Pyrene-fluorene hybrids containing acetylene linkage as color-tunable emitting materials for organic light-emitting diodes

New blue- to yellow-emitting materials have been developed by incorporating fluorene-based chromophores on pyrene core with acetylene linkage and using multifold palladium-catalyzed cross-coupling reactions. Both mono- and tetrasubstituted derivatives have been synthesized and characterized. The tetrasubstituted derivatives displayed red-shifted emission when compared to the monosubstituted derivative indicative of an extended conjugation in the former. End-capping with a diphenylamine unit further red-shifted the absorption and emission profiles and imparted a weak dipolar character to the molecules. Amine-containing derivatives displayed positive solvatochromism in the fluorescence spectra indicating a more polar excited state due to an efficient charge migration from the diphenylamine donor to the pyrene π-acceptor. All of the derivatives were tested as emitting dopants with host material 4,4'-bis(9H-carbazol-9-yl)biphenyl (CBP) in a multilayered OLED and found to exhibit bright blue or yellow electroluminescence. The device utilizing 1,3,6,8-tetrasubstituted pyrene derivative as a dopant emitter displayed highest maximum luminescence 4630 cd/m(2) with power efficiency 3.8 lm/W and current efficiency 7.1 cd/A at 100 cd/m(2) attributable to the proper alignment of energy levels that led to the efficient harvesting of excitons. All of the devices exhibited color purity over a wide range of operating voltages.     

Oligofluorene-based push-pull type functional materials for blue light-emitting diodes

A series of new oligofluorene-based push-pull type blue light-emitting functional materials, namely, 2-(9H-carbazole-9-yl)-7-(4-cyanophenyl)-9,9-dihexylfluorene (F1), 7-(9H-carbazol-9-yl)-7′-(4-cyanophenyl)-2,2′-bi(9,9-dihexylfluorene) (F2), 7-(9H-carbazole-9-yl)-7″-(4-cyanophenyl)-2,2′:7′,2″-ter(9,9-dihexylfluorene) (F3), and 7-(9H-carbazole-9-yl)-7″′-(4-cyanophenyl)-2,2′:7′,2″:7″,2″′-quarter(9,9-dihexylfluorene) (F4) were synthesized and characterized. Their onset decomposition temperatures for the thermal bond cleavage and the glass-transition temperatures were in general increased with increasing number of fluorene units. In dilute toluene solution, the oligofluorenes exhibited main absorption peaks in the range of 343-370 nm, photoluminescence maxima from 403 to 410 nm, and absolute quantum yields (Φ_PLs) of higher than 87%. In contrast, the absorption spectra of these compounds in the thin films had no large differences from those in the solutions except for the slight peak red-shifts (2-8 nm). The main emission maxima of F1, F2, and F3 in the thin films were located at 418-420 nm, while the main emission of F4 was found to be shifted to 446 nm, followed by a shoulder peak at 421 nm. The Φ_PLs of these thin films were estimated in the range of 59.2-68.7%. The existence of the electron-pull and -push end groups could effectively tune the energy levels of the oligofluorenes. By using the organic light emitting device (OLED) configuration of ITO/PEDOT:PSS/oligofluorenes/TPBi/LiF/Al by solution-process, F4 displayed the best performance: the lowest turn-on voltage (4.1 V) and highest maximum luminance (2180 cd/m²) with maximal current efficiency of 1.17 cd/A. When F4 was fabricated into the optimized device of ITO/MoO₃/NPB/CBP:F4(1:4)/TPBi/LiF/Al by vapor deposition, highest brightness of 5135 cd/m² and current efficiency of 1.76 cd/A were achieved with the Commission Internationale de l’Eclairage (CIE) coordinates of (0.16, 0.09).     

Organic host materials for phosphorescent organic light-emitting diodes

Phosphorescent organic light-emitting diodes (PhOLEDs) unfurl a bright future for the next generation of flat-panel displays and lighting sources due to their merit of high quantum efficiency compared with fluorescent OLEDs. This critical review focuses on small-molecular organic host materials as triplet guest emitters in PhOLEDs. At first, some typical hole and electron transport materials used in OLEDs are briefly introduced. Then the hole transport-type, electron transport-type, bipolar transport host materials and the pure-hydrocarbon compounds are comprehensively presented. The molecular design concept, molecular structures and physical properties such as triplet energy, HOMO/LUMO energy levels, thermal and morphological stabilities, and the applications of host materials in PhOLEDs are reviewed (152 references).     

Conjugated asymmetric donor-substituted 1,3,5-triazines: new host materials for blue phosphorescent organic light-emitting diodes

Conjugated asymmetric donor-substituted 1,3,5-triazines (ADTs) have been synthesized by nucleophilic substitution of organolithium catalyzed by [Pd(PPh(3))(4)]. Theoretical and experimental investigations show that ADTs possess high solubility and thermostability, high fluorescent quantum yield (35%), low HOMO (-6.0 eV) and LUMO (-2.8 eV), and high triplet energy (E(T), 3.0 eV) according to the different substitution pattern of triazine. The application as host materials for blue PHOLEDs yielded a maximum current efficiency of 20.9 cd A(-1), a maximum external quantum efficiency of 9.8%, and a brightness of 9671 cd m(-2) at 5.4 V, making ADTs good candidates for optoelectronic devices.     

Organometallic complexes as hole-transporting materials in organic light-emitting diodes

The use of metal complexes fac-tris(1-phenylpyrazolato-N,C(2)('))cobalt(III) [fac-Co(ppz)(3)], fac-tris(2-phenylpyridinato-N,C(2)(') cobalt(III) [fac-Co(ppy)(3)], and [tris[2-((pyrrole-2-ylmethylidene)amino)ethyl]amine]gallium(III) [Ga(pma)] as materials for hole-transporting layers (HTL) in organic light-emitting diodes (OLEDs) is reported. Co(ppz)(3) and Co(ppy)(3) were prepared by following literature procedures and isolated as mixtures of facial (fac) and meridional (mer) isomers. The more stable fac isomers were separated from the unstable mer forms via column chromatography and thermal gradient sublimation. Crystals of fac-Co(ppz)(3) are monoclinic, space group P2(1)/c, with a = 13.6121(12) A, b = 15.5600(12) A, c = 22.9603(17) A, beta = 100.5 degrees, V = 4781.3(7) A(3), and Z = 8. [Tris[2-((pyrrol-2-ylmethylidene)amino)ethyl]amine]gallium [Ga(pma)] was prepared by the reaction of gallium(III) nitrate with the pmaH(3) ligand precursor in methanol. Ga(pma) crystallizes in the cubic space group I3d with cell parameters a = 20.2377(4) A, b = 20.2377(4) A, c = 20.2377(4) A, beta = 90.0 degrees, V = 8288.6(3) A(3), and Z = 16. These cobalt and gallium complexes are pale colored to colorless solids, with optical energy gaps ranging 2.6-3.36 eV. A two-layer HTL/ETL (ETL = electron-transporting layer) device structure using fac-Co(ppz)(3) and fac-Co(ppy)(3) as the HTL does not give efficient electroluminescence. However, the introduction of a thin layer of a hole-transporting material (N,N'-bis(1-naphthyl)-N,N'-diphenylbenzidine, NPD) as an energy "stair-step" and electron/exciton-blocker dramatically improves the device performance. Both fac-Co(ppz)(3) and fac-Co(ppy)(3) devices give external quantum efficiencies higher than 1.0%, with brightness 5000 and 7000 Cd/m(2) at 10 V, respectively. Ga(pma) also functions as an efficient interface layer, giving device performances very similar to those of analogous devices using NPD as the interface layer. Stability tests have been carried out for Co(ppz)(3)/NPD/Alq(3) and Co(ppy)(3)/NPD/Alq(3) devices. While fac-Co(ppy)(3) gave stable OLEDs, the fac-Co(ppz)(3)-based devices had very short lifetimes. On the basis of the experimental results of chemical oxidation of fac-Co(ppz)(3), the major cause for the fast decay of the fac-Co(ppz)(3) device is proposed to be the decomposition of fac-Co(ppz)(3)(+) in the HTL layer during the device operation.     

Progress in small-molecule luminescent materials for organic light-emitting diodes

Organic light-emitting diodes(OLEDs) have been extensively studied since the first efficient device based on small molecular luminescent materials was reported by Tang. Organic electroluminescent material, one of the centerpieces of OLEDs, has been the focus of studies by many material scientists. To obtain high luminosity and to keep material costs low, a few remarkable design concepts have been developed. Aggregation-induced emission(AIE) materials were invented to overcome the common fluorescence-quenching problem, and cross-dipole stacking of fluorescent molecules was shown to be an effective method to get high solid-state luminescence. To exceed the limit of internal quantum efficiency of conventional fluorescent materials, phosphorescent materials were successfully applied in highly efficient electroluminescent devices. Most recently, delayed fluorescent materials via reverse-intersystem crossing(RISC) from triplet to singlet and the "hot exciton" materials based on hybridized local and charge-transfer(HLCT) states were developed to be a new generation of low-cost luminescent materials as efficient as phosphorescent materials. In terms of the device-fabrication process, solution-processible small molecular luminescent materials possess the advantages of high purity(vs. polymers) and low procession cost(vs. vacuum deposition), which are garnering them increasing attention. Herein, we review the progress of the development of small-molecule luminescent materials with different design concepts and features, and also briefly examine future development tendencies of luminescent materials.     

溶液加工型有机电致发光材料与器件研究进展

有机电致发光器件（OLEDs）在平板显示和固体照明领域有着广阔的应用前景,发展十分迅速,已实现了商业化．而可溶液加工的OLEDs采用喷墨打印、卷对卷印刷等低成本方式进行加工,在实现低成本、大面积显示及照明器件等方面具有巨大的应用潜力,引起了广泛关注．实现高效溶液加工型OLEDs的实用性需要在光电材料设计合成及器件制备方法上进一步深入研究．本文总结了发光材料与器件国家重点实验室可溶液加工型OLEDs材料及器件的研究进展．     

Low molecular weight and polymeric heterocyclics as electron transport/hole-blocking materials in organic light-emitting diodes

The use of low molecular weight, oligomeric and polymeric heterocyclics as electron transport/hole-blocking layers in organic light-emitting diodes is reviewed. The most widely applied materials are π-electron deficient heterocyclics carrying imine nitrogen atoms in the aromatic ring, such as 1,3,4-oxadiazoles, 1,2,4-triazoles, 1,3,5-triazines, and 1,4-quinoxalines. Properties such as redox potentials, ionization potential, electron affinity and charge transport mobility of the materials, if known, are taken into consideration to support the electron injection/transport and hole-blocking effectiveness. It can be generalized that heterocyclic moieties with high reduction potential reduce the interface barriers caused by the band offset between organic material and cathode and are most suitable materials for electron injection in organic electroluminescent devices. These materials are generally characterized by high ionization potential values that contribute towards the hole-blocking property. A general comparison of devices and materials is only possible with limitations owing to the variations in device structure, fabrication, electrode materials, emitter materials, etc. © 1998 John Wiley & Sons, Ltd.     

Rare-earth metal 8-hydroxyquinolinate complexes as materials for organic light-emitting diodes

Rare-earth metal 8-hydroxyquinolinates (q) were studied as emission layers for organic light-emitting diodes. Compounds Dyq₃, Tbq₃, and Smq₃ possess weak electroluminescence due to the emission of the ligand, and the electroluminescence of Hoq₃, Tmq₃, and Ybq₃ is due to electronic transitions of the lanthanide ion. The best electroluminescence characteristics were demonstrated by Scq₃ and Yq₃. The power efficiency of the organic light emitter based on ITO/TPD/Scq₃/Yb (ITO is tin-alloyed indium oxide, TPD is N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine) is 2.6 lm W⁻¹ at a luminance of the device of 300 cd m⁻².     

Carbazole compounds as host materials for triplet emitters in organic light-emitting diodes: polymer hosts for high-efficiency light-emitting diodes

A carbazole homopolymer and carbazole copolymers based on 9,9'-dialkyl-[3,3']-bicarbazolyl, 2,5-diphenyl-[1,3,4]-oxadiazole and 9,9-bis(4-[3,7-dimethyloctyloxy]phenyl)fluorene were synthesized and their electrical and photophysical properties were characterized with respect to their application as host in phosphorescent polymer light-emitting diodes. It is shown that the triplet energy of a polymer depends on the specific connections between its building blocks. Without changing the composition of the polymer, its triplet energy can be increased from 2.3 to 2.6 eV by changing the way in which the different building blocks are coupled together. For poly(9-vinylcarbazole) (PVK), a carbazole polymer often used as host for high-energy triplet emitters in polymer light-emitting diodes, a large hole-injection barrier of about 1 eV exists due to the low-lying HOMO level of PVK. For all carbazole polymers presented here, the HOMO levels are much closer to the Fermi level of a commonly used anode such as ITO and/or a commonly used hole-injection layer such as PEDOT:PSS. This makes high current densities and consequently high luminance levels possible at moderate applied voltages in polymer light-emitting diodes. A double-layer polymer light-emitting diode is constructed comprising a PEDOT:PSS layer as hole-injection layer and a carbazole-oxadiazole copolymer doped with a green triplet emitter as emissive layer that shows an efficacy of 23 cd/A independent of current density and light output.     

Through-space charge transfer blue polymers containing acridan donor and oxygen-bridged triphenylboron acceptor for highly efficient solution-processed organic light-emitting diodes

Three kinds of through-space charge transfer(TSCT) blue polymers containing non-conjugated polystyrene backbone together with spatially-separated acridan donor and oxygen-bridged triphenylboron acceptors having different substituents of tert-butyl,hydrogen and fluorine are designed and synthesized. The designed TSCT blue polymers possess photoluminescence quantum yields up to 70% in solid-state film, single-triplet energy splitting below 0.1 eV, and typical thermally activated delayed fluorescence(TADF) effect. Meanwhile, the resulting polymers exhibit aggregation-induced emission(AIE) effect with emission intensity increased by up to ～27 folds from solution to aggregation state. By changing the substituent of acceptors to tune the charge transfer strength, blue emission with peaks from 444 to 480 nm can be realized for the resulting polymers.Solution-processed organic light-emitting diodes based on the polymers exhibit excellent device performance with Commission Internationale de L'Eclairage(CIE) coordinates of(0.16, 0.27), together with the maximum luminous efficiency of 30.7 cd A~(-1) and maximum external quantum efficiency of 15.0%, which is the best device efficiency for blue TADF polymers.     

Fluorene-based copolymers for color-stable blue light-emitting diodes

A series of random conjugated copolymers (PFO-HBT) derived from 9,9-dioctylfluorene (DOF) and 2-hexylbenzotriazole (HBT) is prepared by the palladium-catalyzed Suzuki coupling reaction with the feed HBT molar ratio around 1%, 5% and 15%. By copolymerizing 2-hexylbenzotriazole into the backbone of polyfluorene, an efficient colorfast blue light-emitting polymer system is developed. The device with the structure of ITO (indium tin oxide)/PEDOT/PVK/PFO-HBT1/Ba/Al exhibits the highest external quantum efficiency 1.62% with luminance efficiency of 2.69 cd/A, power efficiency of 1.25 lm/W and the CIE coordinates of (0.15, 0.17). The EL spectra are stable at the increased current density and continuous operation without significant change of CIE.     

Synthesis of phosphorus dendrimers bearing chromophoric end groups: toward organic blue light-emitting diodes

Several series of phosphorus dendrimers decorated by potential fluorescent end groups (naphthalene, anthracene, and pyrene) have been synthesized. Unexpectedly, we found that it is absolutely necessary to link the fluorophore to the dendrimer through an alkyl link, and not directly through heteroelements such as oxygen or nitrogen, in order to preserve the fluorescence. One series of dendrimers from generation 1 (6 pyrene end groups) to generation 4 (48 pyrene end groups) has been tested for the elaboration of organic light-emitting diodes (OLEDs). The threshold voltage for the emission of light is high (over 20 V), however, electroluminescence is observed in all cases.     

Design rules for charge-transport efficient host materials for phosphorescent organic light-emitting diodes

The use of blue phosphorescent emitters in organic light-emitting diodes (OLEDs) imposes demanding requirements on a host material. Among these are large triplet energies, the alignment of levels with respect to the emitter, the ability to form and sustain amorphous order, material processability, and an adequate charge carrier mobility. A possible design strategy is to choose a π-conjugated core with a high triplet level and to fulfill the other requirements by using suitable substituents. Bulky substituents, however, induce large spatial separations between conjugated cores, can substantially reduce intermolecular electronic couplings, and decrease the charge mobility of the host. In this work we analyze charge transport in amorphous 2,8-bis(triphenylsilyl)dibenzofuran, an electron-transporting material synthesized to serve as a host in deep-blue OLEDs. We show that mesomeric effects delocalize the frontier orbitals over the substituents recovering strong electronic couplings and lowering reorganization energies, especially for electrons, while keeping energetic disorder small. Admittance spectroscopy measurements reveal that the material has indeed a high electron mobility and a small Poole-Frenkel slope, supporting our conclusions. By linking electronic structure, molecular packing, and mobility, we provide a pathway to the rational design of hosts with high charge mobilities.     

Quinoline-based aggregation-induced delayed fluorescence materials for highly efficient non-doped organic light-emitting diodes

Three new emitters,namely 10,10'-(quinoline-2,8-diyl)bis(10 H-phenoxazine)(Fene),10,10'-(quinoline-2,8-diyl)bis(10 H-phenothiazine)(Fens) and 10,10'-(quinoline-2,8-diyl)bis(9,9-dimethyl-9,10-dihydroacridine)(Yad),featuring quinoline as a new electron acceptor have been designed and conveniently synthesized.These emitters possessed small singlet-triplet splitting energy(ΔEst) and twisted structures,which not only endowed them show thermally activated delayed fluorescence(TADF)properties but also afforded a remarkable aggregation-induced emission(AIE) feature.Moreover,they also showed aggregation-induced delayed fluorescence(AIDF) property and good photoluminescence(PL) property,which are the ideal emitters for non-doped organic light-emitting diodes(OLEDs).Furthermore,high-performance non-doped OLEDs based on Fene,Fens and Yad were achieved,and excelle nt maximum external quantum efficiencies(EQE_(max)) of 14,9%,13.1% and 17,4%,respectively,were obtained.It was also found that all devices exhibited relatively low turn-on voltages ranging from 3.0 V to3.2 V probably due to their twisted conformation and the AIDF properties.These results demonstrated the quinoline-based emitters could have a promising application in non-doped OLEDs.     

Dendritic macromolecules for organic light-emitting diodes

The general concepts, design criteria, and physical parameters, such as component placement and electroluminescence, that relate to the construction of OLED devices are described, followed by a discussion of the current literature detailing the use of branched and dendritic materials as the key electroluminescent elements of single- and multi-layered fabricated devices. Their configurations, efficiencies, emission intensities, and molecular structural implications are also delineated and discussed. This critical review should appeal to researchers in the synthetic, material, and physical sciences (122 references).     

Planar pn heterojunction organic light-emitting diodes

正Organic light-emitting diodes(OLEDs)are being increasingly applied in flat-panel displays,such as television and mobile phones,and have great potential to become next generation solid-state lighting sources.Along with the     

Phosphorescent dyes for organic light-emitting diodes

This article presents general concepts that have guided important developments in our recent research progress regarding room-temperature phosphorescent dyes and their potential applications. We first elaborate the theoretical background for emissive metal complexes and the strategic design of the chelating C-linked 2-pyridylazolate ligands, followed by their feasibility in functionalization and modification in an aim to fine-tune the chemical and photophysical properties. Subsequently, incorporation of 2-pyridylazolate chromophores is illustrated in the synthesis of the highly emissive, charge-neutral Os, Ru, Ir, and Pt complexes. Insights into their photophysical properties are gained from spectroscopy, relaxation dynamics, and theoretical approaches, from which the lowest-lying excited states, competitive radiative decay, and radiationless processes are then analyzed in detail. In view of applications, their potentials for OLEDs have been evaluated. The results, in combination with the fundamental basis, give a conceptual design contributed to the future advances in the field of OLEDs.