Synthesis and characterization of high Tg carbazole-based amorphous hole-transporting materials for organic light-emitting devices

Novel hole-transporting materials based on carbazole dendrimers, namely G1CBC and G2CBC were synthesized and characterized. They are thermally stable with high glass transition temperatures (T_g) up to 245 °C and exhibit chemically-stable redox processes. Double-layer green OLEDs using these materials as the hole-transporting layer (HTL) with the device configuration of ITO/HTL/Alq3/LiF:Al emit brightly (λ_em 522-534 nm) from the Alq3 layer with a maximum luminance and low turn-on voltage of 15,890 cd/m² and 3.0 V, respectively. Their ability as HTLs in terms of device performance is comparable to the common hole-transporter N,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,1′-biphenyl)-4,4′-diamine (NPB), however their thermal properties were far greater than both NPB and N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)benzidine (TPD).     

Synthesis and properties of novel hole-transporting materials with triphenylamine units

Two novel organic hole-transporting materials have been synthesized by combination of triphenylamines(TPA) viaπ-conjugated bonds using Wittig reaction.The structures were characterized by NMR,FT-IR and HRMS.The optical,electrochemical and thermal properties of the materials were studied in detail.The results show that these two compounds have blue emission,proper HOMO levels and high thermal stability.Furthermore,a quantum chemical calculation on electron distribution of the two compounds was performed, which suggests the current synthesized materials would be promising candidates for hole-transporting materials.     

Triphenylamine and quinoline-containing polyfluorene for blue light-emitting diodes

A novel blue light-emitting polyfluorene-based copolymer PTHD containing electron-rich triphenylamine and electron-poor phenylquinoline side chains in the C-9 position of fluorene unit is described. By comparison of the solution and thin film photoluminescence (PL) spectra of PTHD, a considerable red-shift of Δλ = 10-15 nm was observed in the thin film PL spectrum. The emission intensity of the shoulder peak appeared in dilute solution was also significantly enhanced in the thin film. In contrast to the reference polymer poly{[9,9-dihexylfluorene]-alt-[9,9-di(2,4-diphenylquinoline)fluorene]}, PTHD exhibits higher HOMO energy level, and higher maximum brightness with the PLED device configuration of ITO/PEDOT:PSS/polymer_70% + PBD_30%/TPBI/LiF/Al.     

Novel linear and tri-branched copolymers based on triphenylamine for non-doping emitting materials

Novel linear and tri-branched copolymers with triphenylamine and cyano groups in the main chain were synthesized by a concise route and an environment-friendly procedure without metal catalyst. They show strong fluorescence in solid state and can be used as non-doping emitter to fabricate emitting diodes. The single-layer electroluminescence devices with PVK or PEDOT buffer layer have been made with these copolymers as non-doping red-orange emitter, electron-transporting as well as hole-transporting material. The single-layer devices show preliminary results with maximum efficiency of 0.052% and EL wavelengths around 614 nm.     

Recent studies on small molecular and polymeric hole-transporting materials for high-performance perovskite solar cells

A decade of significant research has led to the emergence of photovoltaic solar cells based on perovskites that have achieved an exceptionally high-power conversion efficiency of 26.08%. A key breakthrough in perovskite solar cells (PSCs) occurred when solid hole-transporting materials (HTMs) replaced liquid electrolytes in dye-sensitized solar cells (DSSCs), because HTMs play a crucial role in improving photovoltaic performance as well as cell stability. This review is mainly focused on the HTMs that are responsible for hole transport and extraction in PSCs, which is one of the crucial components for efficient devices. Here, we have reviewed small molecular as well as polymeric HTMs that have been reported in the last two years and discussed their performance based on the analysis of their molecular architectures. Finally, we include a perspective on the molecular engineering of new functional HTMs for highly efficient stable PSCs.     

Blue light-emitting and hole-transporting amorphous molecular materials based on diarylaminobiphenyl-functionalized bimesitylenes

The diarylaminobiphenyl-functionalized bimesityls and exhibit amorphous nature, high thermal stability and excellent blue emission in the solid state. They serve as both hole-transporting and emissive materials in OLEDs for blue emission with high external quantum efficiencies.     

A new binaphthol based hole-transporting materials for perovskite solar cells

A novel hole-transporting material (Q221) is synthesized by introducing benzyl groups onto the 1,1′-bi-2-naphthol central core as edge chains and bis(4-methoxyphenyl)amine-substituted 9H-carbazole as donor groups. A reference molecule (Q222) is prepared with hexyl edge chains. The introduction of edge chains influences their molecular orbital energy levels. Q221-based CH₃NH₃PbI₃ perovskite solar cells with carbon counter electrode exhibit the highest power conversion efficiency of 10.37% at a low doping level of Li-TFSI/TBP (15 mM/100 mM), and that of Q222-based cells is 8.87%. Q221-based cells doping with Li-TFSI/TBP of 15 mM/100 mM shows much better photovoltaic parameters compared to those doping with Li-TFSI/TBP of 30 mM/200 mM, when aged in ambient air of 30% RH without encapsulation. The new binaphthol based hole-transporting materials shows a great potential in fabricating effective perovskite solar cells.     

酚基吡啶硼配合物发光材料

主要介绍双酚基吡啶硼配合物的合成、分子结构、分子堆积结构及其在有机电致发光器件中的应用.研究结果表明一些双酚基吡啶硼配合物可以作为发光材料制备性能优良的电致发光器件.     

Bis(4-diphenylaminophenyl)carbazole end-capped fluorene as solution-processed deep-blue light-emitting and hole-transporting materials for electroluminescent devices

A new highly fluorescent bis(4-diphenylaminophenyl)carbazole end-capped fluorene (TCF) is synthesized and characterized. TCF is an amorphous molecular glass with a high glass transition temperature of 169 °C, is electrochemically stable, and gives strong blue emission both in solution and solid state. It showed greater ability as a solution processed blue emitter and hole-transporter for OLEDs than commonly used NPB. High-efficiency, deep-blue and Alq3-based green devices with luminance efficiencies and CIE coordinates of 0.93 cd/A and (0.16, 0.09), and 3.78 cd/A and (0.29, 0.45) were achieved, respectively.     

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．     

共轭聚合物材料及电致发光器件

共轭聚合物是一种极有应用前景的有机半导体材料,本文综述其研究进展,包括典型共轭聚合物材料PPV、PT、PF等及PPP的工作原理,发展前景和存在的问题。     

Binaphthalene bridged bipolar transporting materials for blue electroluminescence: toward high EL efficiency via molecular tuning

Two isomeric bipolar transporting molecules containing arylamine and benzimidazole moieties linked by 1,1′-binaphthalene bridge have been synthesized and used for blue light-emitting diodes. The highly twisted binaphthalene bridge is beneficial for amorphous morphology, good solubility, high thermal stability and high photoluminescence quantum efficiency (Φ_PL). The charge transfer bands of these compounds exhibit interesting solvent-polarity dependent fluorescence properties. The physical properties of the compounds were tunable upon binding of the benzimidazole with binaphthalene group via C- (BINAPC) or N- (BINAPN) linkage. Three-layered blue-emitting OLEDs using BINAPC or BINAPN as the emitting layer, NPB as the hole transporting layer, and TPBI as the electron transporting layer as well as hole-blocking layer exhibit good performance. External quantum efficiencies of 2.49% with color coordinates of (0.15, 0.11) and 2.67% with color coordinates of (0.16, 0.16) were achieved for BINAPC and BINAPN, respectively.     

Photoactive amorphous molecular materials based on quinoline amines and their synthesis by Friedländer condensation reaction

A new class of conjugated quinoline amines was prepared by Friedländer condensation reaction. They showed stable amorphous state below glass transition temperatures as examined by differential scanning calorimetry and X-ray diffraction studies. Additionally, they exhibited fluorescence properties in the blue to green region of visible spectrum in both solution and solid state. Their fluorescence quantum efficiencies in chloroform were in a broad range of 3-45%. Interestingly, they formed stable fibers with micrometer thickness drawn from melt, which were characterized by polarizing optical microscopy and scanning electron microscopy studies.     

Blue light-emitting and electron-transporting materials based on dialkyl-functionlized anthracene imidazophenanthrolines

Two novel blue light-emitting materials based on bis(tert-butyl)anthracenyl-imidazophenanthrolines (BAIPs) have been synthesized and extensively characterized. Both materials exhibited a non-aggregate feature with high fluorescent quantum efficiency and excellent thermal stability. They can serve both as emissive and electron-transporting materials used in electroluminescence (EL) device for blue emission with high luminescence and external quantum efficiency. This study demonstrates that they are potentially useful for a wide range of applications in EL technology.     

含硼有机发光二极管材料与器件

硼元素因其独特的价层电子结构——价电子数少于价轨道数,而拥有一个空的p轨道,其三配位化合物既可以和邻近的π体系产生有效共轭,又可以容易地与路易斯碱发生络合,形成四配位化合物。将硼元素引入传统的光电功能分子当中,往往能给整个体系带来独特的光电性质,这已成为新型有机光电功能分子设计的重要思路。本文围绕硼元素的三配位化合物和四配位化合物,从分子设计理念、化合物光电性质、相关器件的结构与效率等方面对含硼有机光电功能分子及其器件的研究进展进行综述,并对其未来发展做出展望。     

蓝色延迟荧光材料及器件的研究进展

有机发光二极管(OLEDs)作为新一代的显示技术,因其启亮电压低、厚度薄、能效高、响应速度快等优点,而被世界各国研究人员所关注。 有机电致发光材料及器件的发展一直备受关注,根据发光机理的不同,有机发光材料可以分为荧光材料和磷光材料。 蓝色荧光材料作为OLEDs发展中的重要部分,拥有磷光材料无法比拟的优势,近年来成为研究热点。 本文介绍了近年来国内外蓝色延迟荧光材料的研究进展,并展望了其发展前景和趋势。     

Synthesis and Characteristics of Organic Red‐Emissive Materials Based on Phenanthro[9,10‐d]imidazole

Red emission is one of the three primary colors that are essential for the realization of full‐color displays and solid‐state lightings. A high solid‐state efficiency is a crucial factor for the applications in organic light‐emitting diodes (OLEDs). In this work, two new donor‐acceptor‐donor type phenanthro[9,10‐d]imidazole (PIM)‐based derivatives, (2Z,2′Z)‐2,2′‐(1,4‐phenylene)bis(3‐(4‐(1‐phenyl‐1H‐phenanthro[9,10‐d]imidazol‐2‐yl)phenyl)acrylonitrile) ( PIDSB ) and 2,3‐bis(4′‐(1‐phenyl‐1H‐phenanthro[9,10‐d]imidazol‐2‐yl)‐[1,1′‐biphenyl]‐4‐yl)fumaronitrile ( PIDPh ), are designed and synthesized. Both of them possess high thermal stabilities. PIDPh shows typical characteristics of aggregation‐induced emission enhancement, while PIDSB displays an aggregation‐caused quenching effect. They both exhibit significant red‐shifted emissions compared with PIM owing to intramolecular charge transfer. In the film state, the emission peaks of PIDSB and PIDPh are located at 538 nm and 605 nm with high photoluminescent quantum yields of 63.82 % and 41.26 %, respectively. The non‐doped OLED using PIDPh as the active layer shows the maximum external quantum efficiency of 2.06 % with a very low efficiency roll‐off, and exhibits the electroluminescent peak at 640 nm with a Commission Internationale de l′Éclairage coordinate of (0.617,0.396), meeting well the criteria of red OLEDs.     

Multifunctional Materials Serving as Efficient Non-Doped Violet-Blue Emitters and Host Materials for Phosphorescence

Efficient multifunctional materials acting as violet-blue emitters, as well as host materials for phosphorescent OLEDs, are crucial but rare due to demand that they should have high first singlet state (S₁) energy and first triplet state (T₁) energy simultaneously. In this study, two new violet-blue bipolar fluorophores, TPA-PI-SBF and SBF-PI-SBF , were designed and synthesized by introducing the hole transporting moiety triphenylamine (TPA) and spirobifluorene (SBF) unit that has high T₁ into high deep blue emission quantum yield group phenanthroimidazole (PI). As the results, the non-doped OLEDs based on TPA-PI-SBF exhibited excellent EL performance with a maximum external quantum efficiency (EQE_max) of 6.76 % and a violet-blue emission with Commission Internationale de L′Eclairage (CIE) of (0.152, 0.059). The device based on SBF-PI-SBF displayed EQE_max of 6.19 % with CIE of (0.159, 0.049), which nearly matches the CIE coordinates of the violet-blue emitters standard of (0.131, 0.046). These EL performances are comparable to the best reported non-doped deep or violet-blue emissive OLEDs with CIEy<0.06 in recent years. Additionally, the green, yellow and red phosphorescent OLEDs with TPA-PI-SBF and SBF-PI-SBF as host materials achieved a high EQE_max of about 20 % and low efficiency roll-off at the ultra-high luminance of 10 000 cd m⁻². These results provided a new construction strategy for designing high-performance violet-blue emitters, as well as efficient host materials for phosphorescent OLEDs.     

交联型小分子空穴传输材料在溶液工艺制备有机发光二极管中的应用

相比蒸镀工艺,溶液工艺制备有机发光二极管（OLEDs）具有材料利用率高、设备要求简单、成本低、可制作大尺寸面板等优点,受到了广泛关注。小分子空穴传输材料是有机发光二极管重要组成部分,起到传输空穴和阻挡电子的作用,在其结构上添加苯乙烯基、氧杂环丁烷等可交联基团,形成适合溶液工艺制备的可交联小分子空穴传输材料,通过热或光的引发形成网络状结构聚合物,进而应用于多层器件结构中,解决层间混溶问题,从而改善器件的效率和稳定性。本文从溶液工艺对材料的要求出发,首先介绍了旋转涂布及喷墨打印工艺的制备方法,评价了不同操作因素对薄膜质量的影响,之后详细介绍各不同交联基团的空穴传输材料,总结并对比各交联基团的优劣,以及对器件性能的影响。最后,展望了可交联空穴传输材料和溶液制备工艺的发展趋势。     

Non‐Doped Sky‐Blue OLEDs Based on Simple Structured AIE Emitters with High Efficiencies at Low Driven Voltages

Blue organic light‐emitting diodes (OLEDs) are necessary for flat‐panel display technologies and lighting applications. To make more energy‐saving, low‐cost and long‐lasting OLEDs, efficient materials as well as simple structured devices are in high demand. However, a very limited number of blue OLEDs achieving high stability and color purity have been reported. Herein, three new sky‐blue emitters, 1,4,5‐triphenyl‐2‐(4‐(1,2,2‐triphenylvinyl)phenyl)‐1H‐imidazole (TPEI), 1‐(4‐methoxyphenyl)‐4,5‐diphenyl‐2‐(4‐(1,2,2‐triphenylvinyl)phenyl)‐1H‐imidazole (TPEMeOPhI) and 1‐phenyl‐2,4,5‐tris(4‐(1,2,2‐triphenylvinyl)phenyl)‐1H‐imidazole (3TPEI), with a combination of imidazole and tetraphenylethene groups, have been developed. High photoluminescence quantum yields are obtained for these materials. All derivatives have demonstrated aggregation‐induced emission (AIE) behavior, excellent thermal stability with high decomposition and glass transition temperatures. Non‐doped sky‐blue OLEDs with simple structure have been fabricated employing these materials as emitters and realized high efficiencies of 2.41 % (4.92 cd A⁻¹, 2.70 lm W⁻¹), 2.16 (4.33 cd A⁻¹, 2.59 lm W⁻¹) and 3.13 % (6.97 cd A⁻¹, 4.74 lm W⁻¹) for TPEI, TPEMeOPhI and 3TPEI, with small efficiency roll‐off. These are among excellent results for molecules constructed from the combination of imidazole and TPE reported so far. The high performance of a 3TPEI‐based device shows the promising potential of the combination of imidazole and AIEgen for synthesizing efficient electroluminescent materials for OLED devices.