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A novel class of o-carboranyl luminophores, 2CB-BuDABNA (1) and 3CB-BuDABNA (2) is reported, in which o-carborane moieties are incorporated at the periphery of the B,N-doped multi-resonance thermally activated delayed fluorescence (MR-TADF) core. Both compounds maintain the inherent local emission characteristics of their MR-emitting core, exhibiting intense MR-TADF with high photoluminescence quantum yields in toluene and rigid states. In contrast, the presence of the dark lowest-energy charge transfer state, induced by cage rotation in THF, is suggested to be responsible for emission quenching in a polar solvent. Despite the different arrangement of the cage on the DABNA core, both 1 and 2 show red-shifted emissions compared to the parent compound BuDABNA (3). By utilizing 1 as the emitter, high-efficiency blue organic light-emitting diodes (OLEDs) are achieved with a remarkable maximum external quantum efficiency of 25%, representing the highest reported efficiency for OLEDs employing an o-carboranyl luminophore as the emitter.
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Narrowband emissive multiple resonance (MR) emitters promise high efficiency and stability in deep-blue organic light-emitting diodes (OLEDs). However, the construction of ideal ultra-narrow-band deep-blue MR emitters still faces formidable challenges, especially in balancing bathochromic-shift emission, spectral narrowing, and aggregation suppression. Here, DICz is chosen, which possesses the smallest full-width-at-half-maximum (FWHM) in MR structures, as the core and solved the above issue by tuning its peripheral substitution sites. The 1-substituted molecule Cz-DICz is able to show a bright deep-blue emission with a peak at 457 nm, an extremely small FWHM of 14 nm, and a CIE coordinate of (0.14, 0.08) in solution. The corresponding OLEDs exhibit high maximum external quantum efficiencies of 22.1%-25.6% and identical small FWHMs of 18 nm over the practical mass-production concentration range (1-4 wt.%). To the best of the knowledge, 14 and 18 nm are currently the smallest FWHM values for deep-blue MR emitters with similar emission maxima under photoluminescence and electroluminescence conditions, respectively. These discoveries will help drive the development of high-performance narrowband deep-blue emitters and bring about a revolution in OLED industry.
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Due to the relatively low photoluminescence quantum yield (PLQY) and horizontal dipole orientation of doped films, anthracene-based fluorescent organic light-emitting diodes (F-OLEDs) have faced a great challenge to achieve high external quantum efficiency (EQE). Herein, a novel approach is introduced by incorporating penta-helicene into anthracene, presented as linear-shaped 3-(4-(10-phenylanthracen-9-yl)phenyl)dibenzo[c,g]phenanthrene (BABH) and 3-(4-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)dibenzo[c,g]phenanthrene (NABH). These blue hosts exhibit minimal intermolecular overlap of π-π stacking, effectively suppressing excimer formation, which facilitates the effective transfer of singlet energy to the fluorescent dopant for PLQY as high as 90%. Additionally, the as-obtained two hosts of BABH and NABH have effectively demonstrated major horizontal components transition dipole moments (TDM) and high thermal stability with glass transitional temperature (Tg) surpassing 188 °C, enhancing the horizontal dipole orientation of their doped films to be 89% and 93%, respectively. The OLEDs based on BABH and NABH exhibit excellent EQE of 10.5% and 12.4% at 462 nm and device lifetime up to 90% of the initial luminance over 4500 h at 100 cd m-2, which has firmly established them as among the most efficient blue F-OLEDs based on anthracene to date to the best knowledge. This work provides an instructive strategy to design an effective host for highly efficient and stable F-OLEDs.
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Organic light-emitting diodes (OLEDs) have outperformed conventional display technologies in smartphones, smartwatches, tablets, and televisions while gradually growing to cover a sizable fraction of the solid-state lighting industry. Blue emission is a crucial chromatic component for realizing high-quality red, green, blue, and yellow (RGBY) and RGB white display technologies and solid-state lighting sources. For consumer products with desirable lifetimes and efficiency, deep blue emissions with much higher power efficiency and operation time are necessary prerequisites. This article reviews over 700 papers covering various factors, namely, the crucial role of blue emission for full-color displays and solid-state lighting, the performance status of blue OLEDs, and the systematic development of fluorescent, phosphorescent, and thermally activated delayed fluorescence blue emitters. In addition, various challenges concerning deep blue efficiency, lifetime, and approaches to realizing deeper blue emission and higher efficacy for blue OLED devices are also described.
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Two newly designed and synthesized [3+2+1] iridium complexes through introducing bulky trimethylsiliyl (TMS) groups are doped with a terminal emitter of v-DABNA to form an coincident overlapping spectra between the emission of these two phosphors and the absorption of v-DABNA, creating cascade resonant energy transfer for efficient triplet harvesting. To boost the color quality and efficiency, the fabricated hyper-OLEDs have been optimized to achieve a high external quantum efficiency of 31.06%, which has been among the highest efficiency results reported for phosphor sensitized saturated-blue hyper-OLEDs, and pure blue emission peak at 467 nm with the full width at half maxima (FWHM) as narrow as 18 nm and the CIEy values down to 0.097, satisfying the National Institute of Standards and Technology (NIST) requirement for saturated blue OLEDs display. Surprisingly, such hyper-OLEDs have obtained the converted lifetime (LT50 ) up to 4552 h at the brightness of 100 cd m-2 , demonstrating effective Förster resonance energy transfer (FRET) process. Therefore, employing these new bulky TMS substituent [3+2+1] iridium(III) complexes for effective sensitizers can greatly pave the way for further development of high efficiency and stable blue OLEDs in display and lighting applications.
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Developing high-efficiency nondoped blue organic light-emitting diodes (OLEDs) with high color purity and low-efficiency roll-off is vital for display and lighting applications. Herein, we developed two asymmetric D-π-A blue emitters, PIAnTP and PyIAnTP, in which triphenylene is first utilized as a functional acceptor. The relatively weak charge transfer (CT) properties, rigid molecular structures, and multiple supramolecular interactions in PIAnTP and PyIAnTP can significantly enhance the fluorescence efficiency and suppress the structural relaxations to obtain a narrowband blue emission. The photophysical experiments and theoretical simulations reveal that they both exhibit a typical hybridized local and charge-transfer (HLCT) excited state and achieve high external quantum efficiency (EQE) via a "hot exciton" channel. As a result, PIAnTP- and PyIAnTP-based nondoped devices realize blue emission at 456 and 464 nm, corresponding to CIE coordinates of (0.16, 0.14) and (0.16, 0.19), narrow full width at half-maximums of 52 and 60 nm, and the high EQEs of 8.36 and 8.69%, respectively. More importantly, the PIAnTP- and PyIAnTP-based nondoped devices show small EQE roll-offs of only 5.9 and 2.4% at 1000 cd m-2, respectively. These results signify an advance in designing a highly efficient blue emitter for nondoped OLEDs.
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In this study, various diffusers are applied to highly efficient ultra-thin emission layer (EML) structure-based blue phosphorescent organic light-emitting diodes (PHOLEDs) to improve the electroluminescence (EL) characteristics and viewing angle. To achieve highly efficient blue PHOLEDs, the EL characteristics of ultra-thin EML PHOLEDs with the various diffusers having different structures of pattern-shape (hemisphere/sphere), size (4~75 µm), distribution (surface/embedded), and packing (close-packed/random) were systematically analyzed. The diffusers showed different enhancements in the overall EL characteristics of efficiencies, viewing angle, and others. The EL characteristics showed apparent dependency on their structure. The external quantum efficiency (EQE) was enhanced mainly by following the orders of pattern, size, and shape. Following the pattern size, the EQE enhancement gradually increased; the largest-sized diffuser with a 75 µm closed-packed hemisphere (diffuser-1) showed a 1.47-fold EQE improvement, which was the highest. Meanwhile, the diffuser with a ~7 µm random embedded sphere with a low density (diffuser 5) showed the lowest 1.02-fold-improved EQE. The reference device with ultra-thin EML structure-based blue PHOLEDs showed a maximum EQE of 16.6%, and the device with diffuser 1 achieved a maximum EQE of 24.3% with a 5.1% wider viewing angle compared to the reference device without a diffuser. For the in-depth analysis, the viewing angle profile of the ultra-thin EML PHOLED device and fluorescent green OLEDs were compared. As a result, the efficiency enhancement characteristics of the diffusers show a difference in the viewing angle profile. Finally, the application of the diffuser successfully demonstrated that the EL efficiency and viewing angle could be selectively improved. Additionally, we found that it was possible to realize a wide viewing angle and achieve considerable EQE enhancement by further investigations using high-density and large-sized embedded structures of light-extraction film.
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Designing multi-resonance (MR) emitters that can simultaneously achieve narrowband emission and suppressed intermolecular interactions is challenging for realizing high color purity and stable blue organic light-emitting diodes (OLEDs). Herein, a sterically shielded yet extremely rigid emitter based on a triptycene-fused B,N core (Tp-DABNA) is proposed to address the issue. Tp-DABNA exhibits intense deep blue emissions with a narrow full width at half maximum (FWHM) and a high horizontal transition dipole ratio, superior to the well-known bulky emitter, t-DABNA. The rigid MR skeleton of Tp-DABNA suppresses structural relaxation in the excited state, with reduced contributions from the medium- and high-frequency vibrational modes to spectral broadening. The hyperfluorescence (HF) film composed of a sensitizer and Tp-DABNA shows reduced Dexter energy transfer compared to those of t-DABNA and DABNA-1. Notably, deep blue TADF-OLEDs with the Tp-DABNA emitter display higher external quantum efficiencies (EQEmax =24.8 %) and narrower FWHMs (≤26â nm) than t-DABNA-based OLEDs (EQEmax =19.8 %). The HF-OLEDs based on the Tp-DABNA emitter further demonstrate improved performance with an EQEmax of 28.7 % and mitigated efficiency roll-offs.
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Significant lifetime enhancement, up to an eight-fold increase in T90, has been demonstrated in blue organic light-emitting diode (OLED) devices through the deuteration of host and hole transport materials. We observed a progressive increase in T90 using a series of anthracene-based hydrocarbon hosts with incremental deuteration in the emitting layer. In addition, we realized further lifetime improvement using a deuterated hole-transport layer along with the deuterated emitting layer. To elucidate the deuteration effects, we utilized laser desorption/ionization-time-of-flight (LDI-TOF) mass spectrometry for in situ UV irradiation to induce photodegradation and immediate chemical analysis of the resultant photodegradation species. Adducts between the host and moieties from transport materials were identified in UV-degraded films comprising a mixture of host and transport materials, indicating that similar species could be produced in OLED devices using these materials. Deuteration, in effect, mediated the formation of these adduct species, presumably electroluminescence quenchers, and thus improved the device lifetime. An approximate agreement was obtained between the kinetic isotope effect of the photodegradation reactions and the enhancement in device lifetime with deuteration.
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Thermally activated delayed fluorescence (TADF) materials, which can harvest all excitons and emit light without the use of noble metals, are an appealing class of functional materials emerging as next-generation organic electroluminescent materials. Triplet excitons can be upconverted to the singlet state with the aid of ambient thermal energy under the reverse inter-system crossing owing to the small singlet-triplet splitting energy (ΔEST). This results from a specific molecular design consisting of minimal overlap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, due to the spatial separation of the electron-donating and electron-releasing part. When a well-designed device structure is applied, high-performance blue-emitting TADF organic light-emitting diodes can be realized with an appropriate molecular design. Unlike the previous literature that has reviewed general blue-emitting TADF materials, in this paper, we focus on materials other than pure organic molecules with twist D-π-A structures, including multi-resonance TADF, through-space charge transfer TADF, and metal-TADF materials. Cutting-edge molecules with extremely small and even negative ΔEST values are also introduced as candidates for next-generation TADF materials. In addition, OLED structures used to exploit the merits of the abovementioned TADF emitters are also described in this review.
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In this study, we synthesized and characterized multiple resonance (MR) type blue thermally activated delayed fluorescence (TADF) emitters. Unlike many boron-based MR-TADF materials, the blue TADF emitters of this work had an asymmetric molecular structure with one boron, one oxygen, and one nitrogen. The aromatic units linked to the nitrogen were changed into diphenylamine, carbazole, dimethylacridine, and diphenylacridine to manage the light emission properties of the emitters. The TADF emitters exhibited a blue emission due to the weak electron-donating oxygen atom and the emission color was controlled by the aromatic unit connected to the nitrogen. The simple diphenylamine unit was effective in achieving real deep-blue emission for the BT2020 standard with a high external quantum efficiency (EQE), while the electron-rich nitrogen-based dimethylacridine and diphenylacridine accelerated the reverse intersystem crossing for high EQE and small EQE roll-off. Among the emitters, a diphenylamine-substituted emitter, 7-(tert-butyl)-9-phenyl-9H-5-oxa-9-aza-13b-boranaphtho[3,2,1-de]anthracene (B-O-dpa), showed a maximum external quantum efficiency of 16.3%, a small full width at half-maximum of 32 nm, and a real deep-blue color coordinate of (0.15, 0.05).
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A novel bis-4Ph-substituted 9,10-dipehnylanthracene deep blue [1931 CIE (0.15, 0.08)] fluorescent compound, AnB4Ph, has been synthesized and characterized for organic light-emitting diode (OLED) applications. Our experimental study of AnB4Ph excludes the possibility of triplet-triplet annihilation, hybridized local and charge transfer, or thermally activated delayed fluorescent characteristics of the material. Since the solid-state photoluminescence quantum yield of AnB4Ph was determined to be 48%, assuming a 100% for the charge recombination efficiency, the light outcoupling efficiency (ηout) of an AnB4Ph non-doped OLED achieving an external quantum efficiency (EQE) of 5.3% is at least 44%, which is more than twofold higher than 20% for conventional OLEDs. Both grazing incidence wide-angle X-ray scattering (GIWAXS) and angle-dependent photoluminescence (ADPL) measurements reveal AnB4Ph having a high value of order parameter (SGIWAXS) of 0.61 for a ππ stacking along the normal direction and an orientation order parameter (SADPL) for a horizontal emitting dipole moment of -0.50 or Θ (horizontal-dipole ratios) of 100%, respectively. Otherwise, a refractive index (n) measurement provides a n = 1.80 for AnB4Ph thin films. Based on ηout = 1.2 × n-2, the calculated ηout is 37%, which is also in accordance with the results of GIWAXS and ADPL. We have also fabricated the classical fluorescent DPAVBi-doped AnB4Ph OLEDs, which display a true blue [1931 CIE (0.15 and 0.16)] electroluminescence with a high efficiency (EQE = 6.9%), surpassing the conventional â¼5% EQE. Based on an ηout of 42% for DPAVBi-doped AnB4Ph OLEDs, our studies suggest that the extremely horizontally aligned AnB4Ph host material exerts the same horizontal alignment on the DPAVBi dopant molecules.
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Tremendous efforts have been made on researching triplet-triplet annihilation (TTA) and thermally activated delayed fluorescence (TADF) materials for realizing high-efficiency blue organic light-emitting diodes (OLEDs) through utilizing triplet exciton conversion to the lowest singlet excited state (S1) from the lowest triplet excited state (T1). However, hot exciton conversion from the upper triplet energy level state (Tn, n > 1) to the lowest singlet excited state (S1) is an increasingly promising method for realizing pure-blue non-doped OLEDs with performances comparable to those of TTA and TADF materials. Herein, two pure-blue fluorescent emitters of donor (D)-π-acceptor (A) type, PIAnCz and PIAnPO, were designed and synthesized. The excited-state characteristics of PIAnCz and PIAnPO, confirmed by theoretical calculations and photophysical experiments, demonstrated these materials' hot exciton properties. Based on PIAnCz and PIAnPO as emission layer materials, the fabricated non-doped devices exhibited pure-blue emission with Commission Internationale de l'Eclairage (CIE) coordinates of (0.16, 0.12) and (0.16, 0.15), maximum luminescences of 10,484 and 15,485 cd m-2, and maximum external quantum efficiencies (EQEs) of 10.9 and 8.3%. Besides, at a luminescence of 1000 cd m-2, the EQEs of PIAnPO-based devices can still be high at 7.7%, and the negligible efficiency roll-off was 6.0%. The device performance of both materials demonstrates their outstanding potential for commercial application.
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Highly efficient sky-blue luminescent gold(III) complexes with emission quantum yields up to 82 %, lifetimes down to 0.67â µs and emission peak maxima at 470-484â nm were prepared through a consideration of pincer gold(III) donor-acceptor complexes. Photophysical studies and time-dependent density functional theory (TDDFT) calculations revealed that the emission nature of these gold(III) complexes is most consistent with TADF. Solution-processed OLEDs with these gold(III) complexes as dopants afforded electroluminescence maxima at 465-473â nm with FWHM of 64-67â nm and maximum external quantum efficiencies (EQEs) of up to 15.25 %. This research demonstrates the first example of gold(III)-OLEDs showing electroluminescence maxima at smaller than 470â nm, and highlights the potential of using gold(III)-TADF emitters in the development of high efficiency blue OLEDs and blue emissive dopant in WOLEDs.
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New thermally activated delayed fluorescence (TADF) blue emitter molecules based on the known donor-acceptor-donor (D-A-D)-type TADF molecule, 2,7-bis(9,9-dimethylacridin-10-yl)-9,9-dimethylthioxanthene-S,S-dioxide (DDMA-TXO2), are reported. The motivation for the present investigation is via the use of rational molecular design, based on DDMA-TXO2, to elevate the organic light emitting diode (OLED) performance and obtain deeper blue color coordinates. To achieve this goal, the strength of the donor (D) unit and acceptor (A) units have been tuned with methyl substituents. The methyl functionality on the acceptor was also expected to modulate the D-A torsion angle in order to obtain a blue shift in the electroluminescence. The effect of regioisomeric structures has also been investigated. Herein, we report the photophysical, electrochemical, and single-crystal X-ray crystallography data to assist with the successful OLED design. The methyl substituents on the DDMA-TXO2 framework have profound effects on the photophysics and color coordinates of the emitters. The weak electron-donating methyl groups alter the redox properties of the D and A units and consequently affect the singlet and triplet levels but not the energy gap (ΔEST). By systematically manipulating all of the aforementioned factors, devices have been obtained with acceptor-substituted III with a maximum external quantum efficiency of 22.6% and Commission Internationale de l'Éclairage coordinates of (0.15, 0.18) at 1000 cd m-2.
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Phosphorescent organic light-emitting diodes (OLEDs) are leading candidates for next-generation displays and solid-state lighting technologies. Much of the academic and commercial pursuits in phosphorescent OLEDs have been dominated by Ir(III) complexes. Over the past decade recent developments have enabled square planar Pt(II) and Pd(II) complexes to meet or exceed the performance of Ir complexes in many aspects. In particular, the development of N-heterocyclic carbene-based emitters and tetradentate cyclometalated Pt and Pd complexes have significantly improved the emission efficiency and reduced their radiative lifetimes making them competitive with the best reported Ir complexes. Furthermore, their unique and diverse molecular design possibilities have enabled exciting photophysical attributes including narrower emission spectra, excimer -based white emission, and thermally activated delayed fluorescence. These developments have enabled the fabrication of efficient and "pure" blue OLEDs, single-doped white devices with EQEs of over 25% and high CRI, and device operational lifetimes which show early promise that square planar metal complexes can be stable enough for commercialization. These accomplishments have brought Pt complexes to the forefront of academic research. The molecular design strategies, photophysical characteristics, and device performance resulting from the major advancements in emissive Pt and Pd square planar complexes are discussed.
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J.-J. Kim and co-workers achieve highly efficient blue organic light-emitting diodes (OLEDs) using a low-refractive-index layer. As described on page 4920, an external quantum efficiency over 34% is achieved, owing to the low refractive index of the materials. A milepost and a shining entrance of the castle are the metaphor indicating the way to highly efficient blue OLEDs. On the way to the castle, the depicted chemical structures serve as the light-emitting layer.
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Blue-phosphorescent organic light-emitting diodes (OLEDs) with 34.1% external quantum efficiency (EQE) and 79.6 lm W(-1) are demonstrated using a hole-transporting layer and electron-transporting layer with low refractive index values. Using optical simulations, it is predicted that outcoupling efficiencies with EQEs > 60% can be achieved if organic layers with a refractive index of 1.5 are used for OLEDs.