2,3-Disubstituted Fluorene Scaffold for Efficient Green Phosphorescent Organic Light-Emitting Diodes

Fluorene is a classic three-membered polycyclic aromatic hydrocarbon, and it has been widely used in optoelectronic devices. Here we explore a simple and efficient strategy for the derivatization at the 2- and 3- positions in fluorene unit. By introducing different types of substituents, we design two pairs of 2,3-disubstituted fluorene isomers and use them as host materials for phosphorescent organic light-emitting diodes (PHOLEDs). The green PHOLEDs hosted by these fluorene derivatives realize high external quantum efficiencies (EQE) over 20 % with low efficiency roll-off. Particularly, the devices hosted by 2TRz3TPA and 2TPA3TRz achieve nearly 24 % EQE and 104 lm W⁻¹ power efficiency. These results clearly demonstrate that the 2,3-disubstituted fluorene platforms are potentially useful for constructing host materials.     

Peripherally Heavy-Atom-Decorated Strategy Towards High-Performance Pure Green Electroluminescence with External Quantum Efficiency over 40 %

Heavy-atom integration into thermally activated delayed fluorescence (TADF) molecule could significantly promote the reverse intersystem crossing (RISC) process. However, simultaneously achieving high efficiency, small roll-off, narrowband emission and good operational lifetime remains a big challenge for the corresponding organic light-emitting diodes (OLEDs). Herein, we report a pure green multi-resonance TADF molecule BN-STO by introducing a peripheral heavy atom selenium onto the parent BN-Cz molecule. The organic light-emitting diode device based on BN-STO exhibited state-of-the-art performance with a maximum external quantum efficiency (EQE) of 40.1 %, power efficiency (PE) of 176.9 lm W⁻¹, well-suppressed efficiency roll-off and pure green gamut. This work reveals a feasible strategy to reach a balance between fast RISC process and narrow full width at half maximum (FWHM) of MR-TADF by heavy atom effect.     

Tailored Design of π-Extended Multi-Resonance Organoboron using Indolo[3,2-b]Indole as a Multi-Nitrogen Bridge

Extending the π-skeletons of multi-resonance (MR) organoboron emitters can feasibly modulate their optoelectronic properties. Here, we first adopt the indolo[3,2-b]indole (32bID) segment as a multi-nitrogen bridge and develop a high-efficiency π-extended narrowband green emitter. This moiety establishes not only a high-yield one-shot multiple Bora–Friedel–Crafts reaction towards a π-extended MR skeleton, but a compact N-ethylene-N motif for a red-shifted narrowband emission. An emission peak at 524 nm, a small full width at half maximum of 25 nm and a high photoluminescence quantum yield of 96 % are concurrently obtained in dilute toluene. The extended molecular plane also results in a large horizontal emitting dipole orientation ratio of 87 %. A maximum external quantum efficiency (EQE) of 36.6 % and a maximum power efficiency of 135.2 lm/W are thereafter recorded for the corresponding device, also allowing a low efficiency roll-off with EQEs of 34.5 % and 28.1 % at luminance of 1,000 cd/m² and 10,000 cd/m², respectively.     

Acridone-Based Host Materials for Green Phosphorescent and Thermally Activated Delayed Fluorescent OLEDs with Low-Efficiency Roll-Offs

By linking the carbazole unit to the nitrogen atom of acridone through phenyl or pyridyl, two compounds, named 10-(4-(9H-carbazol-9-yl)phenyl)acridin-9(10H)-one (AC-Ph-Cz) and 10-(5-(9H-carbazol-9-yl)pyridin-2-yl)acridin-9(10H)-one (AC-Py-Cz) were designed and synthesized. These two materials, characterized with highly twisted and rigid structure, good thermal stability, and balanced carrier-transporting properties, were employed as host materials for green phosphorescent and thermally activated delayed fluorescent organic light-emitting diodes (OLEDs). The carbazole group, despite its small contribution to the highest occupied molecular orbitals (HOMOs) of these two materials, plays an essential role as an intramolecular host in energy delivering and improving the hole transporting ability of these two hosts. The incorporation of the electron-deficient pyridyl group as a linking group slightly improves the electron transporting capability of AC-Py-Cz. The green phosphorescent OLED (PhOLED) based on AC-Py-Cz exhibited excellent device performance with a turn-on voltage of 2.5 V, a maximum power efficiency and an external quantum efficiency (η_ext) of 89.8 lm W⁻¹ and 25.2 %, respectively, benefitting from the better charge-balancing ability of AC-Py-Cz host due to the presence of the pyridyl bridge. More importantly, all the devices based on these two hosts showed low efficiency roll-off at high brightness due to the suppressed non-radiative transition in the emitting layer. In particular, the AC-Py-Cz-hosted green PhOLED exhibited an efficiency roll-off of 1.6 % from the maximum next at a high brightness of 1000 cd m⁻² and a roll-off of 15.9 % at an extremely high brightness of 10000 cd m⁻². This study manifests that acridone-based host materials have great potential in fabricating OLEDs with low efficiency roll-off.     

Efficient deep blue OLEDs with extremely low efficiency roll-off at high brightness based on phenanthroimidazole derivatives

Phosphorescent and thermally activated delayed fluorescence(TADF) emitters can break through the spin statistics rules and achieve great success in external quantum efficiency(over 5%).However,maintaining high efficiency at high brightness is a tremendous challenge for applications of organic light emitting diodes.Hence,we reported two phenanthroimidazole derivatives PPI-An-CN and PPI-An-TP and achieved extremely low efficiency roll-off with about 99% of the maximum external quantum efficiency(EQE_(max)) maintained even at a high luminance of 1000 cd/cm2 based non-doped devices.When doping the two materials in CBP(4,4'-bis(N-carbazolyl)-1,1'-biphenyl),the doped devices still exhibited excellent stability at high brightness with CIE_y≈0.07 and low turn-on voltage of only 2.8 V.The state-ofthe-art low efficiency roll-off makes the new materials attractive for potential applications.It is the first time that the Fragment Contribution Analysis method has been used to analyze the excited state properties of the molecules in the field of OLEDs,which helps us understand the mechanism more intuitively and deeply.     

Selective Introduction of Carbazole and Diphenylamine into Spirofluorenexanthene Core for Different Phosphorescent Hosts

Built on the spiro[fluorene‐9,9′‐xanthene] (SFX) core and two frequently‐used hole‐transporting groups such as carbazole and diphenylamine, two SFX derivatives, namely SFXCz and SFXDPA, have been synthesized by one‐step reaction for red, green and blue phosphorescent organic light‐emitting devices (PHOLEDs). Though the properties of these two groups are very similar, the devices based on SFXCz and SFXDPA exhibit distinct performances. In blue PHOLEDs, the device based on SFXCz exhibited much better performances than that based on SFXDPA. However, the latter was superior to the former in green and red PHOLEDs. And the red PHOLED based on SFXDPA exhibited maximum current efficiency (CE) of 27.1 cd·A^?1, power efficiency (PE) of 25.0 lm·W^?1, and external quantum efficiency (EQE) of 15.0%. The results show that the introduction of diphenylamine group is suitable for constructing green and red host materials, whereas the introduction of carbazole group is suitable for constructing blue host materials.     

Novel thioxanthone host material with thermally activated delayed fluorescence for reduced efficiency roll-off of phosphorescent OLEDs

A symmetrical host material, 2,7-di(9,9-dimethyl-9H-fluoren-1-yl)-9H-thioxanthen-9-one (DMBFTX), with TADF property was firstly developed. The red phosphorescent OLED based on this TADF host displays a lower EQEs rolloff of 38.8% at a luminance of 10 000 cd/m² as compared to 71.2% of commercial mCP host, which is resulted from the upconversion of DMBFTX from triplet to singlet.     

Efficient Pyrazolo[5,4-f]quinoxaline Functionalized Os(II) Based Emitter with an Electroluminescence Peak Maximum at 811 nm

Upon fusing the pyrazinyl pyrazole entity in giving pyrazolo[3,4-f]quinoxaline chelate, the corresponding Os(II) based NIR emitter exhibited “invisible” and efficient electroluminescence with a peak maximum at 811 nm. A maximum external quantum efficiency of 0.97 % and a suppressed efficiency roll-off till a current density of 300 mA cm⁻² was also exhibited.     

Merging Boron and Carbonyl based MR-TADF Emitter Designs to Achieve High Performance Pure Blue OLEDs**

Multiresonant thermally activated delayed fluorescence (MR-TADF) compounds are attractive as emitters for organic light-emitting diodes (OLEDs) as they can simultaneously harvest both singlet and triplet excitons to produce light in the device and show very narrow emission spectra, which translates to excellent color purity. Here, we report the first example of an MR-TADF emitter (DOBDiKTa) that fuses together fragments from the two major classes of MR-TADF compounds, those containing boron (DOBNA) and those containing carbonyl groups (DiKTa) as acceptor fragments in the MR-TADF skeleton. The resulting molecular design, this compound shows desirable narrowband pure blue emission and efficient TADF character. The co-host OLED with DOBDiKTa as the emitter showed a maximum external quantum efficiency (EQE_max) of 17.4 %, an efficiency roll-off of 32 % at 100 cd m⁻², and Commission Internationale de l’Éclairage (CIE) coordinates of (0.14, 0.12). Compared to DOBNA and DiKTa, DOBDiKTa shows higher device efficiency with reduced efficiency roll-off while maintaining a high color purity, which demonstrates the promise of the proposed molecular design.     

Highly efficient non-doped blue fluorescent OLEDs with low efficiency roll-off based on hybridized local and charge transfer excited state emitters

Designing a donor–acceptor (D–A) molecule with a hybridized local and charge transfer (HLCT) excited state is a very effective strategy for producing an organic light-emitting diode (OLED) with a high exciton utilization efficiency and external quantum efficiency. Herein, a novel twisting D–π–A fluorescent molecule (triphenylamine–anthracene–phenanthroimidazole; TPAAnPI) is designed and synthesized. The excited state properties of the TPAAnPI investigated through photophysical experiments and density functional theory (DFT) analysis reveal that its fluorescence is due to the HLCT excited state. The optimized non-doped blue OLED using TPAAnPI as a light-emitting layer exhibits a novel blue emission with an electroluminescence (EL) peak at 470 nm, corresponding to the Commission International de L''Eclairage (CIE) coordinates of (0.15, 0.22). A fabricated device termed Device II exhibits a maximum current efficiency of 18.09 cd A⁻¹, power efficiency of 12.35 lm W⁻¹, luminescence of ≈29 900 cd cm⁻², and external quantum efficiency (EQE) of 11.47%, corresponding to a high exciton utilization efficiency of 91%. Its EQE remains as high as 9.70% at a luminescence of 1000 cd m⁻² with a low efficiency roll-off of 15%. These results are among the best for HLCT blue-emitting materials involved in non-doped blue fluorescent OLEDs. The performance of Device II highlights a great industrial application potential for the TPAAnPI molecule.

A new pure fluorescent blue HLCT-emitter was designed and synthesized. Highly efficient non-doped blue OLEDs with low efficiency roll-off were achieved.     

Bis-tridentate IrIII Phosphors Bearing Two Fused Five-Six-Membered Metallacycles: A Strategy to Improved Photostability of Blue Emitters

Iridium complexes bearing chelating cyclometalates are popular choices as dopant emitters in the fabrication of organic light-emitting diodes (OLEDs). In this contribution, we report a series of blue-emitting, bis-tridentate Ir^III complexes bearing chelates with two fused five-six-membered metallacycles, which are in sharp contrast to the traditional designs of tridentate chelates that form the alternative, fused five-five metallacycles. Five Ir^III complexes, Px-21 – 23 , Cz-4 , and Cz-5 , have been synthesized that contain a coordinated dicarbene pincer chelate incorporating a methylene spacer and a dianionic chromophoric chelate possessing either a phenoxy or carbazolyl appendage to tune the coordination arrangement. All these tridentate chelates afford peripheral ligand–metal–ligand bite angles of 166–170°, which are larger than the typical bite angle of 153–155° observed for their five-five-coordinated tridentate counterparts, thereby leading to reduced geometrical distortion in the octahedral frameworks. Photophysical measurements and TD-DFT studies verified the inherent transition characteristics that give rise to high emission efficiency, and photodegradation experiments confirmed the improved stability in comparison with the benchmark fac-[Ir(ppy)₃] in degassed toluene at room temperature. Phosphorescent OLED devices were also fabricated, among which the carbazolyl-functionalized emitter Cz-5 exhibited the best performance among all the studied bis-tridentate phosphors, showing a maximum external quantum efficiency (EQE_max) of 18.7 % and CIE_x,y coordinates of (0.145, 0.218), with a slightly reduced EQE of 13.7 % at 100 cd m⁻² due to efficiency roll-off.     

Alignment of Heptagonal Diimide and Triazine Enables Narrowband Pure-Blue Organic Light-Emitting Diodes with Low Efficiency Roll-Off

The endeavor to develop high-performance narrowband blue organic light-emitting diodes (OLEDs) with low efficiency roll-off represents an attractive challenge. Herein, we introduce a hetero-acceptor design strategy centered around the heptagonal diimide (BPI) building block to create an efficient thermally activated delayed fluorescence (TADF) sensitizer. The alignment of a twisted BPI unit and a planar diphenyltriazine (TRZ) fragment imparts remarkable exciton dynamic properties to 26tCz-TRZBPI, including a fast radiative decay rate (k_R) of 1.0×10⁷ s⁻¹ and a swift reverse intersystem crossing rate (k_RISC) of 1.8×10⁶ s⁻¹, complemented by a slow non-radiative decay rate (k_NR) of 6.0×10³ s⁻¹. Consequently, 26tCz-TRZBPI facilitates the fabrication of high-performance narrowband pure-blue TADF-sensitized fluorescence OLEDs (TSF-OLEDs) with a maximum external quantum efficiency (EQE_max) of 24.3 % and low efficiency roll-off even at a high brightness level of 10000 cd m⁻² (EQE₁₀₀₀₀: 16.8 %). This showcases a record-breaking external quantum efficiency at a high luminance level of 10000 cd m⁻² for narrowband blue TSF-OLEDs.     

Polyfluorene presenting dipolar pendent groups and its application to electroluminescent devices

We have synthesized a blue-light-emitting polyfluorene derivative (PF-TPAOXD) that presents sterically hindered, dipolar pendent groups functionalized at the C-9 positions of alternating fluorene units. The incorporation of the dipolar side chains, each comprising an electron-rich triphenylamine group and an electron-deficient oxadiazole group connected through a π-conjugated bridge, endows the resultant polymer with higher highest occupied molecular orbital and lower lowest unoccupied molecular orbital energy levels, which, consequently, lead to an increase in both hole and electron affinities. An electroluminescent device incorporating this polymer as the emitting layer exhibited a stable blue emission with a maximum brightness of 2080 cd/m² at 12 V and a maximum external quantum efficiency of 1.4% at a brightness of 137 cd/m². Furthermore, atomic force microscopy measurements indicated that the dipolar nature of PF-TPAOXD, in contrast to the general nonpolarity of polydialkylfluorenes, provided a stabilizing environment allowing the polar organometallic triplet dopant to be dispersed homogeneously. We also fabricated an electrophosphorescent device incorporating PF-TPAOXD as the host material doped with a red-emitting osmium complex to realize red electroluminescence with Commission Internationale de l'Eclairage color coordinates of (0.66, 0.34). The resulting device exhibited a maximum external quantum efficiency of 7.3% at a brightness of 1747 cd/m² and a maximum brightness of 7244 cd/m². © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2073–2084, 2007     

Molecular Design of Non-doped OLEDs Based on a Twisted Heptagonal Acceptor: A Delicate Balance between Rigidity and Rotatability

The development of efficient non-doped organic light-emitting diodes (OLEDs) is highly desired but very challenging because of a severe aggregation-caused quenching effect. Herein, we present a heptagonal diimide acceptor (BPI), which can restrict excessive intramolecular rotation and inhibit close intermolecular π–π stacking due to well-balanced rigidity and rotatability of heptagonal structure. The BPI-based luminogen ( DMAC-BPI ) shows significant aggregation-induced delayed florescence with an extremely high photoluminescence quantum yield (95.8 %) of the neat film, and the corresponding non-doped OLEDs exhibit outstanding electroluminescence performance with maximum external quantum efficiency as high as 24.7 % and remarkably low efficiency roll-off as low as 1.0 % at 1000 cd m⁻², which represents the state-of-the-art performance for non-doped OLEDs. In addition, the synthetic route to DMAC-BPI is greatly streamlined and simplified through oxidative Ar−H/Ar−H homo-coupling reaction.     

Medium-Ring Strategy Enables Multiple Resonance Emitters with Twisted Geometry and Fast Spin-Flip to Suppress Efficiency Roll-Off

Suppressing aggregation-caused quenching (ACQ) effect and reducing device efficiency roll-off are both crucial yet challenging for multi-resonance (MR) emitters. Herein, we put forward a medium-ring strategy to design efficient MR emitters that feature heptagonal tribenzo[b,d,f]azepine (TBA) donors. The highly twisted conformation enlarges the intermolecular distances between the MR-emitting cores, and thus suppresses ACQ effect. Meanwhile, the introduction of heptagonal donors enhances spin-orbital coupling, so as to accelerate reverse intersystem crossing (RISC) process. This medium-ring strategy gives rise to the first example of blue MR emitter that simultaneously possesses radiative decay rate as fast as 10⁸ s⁻¹ and RISC rate as fast as 10⁶ s⁻¹. Accordingly, DTBA-B2N3 enables to assemble high-performance blue organic light-emitting diodes (OLEDs) with maximum external quantum efficiency (EQE_max) of 30.9 % and alleviated efficiency roll-off (EQE₁₀₀₀: 20.5 %).     

Phosphorescent [3 + 2 + 1] coordinated Ir(iii) cyano complexes for achieving efficient phosphors and their application in OLED devices

A series of neutral [3 + 2 + 1] coordinated iridium complexes bearing tridentate bis-NHC carbene chelates (2,6-bisimidazolylidene benzene), bidentate chelates (C^N ligands, e.g. derivatives of 2-phenylpridine), and monodentate ions (halides and pseudo-halides, such as Br, I, OCN and CN ions) have been systematically designed and synthesized. X-ray single crystal structure characterization revealed that the nitrogen atom in C^N ligands is located trans to the carbon atom in the benzene ring in tridentate chelates, while the coordinating carbon atom in C^N ligands is located trans to the monodentate ligands. Photophysical studies reveal that the C^N ligands play a vital role in tuning the UV absorption and emission properties, while the tridentate bis-NHC carbene chelates influence the lowest absorption band and emission energy when compared to heteroleptic Ir(ppy)2(acac) [i.e. molar absorptivities at ∼450 nm for ppy-OCN and Ir(ppy)2(acac) are 350 M⁻¹ cm⁻¹ and 1520 M⁻¹ cm⁻¹ and emission maximum peaks are at 465 nm and 515 nm respectively]. Among monodentate ligands that the complexes bear, the group containing the cyanide ligand displays higher emission energy, higher photophysical quantum yields, longer triplet lifetimes and better electrochemical and thermal stabilities than those of cyanate and bromide. Particularly, a blue organic light-emitting diode (OLED) based on dfppy-CN exhibited a maximum external quantum efficiency of 22.94% with CIE coordinates of (0.14, 0.24). Furthermore, a small efficiency roll-off of 5.7% was observed for this device at 1000 cd m⁻².

Construction of [3 + 2 + 1] coordinated iridium(iii) cyano complexes for achieving high-efficiency phosphors and their application in blue OLEDs with low efficiency roll-off.     

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.     

Efficient deep blue OLEDs with extremely low efficiency roll-off at high brightness based on phenanthroimidazole derivatives

Local emissions located on the PI moiety and anthracene moiety play a key role in alleviating efficiency roll-off at high Brightness in non-doped and doped devices.     

Rational Molecular Design Overcoming the Long Delayed Fluorescence Lifetime and Serious Efficiency Roll-Off in Blue Thermally Activated Delayed Fluorescent Devices

Blue thermally activated delayed fluorescent (TADF) devices with short excited-state lifetime, high reverse intersystem crossing rate, and low-efficiency roll-off were developed by managing the molecular structure of donor–acceptor-type blue emitters. Three isomers of blue TADF emitters with a diphenyltriazine acceptor and three carbazole donors were synthesized. The position of the donor moieties in the phenyl linker connecting the donor and acceptor moieties was controlled to devise compounds with a short delayed fluorescence lifetime. A blue TADF emitter with three carbazole donors at 2-, 3-, and 4- positions of a phenyl linker shortened the excited state lifetime to 4.1 μs, showed a high external quantum efficiency of 20.4 %, and low efficiency roll-off of less than 10 % at 1000 cd m⁻². Therefore, a molecular design distorting the donors by aligning them in a consecutive way is useful to resolve the issues of long delayed fluorescence lifetime and efficiency roll-off of blue TADF devices.     

Electropolymerized AIE-active polymer film with high quantum efficiency and its application in OLED

A carbazole functionalized electro-active AIE-activity molecule, TPE-DFCz , was designed, synthesized, and well characterized. The clear difference in oxidation potentials between tetraphenylethylene (TPE) unit and carbazole groups was found which guaranteed that polymerization occurred only at the peripheral carbazole groups and the TPE unit remained unchanged. Its luminescent network film was prepared conveniently by electrochemical polymerization (EP). The cross-linked film exhibited green emission with high quantum efficiency of 63%, relatively smooth surface, and good thermal stability. The effect of different scan cycles on the optical property was also investigated. The electroluminescent device using the optimized polymer film as active layer showed a maximum luminance of 3200 cd m⁻² and a maximum luminance efficiency of 1.16 cd A⁻¹ with very low roll-off of the efficiency. The AIE-active EP films afford more opportunities to develop polymer films with high quantum efficiency via a simple, effective method and promote the potential applications in display devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 707–715