blue shift the emission, increase PLQY from 58 to 80%, and increase the device EQE from 14.8 to 19.2% by simply diluting the exciplex with an inert high triplet energy host material-here either UGH-3 or DPEPO. These effects are explained in terms of an increasing donor-acceptor distance and associated charge separation, while different behaviors observed in the different hosts are attributed to different energy barriers to electron transfer through the host. We expect that the observed performance-enhancing effects of dilution will be general to different exciplex blends and host materials and offer a new way to optimize the electrical properties of exciplex emission layers with narrow blue emission.
Project description:A deep-blue thermally activated delayed fluorescence (TADF) emitter TXADO-spiro-DMACF has been reported for nondoped organic light-emitting diodes (OLEDs) by integrating an appropriate blocking unit with the donor (D)-acceptor (A)-donor (D)-type TADF emitter via a spiro linkage. Benefiting from the characteristic perpendicular arrangement, the intermolecular interactions are expected to be weakened to some degree. As a result, TXADO-spiro-DMACF shows a very small bathochromic shift of 8 nm associated with a narrowed full width at half maximum of 54 nm on going from solution to the film. The corresponding nondoped device successfully achieves a bright deep-blue emission, revealing Commission Internationale de l'Eclairage coordinates of (0.16, 0.09) and a peak external quantum efficiency of 5.3% (5.3 cd/A, 5.9 lm/W). The results clearly indicate that spiro-blocking is a promising strategy to develop deep-blue TADF emitters capable of nondoped OLEDs.
Project description:Thermally activated delayed fluorescence (TADF) provides great potential for the realization of efficient and stable organic light-emitting diodes (OLEDs). However, it is still challenging for blue TADF emitters to simultaneously achieve high efficiency, high brightness, and low Commission Internationale de l'Eclairage (CIE) y coordinate (CIEy) value. Here, the design and synthesis of two new benzonitrile-based TADF emitters (namely 2,6-di(9H-carbazol-9-yl)-3,5-bis(3,6-diphenyl-9H-carbazol-9-yl)benzonitrile (2PhCz2CzBn) and 2,6-di(9H-carbazol-9-yl)-3,5-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)benzonitrile (2tCz2CzBn)) with a symmetrical and rigid heterodonor configuration are reported. The TADF OLEDs doped with both the emitters can achieve a high external quantum efficiency (EQE) over 20% and narrowband blue emission of 464 nm with a CIEy < 0.2. Moreover, the incorporation of a terminal tert-butyl group can weaken the intermolecular ?-? stacking in the nondoped TADF emitter, and thus significantly suppress self-aggregation-caused emission quenching for enhanced delayed fluorescence. A peak EQE of 21.6% is realized in the 2tCz2CzBn-based nondoped device with an extremely low turn-on voltage of 2.7 V, high color stability, a high brightness over 20 000 cd m-2, a narrow full-width at half-maximum of 70 nm, and CIE color coordinates of (0.167, 0.248).
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.
Project description:In this manuscript, we demonstrated a highly efficient DCJTB emission with delayed fluorescent exciplex TCTA:3P-T2T as the host. For the 1.0% DCJTB doped concentration, a maximum luminance, current efficiency, power efficiency and EQE of 22,767 cd m(-2), 22.7 cd A(-1), 21.5 lm W(-1) and 10.15% were achieved, respectively. The device performance is the best compared to either red OLEDs with traditional fluorescent emitter or traditional red phosphor of Ir(piq)3 doped into CBP host. The extraction of so high efficiency can be explained as the efficient triplet excitons up-conversion of TCTA:3P-T2T and the energy transfer from exciplex host singlet state to DCJTB singlet state.
Project description:Thermally activated delayed fluorescence (TADF) materials have shown great potential for highly efficient organic light-emitting diodes (OLEDs). While the current molecular design of TADF materials primarily focuses on combining donor and acceptor units, we present a novel system based on the use of excited-state intramolecular proton transfer (ESIPT) to achieve efficient TADF without relying on the well-established donor-acceptor scheme. In an appropriately designed acridone-based compound with intramolecular hydrogen bonding, ESIPT leads to separation of the highest occupied and lowest unoccupied molecular orbitals, resulting in TADF emission with a photoluminescence quantum yield of nearly 60%. High external electroluminescence quantum efficiencies of up to 14% in OLEDs using this emitter prove that efficient triplet harvesting is possible with ESIPT-based TADF materials. This work will expand and accelerate the development of a wide variety of TADF materials for high performance OLEDs.
Project description:In organic light-emitting diodes (OLEDs), all triplet excitons can be harvested as light via reverse intersystem crossing (RISC) based on thermally activated delayed fluorescence (TADF) emitters. To realize efficient TADF, RISC should be fast. Thus, to accomplish rapid RISC, in the present study, a novel TADF emitter, namely, TpIBT-tFFO, was reported. TpIBT-tFFO was compared with IB-TRZ, which contains the same electron donor and acceptor segments, specifically iminodibenzyl and triazine moieties. TpIBT-tFFO is based on a recently proposed molecular design strategy called tilted face-to-face alignment with optimal distance (tFFO), whereas IB-TRZ is a conventional through-bond type molecule. According to quantum chemical calculations, a very large RISC rate constant, k RISC, was expected for TpIBT-tFFO because not only the lowest triplet state but also the second lowest triplet state were close to the lowest excited singlet state, as designed in the tFFO strategy. IB-TRZ has two different conformers, leading to dual emission. Conversely, owing to excellent packing, the conformation was fixed to one in the tFFO system, resulting in single-peaked emission for TpIBT-tFFO. TpIBT-tFFO displayed TADF type behavior and afforded higher photoluminescence quantum yield (PLQY) compared to IB-TRZ. The k RISC of TpIBT-tFFO was determined at 6.9 × 106 s-1, which is one of the highest values among molecules composed of only H, C, and N atoms. The external quantum efficiency of the TpIBT-tFFO-based OLED was much higher than that of the IB-TRZ-based one. The present study confirms the effectiveness of the tFFO design to realize rapid RISC. The tFFO-based emitters were found to exhibit an additional feature, enabling the control of the molecular conformations of the donor and/or acceptor segments.
Project description:Construction of core–dendron TADF emitters systematically: changing the behaviour of chromophores from aggregation-caused quenching to aggregation induced emission to develop high-performance fully solution-processed nondoped OLEDs. The amalgamation of thermally activated delayed fluorescence (TADF) and aggregation-induced emission (AIE) properties, termed AIE-TADF, is a promising strategy to design novel robust luminescent materials. Herein, we transform 2,3,4,5,6-penta(9H-carbazol-9-yl)benzonitrile (5CzBN) from an ACQ molecule into an AIEgen by simply decorating the 5CzBN core with alkyl chain-linked spirobifluorene dendrons. By increasing the number of flexible dendrons, these materials can not only show obvious AIE-TADF characteristics and uniform film morphology, but can also exhibit better resistance to isopropyl alcohol, which are beneficial to fully solution-processed OLEDs. Notably, 5CzBN-PSP shows great device efficiency with an external quantum efficiency (EQE), current efficiency and power efficiency of 20.1%, 58.7 cd A–1 and 46.2 lm W–1, respectively and achieved record-breaking efficiency in solution-processed nondoped OLEDs based on AIE emitters. This work demonstrates a general approach to explore new efficient emitters by the marriage of AIE and TADF which could potentially improve their performance in various areas.
Project description:Highly efficient single-stack hybrid cool white organic light-emitting diodes (OLEDs) having blue-yellow-blue multiple emitting layers (EMLs) are designed and constructed by utilizing blue thermally activated delayed fluorescent (TADF) and yellow phosphorescent emitters. The out-coupling efficiencies of yellow and blue emissions are maximized by tuning the ITO and total device thickness that satisfies both of antinode positions for yellow and blue emissions in a limited multiple EML thickness. To obtain a cool white emission, the exciton formation ratio in the blue-yellow-blue multiple EML system is controlled by manipulating the recombination zone through charge conductivity variation of host medium in the blue TADF EML. The resulting device exhibits cool white emission with very high maximum external quantum efficiency of 23.1% and CIE color coordinates of (0.324, 0.337). We anticipate that the studied approach will raise the viability of single-stack hybrid cool white OLEDs for high performance display applications.