水/醇溶共轭聚合物界面材料及其在光电器件中的应用

相对于传统的无机半导体器件,以有机半导体(特别是聚合物半导体)材料为基础的有机光电器件,可采用与传统印刷技术(例如喷墨打印、卷对卷印刷等)相结合的溶液加工方式制备低成本、大面积、柔性光电器件,因而成为广泛关注的焦点,并得到了快速发展.实现溶液加工的高效有机光电器件的一个关键问题是界面问题——如何避免溶液加工时有机层间的互溶以及如何实现可印刷稳定金属电极的高效电子注入等.水/醇溶性共轭聚合物的迅速发展为解决溶液加工多层有机光电器件所面临的界面问题提供了有效手段.研究发现,水/醇溶共轭聚合物不但可以有效避免溶液加工多层器件中的界面互溶,而且还可与高功函数的稳定金属发生界面偶极相互作用而增强其电子注入,从而解决了高功函数稳定金属电子注入的难题,为实现全溶液加工的高效印刷有机光电器件提供了可行的方案.本文介绍了近年来本课题组在水/醇溶共轭聚合物阴极界面材料及器件应用方面的研究进展,并对水/醇溶共轭聚合物阴极界面材料在聚合物发光二极管和聚合物太阳电池中的工作机理进行了探讨.     

Dibenzothiophene Sulfone-Based Ambipolar-Transporting Blue-Emissive Organic Semiconductors Towards Simple-Structured Organic Light-Emitting Transistors

The development of blue-emissive ambipolar organic semiconductor is an arduous target due to the large energy gap, but is an indispensable part for electroluminescent device, especially for the transformative display technology of simple-structured organic light-emitting transistor (SS-OLET). Herein, we designed and synthesized two new dibenzothiophene sulfone-based high mobility blue-emissive organic semiconductors (DNaDBSOs), which demonstrate superior optical property with solid-state photoluminescent quantum yield of 46–67 % and typical ambipolar-transporting properties in SS-OLETs with symmetric gold electrodes. Comprehensive experimental and theoretical characterizations reveal the natural of ambipolar property for such blue-emissive DNaDBSOs-based materials is ascribed to a synergistic effect on lowering LUMO level and reduced electron injection barrier induced by the interfacial dipoles effect on gold electrodes due to the incorporation of appropriate DBSO unit. Finally, efficient electroluminescence properties with high-quality blue emission (CIE (0.179, 0.119)) and a narrow full-width at half-maximum of 48 nm are achieved for DNaDBSO-based SS-OLET, showing good spatial control of the recombination zone in conducting channel. This work provides a new avenue for designing ambipolar emissive organic semiconductors by incorporating the synergistic effect of energy level regulation and molecular-metal interaction, which would advance the development of superior optoelectronic materials and their high-density integrated optoelectronic devices and circuits.     

并五苯及其衍生物在有机场效应晶体管中的应用

有机场效应晶体管（organic field—effect transistors,OFETs）是以有机半导体材料作为有源层,通过电场控制电流的电子器件．与传统的无机半导体器件相比,由于其可应用于生产大面积、柔性、低成本电子设备而备受关注,在有机存储器件、有机太阳能电池、柔性平板显示和电子纸等众多领域具有潜在而广泛的应用前景．并苯类材料因其紧密的分子堆积及优异的半导体性能被广泛研究．其中,并五苯及其衍生物在场效应晶体管中表现出良好的性质,其效果甚至可以与非晶硅相媲美,但并五苯较差的溶解性及环境稳定性阻碍了其进一步应用．科研工作者通过对分子结构进行修饰改造设计,合成了一系列并五苯的衍生物,其不仅在稳定性、电学性能和溶解性方面有很大提高,还可以将该p-型半导体材料拓展到双极性及n-型半导体材料领域．本文对并五苯及其衍生物在有机场效应晶体管中的应用进行了较为全面的综述,期望对该领域的研究起到一定的推动作用．     

水溶性共轭聚电解质

水溶性共轭聚电解质主要是指含离子型官能团侧链的共轭聚合物,可在水或其它极性有机溶剂中能够溶解。这类化合物把传统共轭聚合物的光电性质和聚电解质的水溶性特点结合在一起,显示出的一些独特性质,可在新一代光电器件制作和化学生物荧光传感器中获得多样的应用。本文总结了近10年来报道的水溶性共轭聚电解质的结构特点和合成方法,以及对不同化学或物理条件下光物理性质的研究,归纳了它们在新一代光电器件制作和荧光传感中的应用,并在此基础上提出了水溶性共轭聚电解质研究中尚待解决的问题,并展望了水溶性共轭聚电解质的应用前景。     

Synthesis,Single Crystal,and Physical Properties of Asymmetrical Thiophene/Selenophene‐Fused Twistacenes

Two asymmetrical twistacenes, PyPT and PyPS , have been synthesized and characterized. Single crystal X‐ray analyses show that both of them have twisted structures with a torsion angle of 26.65° for PyPT and 26.59° for PyPS measured between plane C5‐C23‐C25 and plane C13‐C15‐C26. The thiophene/selenophene‐fused acenes emit blue fluorescence with quantum yields of 0.39 for PyPT and 0.04 for PyPS in organic solvents, whereas the all‐carbon molecule HBP emits green fluorescence. Meanwhile, PyPT and PyPS show a similar reversible oxide procedure with the onset potentials of 0.73 and 0.72 V, respectively. In addition, PyPT and PyPS can self‐assemble to form nanoparticles in a mixture of THF/H₂O through re‐precipitation method.     

Synthesis of an electroluminescent polymer and its non‐doped light‐emitting diodes with stable green emission

An electroluminescent polymer was synthesized by Wittig condensation and characterized by the measurements of ¹H‐NMR, IR, gel permeation chromatography (GPC), UV–Vis, PL, and cyclic voltammetry (CV). The polymer can be dissolved in common organic solvents such as tetrahydrofuran (THF), chloroform, and dichloromethane. The electroluminescent investigation showed that the non‐doped devices with a double‐layer configuration (ITO/PEDOT:PSS/Polymer/Mg:Ag) have a stable green emission property. The maximum luminance of the annealed device reaches 2317 cd/m². The emission maximum and the CIE 1931 coordinate values are respectively stabilized at 552 nm and near (x, y) = (0.43, 0.55) with different voltages. Copyright © 2008 John Wiley & Sons, Ltd.     

Fluorene‐ and benzimidazole‐based blue light‐emitting copolymers: Synthesis,photophysical properties,and PLED applications

Blue light‐emitting materials are receiving considerable academic and industrial interest due to their potential applications in optoelectronic devices. In this study, blue light‐emitting copolymers based on 9,9′ ‐ dioctylfluorene and 2,2′‐(1,4‐phenylene)‐bis(benzimidazole) moieties were synthesized through palladium‐catalyzed Suzuki coupling reaction. While the copolymer consisting of unsubstituted benzimidazoles (PFBI0) is insoluble in common organic solvents, its counterpart with N‐octyl substituted benzimidazoles (PFBI8) enjoys good solubility in toluene, tetrahydrofuran, dichloromethane (DCM), and chloroform. The PFBI8 copolymer shows good thermal stability, whose glass transition temperature and onset decomposition temperature are 103 and 428 °C, respectively. Its solutions emit blue light efficiently, with the quantum yield up to 99% in chloroform. The electroluminescence (EL) device of PFBI8 with the configuration of indium‐tin oxide/poly(ethylenedioxythiophene):poly(styrene sulfonic acid)/PFBI8/1,3,5‐tris(1‐phenyl‐1H‐benzimidazole‐2‐yl)benzene/LiF/Al emits blue light with the maximum at 448 nm. Such unoptimized polymer light‐emitting diode (PLED) exhibits a maximum luminance of 1534 cd/m² with the current efficiency and power efficiency of 0.67 cd/A and 0.20 lm/W, respectively. The efficient blue emission and good EL performance make PFBI8 promising for optoelectronic applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

单分子有机电致白光材料及器件

有机电致白光二极管在白光照明和背光源应用中具有材料来源广、驱动电压低、节能和环保等优点,受到了广泛关注。目前实现电致白光的方法主要有小分子掺杂、多层器件、激基复合物和缔合物发光以及单分子白光等方法。其中,单分子白光材料由于要控制能量的不完全传递、单分子实现多色同步发射和优化器件结构等,目前研究得还比较少,器件的总体性能相对还不是很理想。本文从材料合成的角度,简要综述了国内外在单分子白光材料的合成与器件性能优化方面所取得的研究进展,并对下一步需要研究的热点问题作了展望。     

Novel fluorescent 2‐(2‐aminofluorophenyl)benzoxazoles: Syntheses and photophysical properties

2‐(2‐Amino‐3,4,5,6‐tetrafluorophenyl)benzoxazole ( 2 ) absorbs in long wavelength band (λ_abs^max = 346 nm in methanol) and in the normal wavelength band (λ_abs^max = 285.5 nm), and emits blue fluorescence. The emission intensity is highly affected by the solvent polarity and is large in a polar solvent such as methanol. 2‐(2‐Pentafluorobenzamido‐3,4,5,6‐ tetrafluorophenyl)benzoxazole ( 5 ) emits green fluorescence along with the short wavelength emission around 380 nm and their relative intensity depends on the solvent polarity. Green fluorescence is enhanced in nonpolar solvents such as chloroform and toluene, resulting in the considerably large Stokes shift.     

卟啉类化合物分子光电器件研究进展

分子电子器件是未来分子电路的微电子元件,已成为有机功能纳米材料研究的热点。 卟啉类化合物的π共轭体系表现出的独特光电性能和良好的热稳定性,使其作为光电器件、模拟生物酶、分子识别和传感材料在材料化学、医学、生物化学和分析化学等领域展现出良好的应用前景,由于卟啉分子平面结构的易修饰性,常用卟啉化合物组装单元来构建功能化的卟啉光电器件。 本文综述了卟啉类化合物的特点及其在光电器件中的应用进展。     

Electroluminescent properties of anthracene‐containing polyimides

Optical and electroluminescent properties of a new soluble anthracene‐containing polyimide (ACPI) was studied. Solubility of ACPI in organic solvents allows direct spin casting of the polymer films exhibiting intense photo‐ and electroluminescence (EL) in the visible range. This non‐conjugated polymer was used as emitting and electron‐hole transporting layers in polymer light‐emitting devices (LEDs). EL properties of the uni‐ and bilayer LEDs are discussed in terms of the band structure, bipolar transport and electron donor‐acceptor interactions. Copyright © 2000 John Wiley & Sons, Ltd.     

Electroluminochromic Materials and Devices Based on Metal Complexes

Electroluminochromism (ELC) refers to an interesting phenomenon exhibited by a material whose luminescent properties can be reversibly modulated under an electrical stimulus. Such a luminescence‐switching property has been widely used in various organic optoelectronic devices because it can simultaneously detect electrical and optical signals. Metal complexes are the promising candidates for ELC materials due to their sensitivity to an electrical stimulus. Herein, recent progress on electroluminochromic materials and devices based on various metal complexes has been summarized. Meanwhile, the applications of these complexes in data recording and security protection have also been discussed. Finally, a brief conclusion and outlook are presented, pointing out that the development of electroluminochromic metal complexes with excellent performance is important because they play a vital role in future intelligent optoelectronic devices.     

聚集诱导发光分子的光电功能与器件应用

光电功能分子通常以薄膜和聚集体的形式显示功能, 聚集诱导发光（AIE）分子体系的发现为解决固态下聚集诱导荧光猝灭（ACQ）难题提供了新的思路. 本文总结了近年来本课题组发展的一系列AIE 分子, 侧重介绍这些AIE 分子的光电功能与器件应用, 特别是在有机电致发光器件和有机激光方面的应用. AIE 材料显示非常高的电致发光效率, 在显示与白光器件方面潜力巨大. 在发展电泵有机激光方面, AIE 材料特点突出, 是最有前景的一类材料.     

New π-conjugated polymers based on N-(4-(3,5-bis(4-bromophenyl)-[1,2,4]triazol-4-yl)-phenyl)carbazole: Synthesis and photoluminescent, electroluminescent, and electrochromic properties

New π-conjugated copolyfluorenes carrying main-chain electron-acceptor triazole groups and side-chain electron-donor carbazole fragments are synthesized. All copolymers show solubility in common organic solvents and exhibit high thermal stability and excellent film-forming behavior. The absorption, photoluminescent, electroluminescent, and electrochromic properties of the copolymers are investigated. Polymer films feature stable electrochromic properties as their color changes from yellow in the neutral from to lilac in the oxidized form during a change in the applied voltage from 0 to 1.9 V. In addition, copolyfluorenes demonstrate better electroluminescent properties than the standard homopolylfluorene and offer promise as attractive electroactive materials for use as emitting layers in polymer light-emitting devices.     

Design and Synthesis of Conjugated Starburst Molecules for Optoelectronic Applications

In recent years, conjugated starburst molecules, which possess a core unit with radial arms linked to the central axle, have become the research topic owing to their well‐defined chemical structures, good solution processability, excellent reproducibility, and superior optoelectronic properties. The increasing interest in starburst systems is evidenced by progressively more frequent investigation on the use of these materials in optoelectronics. The ability to modify chemical structures through control over the core and arms on a molecular level can directly affect the electronic and electroluminescent characteristics of the resulting materials. In this review, we summarize and discuss main progress in our group concerning the rapidly developing field, in which strategies for the design and construction of starbursts are presented at length. Moreover, their application in organic light‐emitting diodes (OLEDs) and organic semiconductor lasers (OSLs) are demonstrated as well, exploring the influence of molecular structures on the optoelectronic properties. Challenges and outlooks are also given at last.     

Electroluminescent properties of a partially‐conjugated hyperbranched poly(p‐phenylene vinylene)

In this paper, the electroluminescent properties of a new partially‐conjugated hyperbranched poly (p‐phenylene vinylene) (HPPV) were studied. The single layer light‐emitting device with HPPV as the emitting layer emits blue‐green light at 496 nm, with a luminance of 160 cd/m² at 9 V, a turn‐on voltage of 4.3 V and an electroluminescent efficiency of 0.028 cd/A. By doping an electron‐transport material [2‐(4‐biphenylyl)‐5‐phenyl‐1,3,4‐oxadiazole, PBD] into the emitting layer and inserting a thin layer of tris(8‐hydroxy‐quinoline)aluminum (Alq₃) as electron transporting/hole blocking layer for the devices, the electroluminescent efficiency of 1.42 cd/A and luminance of 1700 cd/m² were achieved. The results demonstrate that the devices with the hyperbranched polymers as emitting material can achieve high efficiency through optimization of device structures. Copyright © 2006 John Wiley & Sons, Ltd.     

Characteristics of a single‐layered organic electroluminescent device using a carrier‐transporting copolymer and a nonconjugated light‐emitting polymer

We have synthesized a novel carrier‐transporting copolymer and a nonconjugated light‐emitting polymer. The carrier‐transporting copolymer has a triphenylamine moiety as a hole‐transporting unit and a triazine moiety as an electron‐transporting unit, both of which are located in the polymer side chain. The nonconjugated light‐emitting polymer has a perylene moiety, which acts as an emitting unit in the polymer side chain. These polymers are very soluble in most organic solvents, such as monochlorobenzene, tetrahydrofuran, chloroform, and benzene. A single‐layered electroluminescent device consisting of ITO/copolymer and emitting‐material 4‐(dicyanomethylene)‐2‐methyl‐6‐(4‐dimethylaminostyryl)‐4H‐pyran (DCM) or light‐emitting polymer)/Al mixtures exhibits maximum external quantum efficiency when the concentration of the emitting material is 30 wt %. The device emits red or blue light according to the emitting material. When CsF is used as the electron‐injecting material, the drive voltage decreases drastically to 7 V, and the highest quantum efficiency is 0.5%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2733–2743, 2003     

Giant Star‐Shaped Nitrogen‐Doped Nanographenes

Star‐shaped nanographenes (SNGs) are large monodisperse polycyclic aromatic hydrocarbons that are larger than a nanometer and have shown a lot of promise in a wide range of applications including electronics, energy conversion, and sensing. Herein, we report a new family of giant star‐shaped N‐doped nanographenes with diameters up to 6.5 nm. Furthermore, the high solubility of this SNG family in neutral organic solvents at room temperature allowed a complete structural, optoelectronic, and electrochemical characterisation, which together with charge transport studies illustrate their n‐type semiconducting character.     

Synthesis and Non-linear Optical（NLO） Properties of a Series of Alkoxysilane Derivative Chromophores

1 Introduction Nonlinear optical materials(NLO) have drawn a great intrest of some scholars and scientists in the last dacades because of their tremendous     

Acid Exfoliation of Imine‐linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films

Covalent organic frameworks (COFs) are highly modular porous crystalline polymers that are of interest for applications such as charge‐storage devices, nanofiltration membranes, and optoelectronic devices. COFs are typically synthesized as microcrystalline powders, which limits their performance in these applications, and their limited solubility precludes large‐scale processing into more useful morphologies and devices. We report a general, scalable method to exfoliate two‐dimensional imine‐linked COF powders by temporarily protonating their linkages. The resulting suspensions were cast into continuous crystalline COF films up to 10 cm in diameter, with thicknesses ranging from 50 nm to 20 μm depending on the suspension composition, concentration, and casting protocol. Furthermore, we demonstrate that the film fabrication process proceeds through a partial depolymerization/repolymerization mechanism, providing mechanically robust films that can be easily separated from their substrates.