Tri‐Spiral Donor for High Efficiency and Versatile Blue Thermally Activated Delayed Fluorescence Materials

Blue thermally activated delayed fluorescence (TADF) emitters that can simultaneously achieve high efficiency in doped and nondoped organic light‐emitting diodes (OLEDs) are rarely reported. Reported here is a strategy using a tri‐spiral donor for such versatile blue TADF emitters. Impressively, by simply extending the nonconjugated fragment and molecular length, aggregation‐caused emission quenching (ACQ) can be greatly alleviated to achieve as high as a 90 % horizontal orientation dipole ratio and external quantum efficiencies (EQEs) of up to 33.3 % in doped and 20.0 % in nondoped sky‐blue TADF‐OLEDs. More fascinatingly, a high‐efficiency purely organic white OLED with an outstanding EQE of up to 22.8 % was also achieved by employing TspiroS‐TRZ as a blue emitter and an assistant host. This compound is the first blue TADF emitter that can simultaneously achieve high electroluminescence (EL) efficiency in doped, nondoped sky‐blue, and white TADF‐OLEDs.     

A Simple and Strong Electron‐Deficient 5,6‐Dicyano[2,1,3]benzothiadiazole‐Cored Donor‐Acceptor‐Donor Compound for Efficient Near Infrared Thermally Activated Delayed Fluorescence

Despite the success of thermally activated delayed fluorescent (TADF) materials in steering the next generation of organic light‐emitting diodes (OLEDs), effective near infrared (NIR) TADF emitters are still very rare. Here, we present a simple and extremely high electron‐deficient compound, 5,6‐dicyano[2,1,3]benzothiadiazole (CNBz), as a strong electron‐accepting unit to develop a sufficiently strong donor‐acceptor (D?A) interaction for NIR emission. End‐capping with the electron‐donating triphenylamine (TPA) unit created an effective D?A?D type system, giving rise to an efficient NIR TADF emissive molecule (λ_em=750 nm) with a very small ΔE_ST of 0.06 eV. The electroluminescent device using this NIR TADF emitter exhibited an excellent performance with a high maximum radiance of 10020 mW Sr^?1 m^?2, a maximum EQE of 6.57% and a peak wavelength of 712 nm.     

Carbazole Dendrimers as Solution‐Processable Thermally Activated Delayed‐Fluorescence Materials

Recently, thermally activated delayed fluorescence (TADF) materials have received increasing attention as effective emitters for organic light‐emitting diodes (OLEDs). However, most of them are usually employed as dopants in a host material. In this report, carbazole dendrimers with a triphenyl‐s‐triazine core are reported, which are the first solution‐processable, non‐doped, high‐molecular‐weight TADF materials. The dendrimers were obtained by a new and facile synthetic route using the tert‐butyldimethylsilyl moiety as a protecting group. All dendrimers showed TADF in toluene. Measurements of the temperature‐dependent luminescence lifetime revealed that spin‐coated neat films also showed TADF with moderate quantum yields. OLED devices incorporating these dendrimers as spin‐coated emitting layers gave external quantum efficiencies of up to a 3.4 %, which suggests that this device is harvesting triplet excitons. This result indicates that carbazole dendrimers with attached acceptors are potential TADF materials owing to their polarized electronic structure (with HOMO–LUMO separation).     

Highly Efficient Near‐Infrared Delayed Fluorescence Organic Light Emitting Diodes Using a Phenanthrene‐Based Charge‐Transfer Compound

Significant efforts have been made to develop high‐efficiency organic light‐emitting diodes (OLEDs) employing thermally activated delayed fluorescence (TADF) emitters with blue, green, yellow, and orange–red colors. However, efficient TADF materials with colors ranging from red, to deep‐red, to near‐infrared (NIR) have been rarely reported owing to the difficulty in molecular design. Herein, we report the first NIR TADF molecule TPA‐DCPP (TPA=triphenylamine; DCPP=2,3‐dicyanopyrazino phenanthrene) which has a small singlet–triplet splitting (ΔE_ST) of 0.13 eV. Its nondoped OLED device exhibits a maximum external quantum efficiency (EQE) of 2.1 % with a Commission International de L′Éclairage (CIE) coordinate of (0.70, 0.29). Moreover, an extremely high EQE of nearly 10 % with an emission band at λ=668 nm has been achieved in the doped device, which is comparable to the most‐efficient deep‐red/NIR phosphorescent OLEDs with similar electroluminescent spectra.     

Red/Near‐Infrared Thermally Activated Delayed Fluorescence OLEDs with Near 100 % Internal Quantum Efficiency

Developing red thermally activated delayed fluorescence (TADF) emitters, attainable for both high‐efficient red organic light‐emitting diodes (OLEDs) and non‐doped deep red/near‐infrared (NIR) OLEDs, is challenging. Now, two red emitters, BPPZ‐PXZ and mDPBPZ‐PXZ, with twisted donor–acceptor structures were designed and synthesized to study molecular design strategies of high‐efficiency red TADF emitters. BPPZ‐PXZ employs the strictest molecular restrictions to suppress energy loss and realizes red emission with a photoluminescence quantum yield (Φ_PL) of 100±0.8 % and external quantum efficiency (EQE) of 25.2 % in a doped OLED. Its non‐doped OLED has an EQE of 2.5 % owing to unavoidable intermolecular π–π interactions. mDPBPZ‐PXZ releases two pyridine substituents from its fused acceptor moiety. Although mDPBPZ‐PXZ realizes a lower EQE of 21.7 % in the doped OLED, its non‐doped device shows a superior EQE of 5.2 % with a deep red/NIR emission at peak of 680 nm.     

Peripheral Amplification of Multi‐Resonance Induced Thermally Activated Delayed Fluorescence for Highly Efficient OLEDs

Multi‐resonance induced by boron and nitrogen atoms in opposite resonance positions endows a thermally activated delayed fluorescence (MR‐TADF) emitter with a strikingly small full width at half maximum of only 26 nm and excellent photoluminescence quantum yield of up to 97.48 %. The introduction of a carbazole unit in the para position of the B‐substituted phenyl‐ring can significantly boost up the resonance effect without compromising the color fidelity, subsequently enhancing the performances of the corresponding pure blue TADF‐OLED, with an outstanding external quantum efficiency (EQE) up to 32.1 % and low efficiency roll‐off, making it one of the best TADF‐OLEDs in the blue region to date. Furthermore, utilizing this material as host for a yellow phosphorescent emitter, the device also shows a significantly reduced turn‐on voltage of 3.2 V and an EQE_max of 22.2 %.     

Achieving Pure Deep‐Blue Electroluminescence with CIE y≤0.06 via a Rational Design Approach for Highly Efficient Non‐Doped Solution‐Processed Organic Light‐Emitting Diodes

Deep‐blue fluorescent emitters with Commission Internationale de l'Eclairage (CIE) y≤0.06 are urgently needed for high‐density storage, full‐color displays and solid‐state lighting. However, developing such emitters with high color purity and efficiency in solution‐processable non‐doped organic light‐emitting diodes (OLEDs) remains an important challenge. Here, we present the synthesis of two new deep‐blue fluorescent emitters ( AFpTPI and AFmTPI ) based on 10‐(9,9‐diethyl‐9H‐fluoren‐2‐yl)‐9,9‐dimethyl‐9,10‐dihydroacridine as a core and 1,3‐ and/or 1,4‐phenylene‐linked triphenylimidazole (TPI) analogues for non‐doped solution‐processable OLEDs. Their thermal, photophysical, electrochemical, and device characteristics are explored, and also strongly supported by density functional theory (DFT) study. AFpTPI and AFmTPI exhibit excellent thermal stability (≈450 °C) with high glass transition temperatures (T_g; 141–152 °C) and deep‐blue emission with high quantum yields. Specifically, the solution‐processed non‐doped device with AFpTPI as an emitter exhibits a maximum external quantum efficiency (EQE) of 4.56 % with CIE coordinates of (0.15, 0.06), which exactly matches the European Broadcasting Union (EBU) blue standard. In addition, AFmTPI also displays good efficiency and better color purity (EQE: 3.37 %; CIE (0.15, 0.05)). To the best of our knowledge, the present work is the first report on non‐doped solution‐processable OLEDs with efficiency close to 5 % and CIE y≤0.06.     

Constructing a Novel Dendron for a Self‐Host Blue Emitter with Thermally Activated Delayed Fluorescence: Solution‐Processed Nondoped Organic Light‐Emitting Diodes with Bipolar Charge Transfer and Stable Color Purity

Self‐host thermally activated delayed fluorescence (TADF) materials have recently been identified as effective emitters for solution‐processed nondoped organic light‐emitting diodes (OLEDs). However, except for the carbazole unit, few novel dendrons have been developed to build self‐host TADF emitters. This study reports two self‐host blue materials, tbCz‐SO and poCz‐SO, with the same TADF emissive core and different dendrons. The influence of the peripheral dendrons on the photophysical properties and electroluminescent performances of the self‐host materials were systematically investigated. The transient fluorescence and electroluminescence spectra indicated that the diphenylphosphoryl carbazole units could effectively encapsulate the emissive core to reduce the concentration quenching effect and to enhance reverse intersystem crossing. By using tbCz‐SO and poCz‐SO as host‐free blue emitters, the performance of the solution‐processed nondoped OLED device demonstrated that a more balanced charge transfer from the bipolar dendrons would offer a better current efficiency of 10.5 cd A⁻¹ and stable color purity with Commission Internationale de L'Eclairage units of (0.18, 0.27).     

Intermolecular Charge‐Transfer Transition Emitter Showing Thermally Activated Delayed Fluorescence for Efficient Non‐Doped OLEDs

A novel molecular model of connecting electron‐donating (D) and electron‐withdrawing (A) moieties via a space‐enough and conjugation‐forbidden linkage (D‐Spacer‐A) is proposed to develop efficient non‐doped thermally activated delayed fluorescence (TADF) emitters. 10‐(4‐(4‐(4,6‐diphenyl‐1,3,5‐triazin‐2‐yl) phenoxy) phenyl)‐9,9‐dimethyl‐9,10‐dihydroacridine (DMAC‐o‐TRZ) was designed and synthesized accordingly. As expected, it exhibits local excited properties in single‐molecule state as D‐Spacer‐A molecular backbone strongly suppress the intramolecular charge‐transfer (CT) transition. And intermolecular CT transition acted as the vital radiation channel for neat DMAC‐o‐TRZ film. As in return, the non‐doped device exhibits a remarkable maximum external quantum efficiency (EQE) of 14.7 %. These results prove the feasibility of D‐Spacer‐A molecules to develop intermolecular CT transition TADF emitters for efficient non‐doped OLEDs.     

Synthesis and electroluminescent performance of thermally activated delayed fluorescence‐conjugated polymers with simple formylphenyl as pendant acceptor

Formylphenyl has been demonstrated to act as an acceptor to construct thermally activated delayed fluorescence (TADF) emitter, and therefore a series of the TADF‐conjugated polymers with formylphenyl as pendant acceptor and carbazole/acridine as backbone donor are designed and synthesized. All polymers involve the twisted donor/acceptor structural moieties with the sufficiently spatial separation between the highest occupied molecular orbital and the lowest unoccupied molecular orbital as well as a small singlet/triplet splitting, and exhibit the legible TADF features confirmed by theoretical calculation and their transient decay spectra. The solution‐processed organic light‐emitting diodes using neat film of the polymers as emissive layer achieve excellent performance with the maximum external quantum efficiency (EQE) of up to 10.6%, the maximum current efficiency of up to 35.3 cd A⁻¹ and the low turn‐on voltage of 2.7 V. Moreover, the EQE still remains 10.3% at the luminance of 1000 cd m⁻² with the low driving voltage of 4.4 V and extremely small efficiency roll‐off. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1989–1996     

Highly Air‐Stable Electron‐Transport Material for Ink‐Jet‐Printed OLEDs

A novel cross‐linkable electron‐transport material has been designed and synthesized for use in the fabrication of solution‐processed OLEDs. The material exhibits a low LUMO level of ?3.51 eV, a high electron mobility of 1.5×10^?5 cm² V^?1 s^?1, and excellent stability. An average 9.3 % shrinkage in film thickness was observed for the film after thermal curing. A maximum external quantum efficiency (EQE) of 15.6 % (35.0 cd A^?1) was achieved for blue‐phosphorescent OLEDs by spin‐coating and 13.8 % (31.0 cd A^?1) for an ink‐jet‐printed device, both of which are better than the EQE of a control device prepared by vacuum‐deposition (see figure).     

Effect of a Pendant Acceptor on Thermally Activated Delayed Fluorescence Properties of Conjugated Polymers with Backbone‐Donor/Pendant‐Acceptor Architecture

Three sets of conjugated polymers with backbone‐donor/pendant‐acceptor architectures, named PCzA3PyB, PCzAB2Py, and PCzAB3Py, are designed and synthesized. The three isomeric benzoylpyridine‐based pendant acceptor groups are 6‐benzoylpyridin‐3‐yl (3PyB), 4‐((pyridin‐2‐yl)carbonyl)phenyl (B2Py) and 4‐((pyridin‐3‐yl)carbonyl)phenyl (B3Py), whereas the identical backbone consists of 3,6‐carbazolyl and 2,7‐acridinyl rings. One acridine ring and each acceptor group constitute a definite thermally activated delayed fluorescence (TADF) unit, incorporated into the main chain of the polymers through the 2,7‐position of the acridine ring with the varied content. All of the polymers display legible TADF features with a short microsecond‐scale delayed lifetime (0.56–1.62 μs) and a small singlet/triplet energy gap (0.10–0.19 eV). Progressively redshifted emissions are observed in the order PCzAB3Py, PCzA3PyB, and PCzAB2Py owing to the different substitution patterns of the pyridyl group. Photoluminescence quantum yields can be improved by regulating the molar content of the TADF unit in the range 0.5–50 %. The non‐doped organic light‐emitting devices (OLEDs) fabricated by solution‐processing technology emit yellow‐green to orange light. The polymers with 5 mol % of the TADF unit exhibit excellent comprehensive electroluminescence performance, in which PCzAB2Py5 achieves a maximum external quantum efficiency (EQE) of 11.9 %, low turn‐on voltage of 3.0 V, yellow emission with a wavelength of 573 nm and slow roll‐off with EQE of 11.6 % at a luminance of 1000 cd m^?2 and driving voltage of 5.5 V.     

Meta Junction Promoting Efficient Thermally Activated Delayed Fluorescence in Donor‐Acceptor Conjugated Polymers

The meta junction is proposed to realize efficient thermally activated delayed fluorescence (TADF) in donor–acceptor (D‐A) conjugated polymers. Based on triphenylamine as D and dicyanobenzene as A, as a proof of concept, a series of D‐A conjugated polymers has been developed by changing their connection sites. When the junction between D and A is tuned from para to meta, the singlet–triplet energy splitting (ΔE_ST) is found to be significantly decreased from 0.44 to 0.10 eV because of the increasing hole–electron separation. Unlike the para‐linked analogue with no TADF, consequently, the meta‐linked polymer shows a strong delayed fluorescence. Its corresponding solution‐processed organic light‐emitting diodes (OLEDs) achieve a promising external quantum efficiency (EQE) of 15.4 % (51.9 cd A^?1, 50.9 lm W^?1) and CIE coordinates of (0.34, 0.57). The results highlight the bright future of D‐A conjugated polymers used for TADF OLEDs.     

Molecular Design Strategy of Thermally Activated Delayed Fluorescent Emitters Using CN‐Substituted Imidazopyrazine as a New Electron‐Accepting Unit

Thermally activated delayed fluorescence (TADF)‐based organic light‐emitting diodes (OLEDs) have attracted enormous attention recently due to their capability to replace conventional phosphorescent organic light‐emitting diodes for practical applications. In this work, a newly designed CN‐substituted imidazopyrazine moiety was utilized as an electron‐accepting unit in a TADF emitter. Two TADF emitters, 8‐(3‐cyano‐4‐(9,9‐dimethylacridin‐10(9H)‐yl)phenyl)‐2‐phenylimidazo[1,2‐a]pyrazine‐3‐carbonitrile (Ac‐CNImPyr) and 8‐(3‐cyano‐4‐(10H‐phenoxazin‐10‐yl)phenyl)‐2‐phenylimidazo[1,2‐a]pyrazine‐3‐carbonitrile (PXZ‐CNImPyr), were developed based on the CN‐substituted imidazopyrazine acceptor combined with acridine and phenoxazine donor, respectively. A CN‐substituted phenyl spacer was introduced between the donor and acceptor for a sufficiently small singlet‐triplet energy gap (ΔE_ST) and molecular orbital management. Small ΔE_ST of 0.07 eV was achieved for the phenoxazine donor‐based PXZ‐CNImPyr emitter. As a result, an organic light‐emitting diode based on the PXZ‐CNImPyr emitter exhibited a high external quantum efficiency of up to 12.7 %, which surpassed the EQE limit of common fluorescent emitters. Hence, the CN‐modified imidazopyrazine unit can be introduced as a new acceptor for further modifications to develop efficient TADF‐based OLEDs.     

Strongly Luminescent Tungsten Emitters with Emission Quantum Yields of up to 84 %: TADF and High‐Efficiency Molecular Tungsten OLEDs

Metal‐TADF (thermally activated delayed fluorescence) emitters hold promise in the development of next generation light‐emitting materials for display and lighting applications, examples of which are, however, largely confined to Cu^I and recently Au^I, Ag^I, and Au^III emitters. Herein is described the design strategy for an unprecedented type of metal‐TADF emitter based on inexpensive tungsten metal chelated with Schiff base ligand that exhibit high emission quantum yields of up to 56 % in solutions and 84 % in thin‐film (5 wt % in 1,3‐bis(N‐carbazolyl)benzene, mCP) at room temperature. Femtosecond time‐resolved emission (fs‐TRE) spectroscopy and DFT calculations were undertaken to decipher the TADF properties. Solution‐processed OLEDs fabricated with the W‐TADF emitter demonstrated external quantum efficiency (EQE) and luminance of up to 15.6 % and 16890 cd m^?2, respectively.     

Multi-Resonance Building-Block-Based Electroluminescent Material: Lengthening Emission Maximum and Shortening Delayed Fluorescence Lifetime

Multi-resonance thermally activated delayed fluorescence (MR-TADF) materials are considered a class of organic materials with exceptional electronic and optical properties, which make them promising for the applications in organic light-emitting diodes (OLEDs). In this study, we improved, synthesized, and characterized a multiple-resonance type emitter based on the assembly of MR-building blocks (MR-BBs). By optimizing the geometric arrangement of MR-BBs, we were able to generate narrowband emission in the longer wavelength region and shorten the delayed excited-state lifetime, resulting in improved emission efficiency compared to the parent molecule. Our proof-of-concept molecule, m-DBCz, exhibited narrowband yellowish-green TADF emission with a full width at half-maximum of 32 nm and a small singlet-triplet energy gap of 0.04 eV. The OLED developed using m-DBCz as the emitter demonstrated electroluminescence at 548 nm and achieved a high external quantum efficiency (EQE) of 34.9 %. Further optimization of the device resulted in a high external quantum efficiency of 36.3 % and extremely low efficiency roll-off, with EQE values of 30.1 % and 27.7 % obtained even at high luminance levels of 50 000 and 100 000 cd m⁻². These results demonstrate the full potential of MR-TADF materials for applications on ultrahigh-luminance OLEDs.     

High‐Performance Non‐doped OLEDs with Nearly 100 % Exciton Use and Negligible Efficiency Roll‐Off

Non‐doped organic light‐emitting diodes (OLEDs) possess merits of higher stability and easier fabrication than doped devices. However, luminescent materials with high exciton use are generally unsuitable for non‐doped OLEDs because of severe emission quenching and exciton annihilation in neat films. Herein, we wish to report a novel molecular design of integrating aggregation‐induced delayed fluorescence (AIDF) moiety within host materials to explore efficient luminogens for non‐doped OLEDs. By grafting 4‐(phenoxazin‐10‐yl)benzoyl to common host materials, we develop a series of new luminescent materials with prominent AIDF property. Their neat films fluoresce strongly and can fully harvest both singlet and triplet excitons with suppressed exciton annihilation. Non‐doped OLEDs of these AIDF luminogens exhibit excellent luminance (ca. 100000 cd m^?2), outstanding external quantum efficiencies (21.4–22.6 %), negligible efficiency roll‐off and improved operational stability. To the best of our knowledge, these are the most efficient non‐doped OLEDs reported so far. This convenient and versatile molecular design is of high significance for the advance of non‐doped OLEDs.     

Acridan‐Grafted Poly(biphenyl germanium) with High Triplet Energy,Low Polarizability,and an External Heavy‐Atom Effect for Highly Efficient Sky‐Blue TADF Electroluminescence

We propose the novel σ–π conjugated polymer poly(biphenyl germanium) grafted with two electron‐donating acridan moieties on the Ge atom for use as the host material in a polymer light‐emitting diode (PLED) with the sky‐blue‐emitting thermally activated delayed fluorescence (TADF) material DMAC‐TRZ as the guest. Its high triplet energy (E_T) of 2.86 eV is significantly higher than those of conventional π–π conjugated polymers (E_T=2.65 eV as the limit) and this guest emitter (E_T=2.77 eV). The TADF emitter emits bluer emission than in other host materials owing to the low orientation polarizability of the germanium‐based polymer host. The Ge atom also provides an external heavy‐atom effect, which increases the rate of reverse intersystem crossing in this TADF guest, so that more triplet excitons are harvested for light emission. The sky‐blue TADF electroluminescence with this host/guest pair gave a record‐high external quantum efficiency of 24.1 % at maximum and 22.8 % at 500 cd m^?2.     

Acridan‐Grafted Poly(biphenyl germanium) with High Triplet Energy,Low Polarizability,and an External Heavy‐Atom Effect for Highly Efficient Sky‐Blue TADF Electroluminescence

We propose the novel σ–π conjugated polymer poly(biphenyl germanium) grafted with two electron‐donating acridan moieties on the Ge atom for use as the host material in a polymer light‐emitting diode (PLED) with the sky‐blue‐emitting thermally activated delayed fluorescence (TADF) material DMAC‐TRZ as the guest. Its high triplet energy (E_T) of 2.86 eV is significantly higher than those of conventional π–π conjugated polymers (E_T=2.65 eV as the limit) and this guest emitter (E_T=2.77 eV). The TADF emitter emits bluer emission than in other host materials owing to the low orientation polarizability of the germanium‐based polymer host. The Ge atom also provides an external heavy‐atom effect, which increases the rate of reverse intersystem crossing in this TADF guest, so that more triplet excitons are harvested for light emission. The sky‐blue TADF electroluminescence with this host/guest pair gave a record‐high external quantum efficiency of 24.1 % at maximum and 22.8 % at 500 cd m^?2.     

Dibenzo[a,j]phenazine‐Cored Donor–Acceptor–Donor Compounds as Green‐to‐Red/NIR Thermally Activated Delayed Fluorescence Organic Light Emitters

A new family of thermally activated delayed fluorescence (TADF) emitters based on U‐shaped D‐A‐D architecture with a novel accepting unit has been developed. All investigated compounds have small singlet‐triplet energy splitting (ΔE_ST) ranging from 0.02 to 0.20 eV and showed efficient TADF properties. The lowest triplet state of the acceptor unit plays the key role in the TADF mechanism. OLEDs fabricated with these TADF emitters achieved excellent efficiencies up to 16 % external quantum efficiency (EQE).