Over 10% EQE Near‐Infrared Electroluminescence Based on a Thermally Activated Delayed Fluorescence Emitter

Significant effort has been made to develop novel material systems to improve the efficiency of near‐infrared organic light‐emitting diodes (NIR OLEDs). Of those, fluorescent chromophores are mostly studied because of their advantages in cost and tunability. However, it is still rare for fluorescent NIR emitters to present good color purities in the NIR range and to have high external quantum efficiency (EQE). Here, a wedge‐shaped D‐π‐A‐π‐D emitter APDC‐DTPA with thermally activated delayed fluorescence property and a small single‐triplet splitting (ΔE_st) of 0.14 eV is presented. The non‐doped NIR device exhibits excellent performance with a maximum EQE of 2.19% and a peak wavelength of 777 nm. Remarkably, when 10 wt% of APDC‐DTPA is doped in 1,3,5‐tris(1‐phenyl‐1H‐benzimidazol‐2‐yl)benzene host, an extremely high EQE of 10.19% with an emission peak of 693 nm is achieved. All these values represent the best result for NIR OLEDs based on a pure organic fluorescent emitter with similar device structure and color gamut.     

20% External Quantum Efficiency in Solution‐Processed Blue Thermally Activated Delayed Fluorescent Devices

Highly efficient solution‐processed blue thermally activated delayed fluorescent (TADF) devices are developed by designing soluble blue TADF emitters. The solubility and emission color could be managed by introducing F as an electron withdrawing unit instead of CN. Two soluble blue TADF emitters are synthesized and show a high external quantum efficiency of 20.0% with a color coordinate of (0.16,0.26), and it is the best quantum efficiency reported in solution‐processed TADF devices. The device performances of the solution‐processed blue TADF devices are comparable to those of vacuum‐processed blue TADF devices.     

Singlet–Triplet Splitting Energy Management via Acceptor Substitution: Complanation Molecular Design for Deep‐Blue Thermally Activated Delayed Fluorescence Emitters and Organic Light‐Emitting Diodes Application

A barely reached balance between weak intramolecular‐charge‐transfer (ICT) and small singlet–triplet splitting energy (ΔE_ST) for reverse intersystem crossing from non‐emissive triplet state to radiative singlet state impedes the realization of deep‐blue thermally activated delayed fluorescence (TADF) materials. By discarding the twisted‐ICT framework for a flattened molecular backbone and introducing a strong acceptor possessing n–π* transition character, hypsochromic color, a large radiative rate (k_F), and small ΔE_ST are achieved simultaneously. Six molecules with a 9,9‐dimethyl‐10‐phenyl‐9,10‐dihydroacridine (i‐DMAc) donor are synthesized and investigated. Coinciding with time‐dependent density functional theory, the reduced dihedral angles between donor (D) and acceptor (A) weaken ICT from dispersed charge density and enable a large k_F from increased frontier molecular orbitals overlap. Despite the separated highest occupied (HOMO) and lowest unoccupied molecular orbital (LUMO) population, the intercalation of phenyl bridges between D–A increases k_F but significantly lowers the local triplet excited state, indicating small HOMO and LUMO overlap is not a sufficient, but necessary condition for reduced ΔE_ST. Integrating short conjugation length and carbonyl or triazine acceptors into the complanation molecules, deep‐blue TADF organic light‐emitting diodes demonstrate maximum external quantum efficiencies of 11.5% and 10.9% with Commission Internationale de l'Eclairage coordinates of (0.16, 0.09) and (0.15, 0.11), respectively, which is quite close to the stringent National Television System Committee blue standard.     

Multifunctional Crosslinkable Iridium Complexes as Hole Transporting/Electron Blocking and Emitting Materials for Solution‐Processed Multilayer Organic Light‐Emitting Diodes

Here, a new series of crosslinkable heteroleptic iridium (III) complexes for use in solution processed phosphorescent organic light emitting diodes (OLEDs) is reported. These iridium compounds have the general formula of (PPZ‐VB)₂Ir(CˆN), where PPZ‐VB is phenylpyrazole (PPZ) vinyl benzyl (VB) ether; and the CˆN ligands represent a family of four different cyclometallating ligands including 1‐phenylpyrazolyl (PPZ) (1), 2‐(4,6‐difluorophenyl)pyridyl (DFPPY) (2), 2‐(p‐tolyl)pyridyl (TPY) (3), and 2‐phenylquinolyl (PQ) (4). With the incorporation of two crosslinkable VB ether groups, these compounds can be fully crosslinked after heating at 180 °C for 30 min. The crosslinked films exhibit excellent solvent resistance and film smoothness which enables fabrication of high‐performance multilayer OLEDs by sequential solution processing of multiple layers. Furthermore, the photophysical properties of these compounds can be easily controlled by simply changing the cyclometallating CˆN ligand in order to tune the triplet energy within the range of 3.0–2.2 eV. This diversity makes these materials not only suitable for use in hole transporting and electron blocking but also as emissive layers of several colors. Therefore, these compounds are applied as effective materials for all‐solution processed OLEDs with (PPZ‐VB)₂IrPPZ (1) acting as hole transporting and electron blocking layer and host material, as well as three other compounds, (PPZ‐VB)₂IrDFPPY ( 2 ), (PPZ‐VB)₂IrTPY(3), and (PPZ‐VB)₂IrPQ( 4 ), used as crosslinkable phosphorescent emitters.     

Multiresonant Thermally Activated Delayed Fluorescence Emitters Based on Heteroatom‐Doped Nanographenes: Recent Advances and Prospects for Organic Light‐Emitting Diodes

Since the first report in 2015, multiresonant thermally activated delayed fluorescent (MR‐TADF) compounds, a subclass of TADF emitters based on a heteroatom‐doped nanographene material, have come to the fore as attractive hosts as well as emitters for organic light‐emitting diodes (OLEDs). MR‐TADF compounds typically show very narrow‐band emission, high photoluminescence quantum yields, and small ΔE_ST values, typically around 200 meV, coupled with high chemical and thermal stabilities. These materials properties have translated into some of the best reported deep‐blue TADF OLEDs. Here, a detailed review of MR‐TADF compounds and their derivatives reported so far is presented. This review comprehensively documents all MR‐TADF compounds, with a focus on the synthesis, optoelectronic behavior, and OLED performance. In addition, computational approaches are surveyed to accurately model the excited state properties of these compounds.     

High‐Performance Hybrid White Organic Light‐Emitting Diodes with Superior Efficiency/Color Rendering Index/Color Stability and Low Efficiency Roll‐Off Based on a Blue Thermally Activated Delayed Fluorescent Emitter

Thermally activated delayed fluorescence (TADF)‐based white organic light‐emitting diodes (WOLEDs) are highly attractive because the TADF emitters provide a promising alternative route to harvest triplet excitons. One of the major challenges is to achieve superior efficiency/color rendering index/color stability and low efficiency roll‐off simultaneously. In this paper, high‐performance hybrid WOLEDs are demonstrated by employing an efficient blue TADF emitter combined with red and green phosphorescent emitters. The resulting WOLED shows the maximum external quantum efficiency, current efficiency, and power efficiency of 23.0%, 51.0 cd A^?1, and 51.7 lm W^?1, respectively. Moreover, the device exhibits extremely stable electroluminescence spectra with a high color rendering index of 89 and Commission Internationale de L'Eclairage coordinates of (0.438, 0.438) at the practical brightness of 1000 cd m^?2. The achievement of these excellent performances is systematically investigated by versatile experimental and theoretical evidences, from which it is concluded that the utilization of a blue‐green‐red cascade energy transfer structure and the precise manipulation of charges and excitons are the key points. It can be anticipated that this work might be a starting point for further research towards high‐performance hybrid WOLEDs.     

High Performance p‐ and n‐Type Light‐Emitting Field‐Effect Transistors Employing Thermally Activated Delayed Fluorescence

Light‐emitting field‐effect transistors (LEFETs) are an emerging type of devices that combine light‐emitting properties with logical switching function. One of the factors limiting their efficiency stems from the spin statistics of electrically generated excitons. Only 25% of them, short lived singlet states, are capable of light emission, with the other 75% being long lived triplet states that are wasted as heat due to spin‐forbidden processes. Traditionally, the way to overcome this limitation is to use phosphorescent materials as additional emission channel harnessing the triplet excitons. Here, an alternative strategy for triplet usage in LEFETs in the form of thermally activated delayed fluorescence (TADF) is presented. Devices employing a TADF capable material, 4CzIPN (2,4,5,6‐tetra[9H‐carbazol‐9‐yl]isophthalonitrile), in both n‐type and p‐type configurations are shown. They manifest excellent electrical characteristics, consistent brightness in the range of 100–1,000 cd m^‐2 and external quantum efficiency (EQE) of up to 0.1%, which is comparable to the equivalent organic light‐emitting diode (OLED) based on the same materials. Simulation identifies the poor light out‐coupling as the main reason for lower than expected EQEs. Transmission measurements show it can be partially alleviated using a more transparent top contact, however more structural optimization is needed to tap the full potential of the device.     

Improving the Efficiency of Red Thermally Activated Delayed Fluorescence Organic Light‐Emitting Diode by Rational Isomer Engineering

The development of efficient red thermally activated delayed fluorescence (TADF) emitters with an emission wavelength beyond 600 nm remains a great challenge for organic light‐emitting diodes (OLEDs). Herein, two pairs of isomers are designed and synthesized by attaching electron‐donor 9,9‐diphenyl‐9,10‐dihydroacridine (DPAC) moiety to the different positions of two kinds of highly rigid planar acceptor cores (PDCN and PPDCN). Their TADF efficiencies and emission maxima (599–726 nm) are regulated by molecular isomer manipulation. Interestingly, the photoluminescence quantum yields (Φ_PLs) of trans‐isomers T‐DA‐1 and T‐DA‐2 (78% and 89%) are remarkably higher than those of their corresponding cis‐isomers C‐DA‐1 and C‐DA‐2 (12% and 14%). Significantly increased Φ_PL values can be explained by single crystal structures and theoretical simulation. As a result, a deep red TADF‐OLED based on T‐DA‐2 displays a maximum external quantum efficiency (EQE) of 26.26% at 640 nm. Notably, at a brightness of 100 cd m^?2, the EQE value of T‐DA‐2‐based device still remains at an extremely high level of 23.95%, representing the highest value for reported red TADF‐OLEDs at the same brightness. These results provide a reasonable pathway to optimize optoelectronic properties and thereby construct efficient red TADF emitters through rational isomer engineering.     

Rational Molecular Design for Deep‐Blue Thermally Activated Delayed Fluorescence Emitters

By simple modification of the functional groups on the donor unit, the thermally activated delayed fluorescence (TADF) properties of emitters can easily be manipulated. A series of deep blue to blue emissive TADF derivatives is developed, capable of deep‐blue emissions from 403 to 460 nm in toluene. Deep‐blue organic light‐emitting diodes (OLEDs) based on this series of TADF emitters are fabricated, resulting in an electroluminescence peak at 428 nm and a high external quantum efficiency of up to 10.3%. One deep‐blue OLED has achieved the commission internationale de l'eclairage (CIE) coordinates of (0.156, 0.063), which is among the best reported TADF performances for deep‐blue OLEDs with CIE_y < 0.07.     

Design Strategy of Blue and Yellow Thermally Activated Delayed Fluorescence Emitters and Their All‐Fluorescence White OLEDs with External Quantum Efficiency beyond 20%

Two thioxanthone‐derived isomeric series of thermally activated delayed fluorescence (TADF) emitters 1,6‐2TPA‐TX/3,6‐2TPA‐TX and 1,6‐2TPA‐TXO/3,6‐2TPA‐TXO are developed for organic light‐emitting diodes (OLEDs). Blue emission devices based on symmetrical 3,6‐2TPA‐TX with common vertical transition route realize an extremely high external quantum efficiency (EQE) of 23.7%, and an ever highest EQE of 24.3% is achieved for yellow emission devices based on 3,6‐2TPA‐TXO by solely changing the sulfur atom valence state of the thioxanthone core. In contrast, their corresponding asymmetric isomers are affected by intramolecular energy transfer and more severely by a nonradiative deactivation pathway, to give much low EQE values (<5%). By utilizing 3,6‐2TPA‐TX as a blue emitter and 3,6‐2TPA‐TXO as a yellow emitter, an ever highest EQE of 20.4% is achieved for all‐fluorescence white OLEDs.     

Deep‐Red/Near‐Infrared Electroluminescence from Single‐Component Charge‐Transfer Complex via Thermally Activated Delayed Fluorescence Channel

Formation of a single‐component charge‐transfer complex (SCCTC) is unveiled in solid state of an intermolecular charge‐transfer molecule 2‐(4‐(1‐phenyl‐1H‐phenanthro[9,10‐d]imidazol‐2‐yl)phenyl)anthracene‐9,10‐dione (PIPAQ). Intermolecular donor–acceptor interactions between two PIPAQ molecules is the primary driving force for self‐association and contributes to intermolecular charge transfer. The SCCTC character is fully verified by crystallographic, photophysical, electron spin resonance, and vibrational characterizations. The PIPAQ‐based SCCTC is first applied in light‐emitting devices as an emissive layer to realize efficient deep‐red/near‐infrared electroluminescence. This work provides new insights into SCCTC and represents an important step toward their applications in optoelectronic devices.     

Crosslinkable TAPC‐Based Hole‐Transport Materials for Solution‐Processed Organic Light‐Emitting Diodes with Reduced Efficiency Roll‐Off

1‐Bis[4‐[N,N‐di(4‐tolyl)amino]phenyl]‐cyclohexane (TAPC) has been widely used in xerography and organic light‐emitting diodes (OLEDs), but derivatives are little known. Here, a new series of solution‐processable, crosslinkable hole conductors based on TAPC with varying highest occupied molecular orbital (HOMO) energies from ?5.23 eV to ?5.69 eV is implemented in blue phosphorescent OLEDs. Their superior perfomance compared with the well‐known N4,N4,N4′,N4′‐tetraphenylbiphenyl‐4,4′‐diamine (TPDs) analogues regarding hole‐injection and mobility, electron and exciton blocking capabilities, efficiency, and efficiency roll‐off is demonstrated. Overall, the TAPC‐based devices feature higher luminous and power efficiency over a broader range of brightness levels and reduced efficiency roll off. A systematic broadening of the emission zone is observed as the hole‐injection barrier between the anode and the hole‐transporting layer increased.     

A Red Thermally Activated Delayed Fluorescence Emitter Simultaneously Having High Photoluminescence Quantum Efficiency and Preferentially Horizontal Emitting Dipole Orientation

The development of red thermally activated delayed fluorescence (TADF) emitters having excellent optoelectronic properties and satisfactory electroluminescence efficiency is full of challenges due to strict molecular design principles. Two red TADF molecules, 3‐(9,9‐dimethylacridin‐10(9H)‐yl)acenaphtho[1,2‐b]quinoxaline‐9,10‐dicarbonitrile and 3‐(2,7‐dimethyl‐10H‐spiro[acridine‐9,9′‐fluoren]‐10‐yl)acenaphtho[1,2‐b]quinoxaline‐9,10‐dicarbonitrile, are developed by adopting a donor–acceptor molecular architecture bearing an electron‐accepting acenaphtho[1,2‐b]quinoxaline‐9,10‐dicarbonitrile (ANQDC) moiety and a 9,9‐dimethyl‐9,10‐dihydroacridine or 2,7‐dimethyl‐10H‐spiro[acridine‐9,9′‐fluorene] electron donor. The combined effects of rigid and planar D/A moieties and highly steric hindrance between D and A groups endow both molecules with high rigidity to suppress nonradiative decay processes, resulting in high photoluminescence quantum efficiencies (Φ_PLs) of up to 95%. Attributed to the linear and planar acceptor motif and rod‐like molecular configuration, both emitters achieve high horizontal ratios of emitting dipole orientation of ≈80%. The organic light‐emitting diodes (OLEDs) based on both emitters exhibit red emissions peaking at ≈615 nm and successfully afford ultrahigh electroluminescence performance with an external quantum efficiency of nearly 28% and a power efficiency of above 50 lm W^?1, on par with the state‐of‐the‐art device efficiency for red TADF OLEDs. This presents a feasible design strategy for excellent TADF emitters simultaneously possessing high Φ_PLs and horizontally aligned emitting dipoles.     

Ultra-Deep-Blue Aggregation-Induced Delayed Fluorescence Emitters: Achieving Nearly 16% EQE in Solution-Processed Nondoped and Doped OLEDs with CIEy < 0.1

Ultra-deep-blue aggregation-induced delayed fluorescence (AIDF) emitters (TB-tCz and TB-tPCz) bearing organoboron-based cores as acceptors and 3,6-substituted carbazoles as donors are presented. The thermally activated delayed fluorescence (TADF) properties of the two emitters are confirmed by theoretical calculations and time-resolved photoluminescence experiments. TB-tCz and TB-tPCz exhibit fast reverse intersystem crossing rate constants owing to efficient spin–orbit coupling between the singlet and triplet states. When applied in solution-processed organic light-emitting diodes (OLEDs), the TB-tCz- and TB-tPCz-based nondoped devices exhibit ultra-deep-blue emissions of 416–428 nm and high color purity owing to their narrow bandwidths of 42.2–44.4 nm, corresponding to the Commission International de l´Eclairage color coordinates of (x = 0.16–0.17, y = 0.05–0.06). They show a maximum external quantum efficiency (EQE_max) of 8.21% and 15.8%, respectively, exhibiting an unprecedented high performance in solution-processed deep-blue TADF-OLEDs. Furthermore, both emitters exhibit excellent device performances (EQE_max = 14.1–15.9%) and color purity in solution-processed doped OLEDs. The current study provides an AIDF emitter design strategy to implement high-efficiency deep-blue OLEDs in the future.     

High‐Performance Dibenzoheteraborin‐Based Thermally Activated Delayed Fluorescence Emitters: Molecular Architectonics for Concurrently Achieving Narrowband Emission and Efficient Triplet–Singlet Spin Conversion

Thermally activated delayed fluorescence (TADF) materials, which enable the full harvesting of singlet and triplet excited states for light emission, are expected as the third‐generation emitters for organic light‐emitting diodes (OLEDs), superseding the conventional fluorescence and phosphorescence materials. High photoluminescence quantum yield (Φ_PL), narrow‐band emission (or high color purity), and short delayed fluorescence lifetime are all strongly desired for practical applications. However, to date, no rational design strategy of TADF emitters is established to fulfill these requirements. Here, an epoch‐making design strategy is proposed for producing high‐performance TADF emitters that concurrently exhibiting high Φ_PL values close to 100%, narrow emission bandwidths, and short emission lifetimes of ≈1 µs, with a fast reverse intersystem crossing rate of over 10⁶ s^?1. A new family of TADF emitters based on dibenzoheteraborins is introduced, which enable both doped and non‐doped TADF‐OLEDs to achieve markedly high external electroluminescence quantum efficiencies, exceeding 20%, and negligible efficiency roll‐offs at a practical high luminance. Systematic photophysical and theoretical investigations and device evaluations for these dibenzoheteraborin‐based TADF emitters are reported here.     

Achieving High‐Performance Nondoped OLEDs with Extremely Small Efficiency Roll‐Off by Combining Aggregation‐Induced Emission and Thermally Activated Delayed Fluorescence

Luminescent materials with thermally activated delayed fluorescence (TADF) can harvest singlet and triplet excitons to afford high electroluminescence (EL) efficiencies for organic light‐emitting diodes (OLEDs). However, TADF emitters generally have to be dispersed into host matrices to suppress emission quenching and/or exciton annihilation, and most doped OLEDs of TADF emitters encounter a thorny problem of swift efficiency roll‐off as luminance increases. To address this issue, in this study, a new tailor‐made luminogen (dibenzothiophene‐benzoyl‐9,9‐dimethyl‐9,10‐dihydroacridine, DBT‐BZ‐DMAC) with an unsymmetrical structure is synthesized and investigated by crystallography, theoretical calculation, spectroscopies, etc. It shows aggregation‐induced emission, prominent TADF, and interesting mechanoluminescence property. Doped OLEDs of DBT‐BZ‐DMAC show high peak current and external quantum efficiencies of up to 51.7 cd A^?1 and 17.9%, respectively, but the efficiency roll‐off is large at high luminance. High‐performance nondoped OLED is also achieved with neat film of DBT‐BZ‐DMAC, providing excellent maxima EL efficiencies of 43.3 cd A^?1 and 14.2%, negligible current efficiency roll‐off of 0.46%, and external quantum efficiency roll‐off approaching null from peak values to those at 1000 cd m^?2. To the best of the authors' knowledge, this is one of the most efficient nondoped TADF OLEDs with small efficiency roll‐off reported so far.     

“Trade‐Off” Hidden in Condensed State Solvation: Multiradiative Channels Design for Highly Efficient Solution‐Processed Purely Organic Electroluminescence at High Brightness

Actualizing highly efficient solution‐processed thermally activated delayed fluorescent (TADF) organic light‐emitting diodes (OLEDs) at high brightness becomes significant to the popularization of purely organic electroluminescence. Herein, a highly soluble emitter benzene‐1,3,5‐triyltris((4‐(9,9‐dimethylacridin‐10(9H)‐yl)phenyl)methanone was developed, yielding high delayed fluorescence rate (k_TADF > 10⁵ s^?1) ascribed to the multitransition channels and tiny singlet–triplet splitting energy (ΔE_ST ≈ 32.7 meV). The triplet locally excited state is 0.38 eV above the lowest triplet charge‐transfer state, assuring a solely thermal equilibrium route for reverse intersystem crossing. Condensed state solvation effect unveils a hidden “trade‐off”: the reverse upconversion and triplet concentration quenching processes can be promoted but with a reduced radiative rate from the increased dopant concentration and the more polarized surroundings. Striking a delicate balance, corresponding vacuum‐evaporated and solution‐processed TADF‐OLEDs realized maximum external quantum efficiencies (EQEs) of ≈26% and ≈22% with extremely suppressed efficiency roll‐off. Notably, the wet‐processed one achieves to date the highest EQEs of 20.7%, 18.5%, 17.1%, and 13.6%, among its counterparts at the luminance of 1000, 3000, 5000, and 10 000 cd m^?2, respectively.     

Thermally Activated Delayed Fluorescence Material as Host with Novel Spiro‐Based Skeleton for High Power Efficiency and Low Roll‐Off Blue and White Phosphorescent Devices

Efficiency roll‐off in blue organic light‐emitting diodes especially at high brightness still remains a vital issue for which the excitons density‐dependent mechanism of host materials takes most responsibility. Additionally, the efficiency roll‐off leads to high power consumption and reduces the operating lifetime because higher driving voltage and current are required. Here, by subtly modifying the triphenylamine to oxygen‐bridged quasi‐planar structure, a novel thermally activated delayed fluorescence type blue host Tri‐o‐2PO is successfully developed. Efficiency roll‐off based on Tri‐o‐2PO is ultralow with external quantum efficiency (EQE) just dropping by around 2% in the high luminance range from 1000 cd m^?2 to 10 000 cd m^?2. As expected, low turn‐on voltage (≈2.9 V) of device is also achieved, which is close to the theory limit value (≈2.62 V). Super‐high power efficiency (≈60 lm W^?1) and EQE (>22%) are also achieved when utilizing Tri‐o‐2PO as host. Furthermore, two‐color warm‐white light with CIE of (0.45, 0.43) and correlated color temperature of 2921 K is also fabricated and a champion EQE of 21% is delivered. These excellent performances prove the strategy of bridging the triphenylamine to reduce ΔE_st is validated and suggest the great potential of this novel skeleton.     

Charge‐Transfer Exciton Manipulation Based on Hydrogen Bond for Efficient White Thermally Activated Delayed Fluorescence

Despite the success of thermally activated delayed fluorescence (TADF) emitters in monochromatic organic light‐emitting diodes (OLED), only few efficient full‐TADF white OLEDs (WOLED) are reported because of the challenge in rational exciton allocation between blue and other color emitters. Herein, it is demonstrated that the appropriate exciton delocalization in blue TADF matrixes can simultaneously support the sufficient blue emission and the energy loss–free charge and exciton transfer to yellow TADF emitters. Through introducing steric hindrance–modulated intermolecular hydrogen bond networks, a fluorinated carbazole‐phosphine oxide hybrid realizes the balance of exciton localization and delocalization, giving rise to state‐of‐the‐art external quantum efficiency beyond 20% from its simple trilayer full‐TADF WOLEDs, accompanied by excellent spectral stability. The correlation between the efficiencies of the blue TADF matrixes and their intermolecular interactions reveals that the exciton delocalization is crucial for the exciton allocation optimization in multicomponent emission systems.