Impact of Spontaneous Orientational Polarization on Triplet-Triplet Upconversion-Based Blue Organic Light-Emitting Diodes.

The spontaneous orientation polarization (SOP) of a permanent dipole moment of the molecule induces a giant surface potential (GSP) in an organic semiconductor film, and GSP is expected to be a crucial parameter for understanding the operational mechanism of organic light-emitting diodes (OLEDs). This study demonstrates that the voltage-dependent migration of a carrier recombination zone induced by a polar electron transporting layer (ETL) having a positive SOP causes a decline in the overall performance of the OLED in triplet-triplet upconversion (TTU) based on OLEDs. Specifically, the TTU efficiency in an OLED with 2,2',2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi) as the ETL decreased by 20% due to the reduction of electrically generated triplet exciton density. This decrease resulted in a lower external electroluminescence (EL) quantum efficiency (EQE) of 5.4% at 1 mA cm-2, while the OLED with a nonpolar ETL resulted in an EQE of around 8.1% at 1 mA cm-2. We confirmed a shift in the recombination zone from the current density dependence of the EL spectra in the OLEDs. Our results indicate that the fixed carrier recombination zone near a hole transport layer and an emitting layer (HTL/EML) strongly enhanced the TTU process, while the polar EML/ETL interface induced the migration of the recombination zone depending on voltage, resulting in the decrease of triplet exciton density.

Hexacarbazolylbenzene: An Excellent Host Molecule Causing Strong Guest Molecular Orientation and the High-Performance OLEDs.

Hexacarbazolylbenzene (6CzPh), which is benzene substituted by six carbazole rings, is a simple and attractive compound. Despite the success of a wide variety of carbazole derivatives in organic light-emitting diodes (OLEDs), 6CzPh has not received attention so far. Here, excellent performances of 6CzPh are revealed as a host material in OLEDs regarding conventional host materials. Various strategies are implemented to improve the performance of OLEDs, e.g., triplet utilization by thermally activated delayed fluorescence (TADF) and phosphorescence emitters for maximizing internal quantum efficiency, and molecular orientation control for increasing outcoupling efficiency. The present host material is suited for both criteria. Robustness of the structure and sufficiently high triplet energy enables a high external quantum efficiency with a long device lifetime. Besides, the host material boosts the horizontal molecular orientations of several guest emitters. It is noteworthy that disk-shaped 4CzIPN marks the complete horizontal molecular orientations (Θh = 100%, S = -0.50). These results provide an effective way of improving efficiencies without sacrificing device durability for future OLEDs.

Three-dimensional sensing of surfaces by projection of invisible electroluminescence from organic light-emitting diodes.

Organic light-emitting diodes (OLEDs) that efficiently emit near-infrared (NIR) light and consume little power will create valuable applications for OLEDs beyond just displays. Here, we report such a NIR-OLED with high operational stability that can be used as a light source for three-dimensional sensing of object's surfaces. Using a narrow-energy-gap material as a host for producing NIR hyperfluorescence system, we fabricated a NIR-OLED exhibiting intense emission at 930 nm with a high external electroluminescence quantum efficiency of more than 1% at a current density of 100 milliamperes per square meter without any degradation even after more than 300 hours of operation. The NIR-OLEDs were integrated with dense complementary metal-oxide semiconductor circuits to make a micro-NIR-OLED projector (0.21 inch, 230,400 pixels). By actively driving the projector on a pixel by pixel and projecting their emission onto objects, we successfully scanned and sensed the surfaces in three dimensions with invisible NIR.

Anti-Stokes Luminescence in Multi-Resonance-Type Thermally-Activated Delayed Fluorescence Molecules.

Photon-upconversion in organic molecular systems is one of the promising technologies for future energy harvesting systems because these systems can generate excitons that possess higher energy than excitation energy. The photon-upconversion caused by absorbing ambient heat as additional energy is particularly interesting because it could ideally provide a light-driving cooling system. However, only a few organic molecular systems have been reported. Here, we report the anti-Stokes photoluminescence (ASPL) derived from hot-band absorption in a series of multi-resonance-type thermally-activated delayed fluorescence (MR-TADF) molecules. The MR-TADF molecules exhibited an anti-Stokes shift of approximately 0.1 eV with a high PL quantum yield in the solution state. The anti-Stokes shift corresponded well to the 1-0 vibration transition from the ground state to the excited singlet state, and we further evaluated a correlation between the activation energy for the ASPL intensity and the TADF process. Our demonstration underlines that MR-TADF molecules have become a novel class of ASPL materials for various future applications, such as light-driving cooling systems.

Multiple donor-acceptor design for highly luminescent and stable thermally activated delayed fluorescence emitters.

A considerable variety of donor-acceptor (D-A) combinations offers the potential for realizing highly efficient thermally activated delayed fluorescence (TADF) materials. Multiple D-A type compounds are one of the promising families of TADF materials in terms of stability as well as efficiencies. However, those emitters are always composed of carbazole-based donors despite a wide choice of moieties used in linearly linked single D-A molecules. Herein, we developed a multiple D-A type TADF compound with two distinct donor units of 9,10-dihydro-9,9-dimethylacridine (DMAC) and carbazole as the hetero-donor design. The new emitter exhibits high photoluminescence quantum yield (PLQY) in various conditions including polar media blend and high concentrations. Organic light-emitting diodes (OLEDs) showed a reasonably high external quantum efficiency (EQE). In addition, we revealed that the multiple-D-A type molecules showed better photostability than the single D-A type molecules, while the operational stability in OLEDs involves dominant other factors.

Enhancing Triplet-Triplet Upconversion Efficiency and Operational Lifetime in Blue Organic Light-Emitting Diodes by Utilizing Thermally Activated Delayed Fluorescence Materials.

In the process of triplet-triplet upconversion (TTU), a bright excited singlet can be generated because of the collision of two dark excited triplets. In particular, the efficiency of TTU is crucial for achieving a high exciton production yield in blue fluorescence organic light-emitting diodes (OLEDs) beyond the theoretical limit. While the theoretical upper limit of TTU contribution yield is expected to be 60%, blue OLEDs with the maximum TTU contribution are still scarce. Herein, we present a proof of concept for realizing the maximum TTU contribution yield in blue OLEDs, achieved through the doping of thermally activated delayed fluorescence (TADF) molecules in the carrier recombination zone. The bipolar carrier transport ability of TADF materials enables direct carrier recombination on the molecules, resulting in the expansion of the recombination zone. Although the external electroluminescence quantum efficiency of OLEDs is slightly lower than that of conventional TTU-OLEDs due to the low photoluminescence quantum yield of the doped layer, the TTU efficiency approaches the upper limit. Furthermore, the operational device lifetime of OLEDs employing TADF molecules increased by five times compared to the conventional ones, highlighting the expansion of the recombination zone as a crucial factor for enhancing overall OLED performance in TTU-OLEDs.

Post-Modification of Pyrrolopyrrole Aza-BODIPY toward High Near-Infrared Fluorescence Brightness.

Pyrrolopyrrole aza-BODIPYs (PPABs), dimeric aza-BODIPY analogues, exhibit intense absorption and fluorescence in the visible and near-infrared (NIR) regions. Here, we developed a facile postmodification by palladium-catalyzed coupling reactions to synthesize a series of donor-acceptor-donor (D-A-D) PPABs. Despite the possible fluorescence quenching dictated by the energy-gap low, D-A-D PPABs exhibit high-fluorescence brightness in the NIR region, implying their potential use as a bright NIR emitter.

Electron Lifetime of Over One Month in Disordered Organic Solid-State Films.

Understanding intrinsic carrier lifetime in disordered organic solid-state semiconductors is essential for improving device performance in not only molecule-based optoelectronic devices such as organic solar cells (OSC) but also photocatalysts used for producing solar fuel cells. Carriers in disordered films are generally thought to have short lifetimes on a scale ranging from nanoseconds to milliseconds. These short carrier lifetimes cause loss of charges in OSCs and low quantum yields in photocatalysts and impede the future application of organic semiconductors to, for example, charge-storage-based memory devices. This study reports an ultralong intrinsic carrier lifetime of more than one month in a disordered film of an organic semiconductor stored at room temperature without external power. This extraordinary lifetime, which is several orders of magnitude longer than that generally believed possible in conventional organic semiconductors, arises from carrier stabilization by spontaneous orientation polarization, excited spin-triplet recycling, and blocking of recombination processes in disordered films.

Multiple resonance type thermally activated delayed fluorescence by dibenzo [1,4] azaborine derivatives.

We studied the photophysical and electroluminescent (EL) characteristics of a series of azaborine derivatives having a pair of boron and nitrogen aimed at the multi-resonance (MR) effect. The computational study with the STEOM-DLPNO-CCSD method clarified that the combination of a BN ring-fusion and a terminal carbazole enhanced the MR effect and spin-orbit coupling matrix element (SOCME), simultaneously. Also, we clarified that the second triplet excited state (T2) plays an important role in efficient MR-based thermally activated delayed fluorescence (TADF). Furthermore, we obtained a blue-violet OLED with an external EL quantum efficiency (EQE) of 9.1%, implying the presence of a pronounced nonradiative decay path from the lowest triplet excited state (T1).

Carbazole-2-carbonitrile as an acceptor in deep-blue thermally activated delayed fluorescence emitters for narrowing charge-transfer emissions.

This work reports a new acceptor for constructing donor-acceptor type (D-A type) blue thermally activated delayed fluorescence (TADF) emitters with narrowed charge-transfer (CT) emissions. A new acceptor core, carbazole-2-carbonitrile (CCN), is formed by the fusion of carbazole and benzonitrile. Three D-A type TADF emitters based on the CCN acceptor, namely 3CzCCN, 3MeCzCCN, and 3PhCzCCN, have been successfully synthesized and characterized. These emitters show deep-blue emissions from 439 to 457 nm with high photoluminescence quantum yields of up to 85% in degassed toluene solutions. Interestingly, all CCN-based deep-blue TADF emitters result in narrow CT emissions with full-width at half-maximums (FWHMs) of less than 50 nm in toluene solutions, which are pretty narrower compared with those of typical D-A type TADF emitters. Devices based on these emitters show high maximum external quantum efficiencies of up to 17.5%.

Spontaneous formation of metastable orientation with well-organized permanent dipole moment in organic glassy films.

The performance of organic optoelectronic and energy-harvesting devices is largely determined by the molecular orientation and resultant permanent dipole moment, yet this property is difficult to control during film preparation. Here, we demonstrate the active control of dipole direction-that is, vector direction and magnitude-in organic glassy films by physical vapour deposition. An organic glassy film with metastable permanent dipole moment orientation can be obtained by utilizing the small surface free energy of a trifluoromethyl unit and intramolecular permanent dipole moment induced by functional groups. The proposed molecular design rule could pave a way toward the formation of spontaneously polarized organic glassy films, leading to improvement in the performance of organic molecular devices.

Significant role of spin-triplet state for exciton dissociation in organic solids.

Clarification of the role of the spin state that initiates exciton dissociation is critical to attaining a fundamental understanding of the mechanism of organic photovoltaics. Although an excited spin-triplet state with an energy lower than that of excited spin-singlet state is disadvantageous in exciton dissociation, a small electron exchange integral results in small singlet-triplet energy splitting in some material systems. This energy splitting leads to a nearly isoenergetic alignment of both excited states, raising a question about the role of excited spin states in exciton dissociation. Herein, we show that the spin-triplet rather than the spin-singlet plays a critical role in the exciton dissociation that leads to the formation of free carriers. This result indicates that the spin-triplet inherently acts as an intermediate, leading to exciton dissociation. Thus, our demonstration provides a fundamental understanding of the role of excited spin states of organic molecular systems in photoinduced charge-carrier generation.

Efficiency of Thermally Activated Delayed Fluorescence Sensitized Triplet Upconversion Doubled in Three-Component System.

As in many fields, the most exciting endeavors in photon upconversion research focus on increasing the efficiency (upconversion quantum yield) and performance (anti-Stokes shift) while diminishing the cost of production. In this vein, studies employing metal-free thermally activated delayed fluorescence (TADF) sensitizers have garnered increased interest. Here, for the first time, the strategy of ternary photon upconversion is utilized with the TADF sensitizer 2,4,5,6-tetrakis(carbazol-9-yl)isophthalonitrile (4CzIPN), resulting in a doubling of the upconversion quantum yield in comparison to the binary system employing p-terphenyl as the emitter. In this ternary blend, the sensitizer 4CzIPN is paired with an intermediate acceptor, 1-methylnaphthalene, in addition to the emitter molecule, p-terphenyl, yielding a normalized upconversion quantum yield of 7.6% while maintaining the 0.83 eV anti-Stokes shift. These results illustrate the potential benefits of utilizing this strategy of energy-funneling, previously used only with heavy-metal based sensitizers, to increase the performance of these photon upconversion systems.

Tetrabenzo[a,c]phenazine Backbone for Highly Efficient Orange-Red Thermally Activated Delayed Fluorescence with Completely Horizontal Molecular Orientation.

Three thermally activated delayed fluorescence (TADF) molecules, namely PQ1, PQ2, and PQ3, are composed of electron-accepting (A) tetrabenzo[a,c]phenazine (TBPZ) and electron-donating (D) phenoxazine (PXZ) units are designed and characterized. The combined effects of planar acceptor manipulation and high steric hindrance between D and A units endow high molecular rigidity that suppresses nonradiative decay of the excitons with improved photoluminescence quantum yields (PLQYs). Particularly, the well-aligned excited states involving a singlet and a triplet charge-transfer excited states and a localized excited triplet state in PQ3 enhances the reverse intersystem crossing rate constant (kRISC ) with a short delay lifetime (τd ). The orange-red OLED based on PQ3 displays a maximum external EL quantum efficiency (EQE) of 27.4 % with a well-suppressed EL efficiency roll-off owing to a completely horizontal orientation of the transition dipole moment in the film state.

Highly Efficient Near-Infrared Electrofluorescence from a Thermally Activated Delayed Fluorescence Molecule.

Near-IR organic light-emitting diodes (NIR-OLEDs) are potential light-sources for various sensing applications as OLEDs have unique features such as ultra-flexibility and low-cost fabrication. However, the low external electroluminescence (EL) quantum efficiency (EQE) of NIR-OLEDs is a critical obstacle for potential applications. Here, we demonstrate a highly efficient NIR emitter with thermally activated delayed fluorescence (TADF) and its application to NIR-OLEDs. The NIR-TADF emitter, TPA-PZTCN, has a high photoluminescence quantum yield of over 40 % with a peak wavelength at 729 nm even in a highly doped co-deposited film. The EL peak wavelength of the NIR-OLED is 734 nm with an EQE of 13.4 %, unprecedented among rare-metal-free NIR-OLEDs in this spectral range. TPA-PZTCN can sensitize a deeper NIR fluorophore to achieve a peak wavelength of approximately 900 nm, resulting in an EQE of over 1 % in a TADF-sensitized NIR-OLED with high operational device durability (LT95 >600 h.).

Precise Exciton Management of Quaternary Emission Layers for Highly Stable Organic Light-Emitting Diodes Based on Thermally Activated Delayed Fluorescence.

Simultaneous achievement of both high electroluminescence efficiency and high operational stability in organic light-emitting diodes (OLEDs) is required for their use in various practical applications. Although OLEDs based on thermally activated delayed fluorescence-assisted fluorescence (TAF) are considered to possess a promising device architecture to exploit the full potential of OLEDs, the operational stability of such systems still requires further improvement. In this study, a quaternary emission layer consisting of a combination of TAF and mixed-host systems is developed. OLEDs containing this emission layer show improved operational stability through the management of exciton generation processes while maintaining high electroluminescence efficiency. Furthermore, a gradient of the mixed ratio of the co-host matrix is used to optimize the recombination zone profile in the emission layer, leading to 17 times improvement of the operational lifetime compared with that of the corresponding single-host-based device. This research provides a simple and general method to develop highly stable TAF-OLEDs.

Molecular Design Based on Donor-Weak Donor Scaffold for Blue Thermally-Activated Delayed Fluorescence Designed by Combinatorial DFT Calculations.

Quantum chemical calculations are necessary to develop advanced emitter materials showing thermally-activated delayed fluorescence (TADF) for organic light-emitting diodes (OLEDs). However, calculation costs become problematic when more accurate functionals were used, therefore it is judicious to use a multimethod approach for efficiency. Here we employed combinatorial chemistry in silico to develop the deep blue TADF materials with a new concept of homo-junction design. The homo-junction materials containing TADF candidates designed by calculation were synthesized and analyzed. We found that these materials showed the emission from charge transfer (CT) state, and the clear delayed emission was provided in solid state. Because the homo-junction TADF materials showed three exponential decayed emission in solid state, we employed novel four-state kinetic analysis.

Nanosecond-time-scale delayed fluorescence molecule for deep-blue OLEDs with small efficiency rolloff.

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.

Utilization of Multi-Heterodonors in Thermally Activated Delayed Fluorescence Molecules and Their High Performance Bluish-Green Organic Light-Emitting Diodes.

We report a series of pentacarbazolyl-benzonitrile derivatives such as 2,4,6-tri(9H-carbazol-9-yl)-3,5-bis(3,6-di(pyridin-3-yl)-9H-carbazol-9-yl)benzonitrile (mPyBN), 3,5-bis(3,6-bis(4-(trifluoromethyl)phenyl)-9H-carbazol-9-yl)-2,4,6-tri(9H-carbazol-9-yl)benzonitrile (pCF3BN), 2,4,6-tri(9H-carbazol-9-yl)-3-(3,6-di(pyridin-3-yl)-9H-carbazol-9-yl)-5-(3,6-diphenyl-9H-carbazol-9-yl)benzonitrile (PyPhBN), 3-(3,6-bis(4-(trifluoromethyl)phenyl)-9H-carbazol-9-yl)-2,4,6-tri(9H-carbazol-9-yl)-5-(3,6-di(pyridin-3-yl)-9H-carbazol-9-yl)benzonitrile (PyCF3BN), and 3-(3,6-bis(4-(trifluoromethyl)phenyl)-9H-carbazol-9-yl)-2,6-di(9H-carbazol-9-yl)-5-(3,6-di(pyridin-3-yl)-9H-carbazol-9-yl)-4-(9H-pyrido[3,4-b]indol-9-yl)benzonitrile (CbPyCF3BN) in which some of the carbazoles are substituted with modified 3,5-diphenyl carbazoles, exhibiting thermally activated delayed fluorescence (TADF) properties. These emitters comprised two, three, and four different types of donors, capable of bluish-green emission of around 480 nm with relatively high photoluminescence quantum yields over 90% in solution. Emitters, namely, PyPhBN, PyCF3BN, and CbPyCF3BN, composed of three and four different types of donors endowed a rather short delayed lifetime (τd) of 4.25, 5.01, and 3.65 µs in their film state, respectively. Bluish-green organic light-emitting diodes based on PyPhBN, PyCF3BN, and CbPyCF3BN exhibit a high external quantum efficiency of 20.6, 19.5, and 19.6%, respectively, with unsurpassed efficiency roll-off behavior. These results indicate that the TADF properties of multidonor type molecules can be manipulated by controlling the types and number of electron donor units.

The Role of Reverse Intersystem Crossing Using a TADF-Type Acceptor Molecule on the Device Stability of Exciplex-Based Organic Light-Emitting Diodes.

Exciplex system exhibiting thermally activated delayed fluorescence (TADF) holds a considerable potential to improve organic light-emitting diode (OLED) performances. However, the operational lifetime of current exciplex-based devices, unfortunately, falls far behind the requirement for commercialization. Herein, rationally choosing a TADF-type electron acceptor molecule is reported as a new strategy to enhance OLEDs' operating lifetime. A comprehensive study of the exciplex system containing 9,9',9''-triphenyl-9H,9'H,9''H-3,3':6',3''-tercarbazole (Tris-PCz) and triazine (TRZ) derivatives clarifies the relationship between unwanted carrier recombination on acceptor molecules, TADF property of acceptors, and the device degradation event. By employing a proposed "exciton recycling" strategy, a threefold increased operational lifetime can be achieved while still maintaining high-performance OLED properties. In particular, a stable blue OLED that employs this strategy is successfully demonstrated. This research provides an important step for exciplex-based devices toward the significant improvement of operational stability.