高分子化8-羟基喹啉锂的合成与静电自组装研究

设计合成了甲基丙烯酸二甲氨基乙酯(DM)含量为9.69%的丙烯酸甲酯共聚物(CPA),将制得的5-氯甲基-8-羟基喹啉(CHQ)挂接到CPA上,得到季铵型高分子化8-羟基喹啉(CPA-HQ)后,与金属离子Li+配位得到CPA-HQ-Li.化合物结构通过红外、紫外和荧光光谱等表征.多层超薄膜用CPA-HQ-Li和聚阴离子电解质(全氟磺酸)通过静电自组装制得.自组装膜的紫外和荧光相对于溶液(溶剂为四氢呋喃)发生了红移,膜的紫外吸收强度随组装膜层数增加线性增大,荧光强度随膜层数增加线性递减.高分子化8-羟基喹啉锂溶液和自组装膜的紫外和荧光光谱与文献报道一致.实验结果表明这种材料可用于有机电致发光器件(OLEDs)的制备.     

Rational design of functional oxide thin films with embedded magnetic or plasmonic metallic nanoparticles

Getting into films: Semiconductor thin films containing magnetic or plasmonic metal nanoparticles are key materials for the development of high-efficiency solar cells, bright light-emitting diodes, and new magnetoelectric devices. The catalytically driven chemical vapor deposition offers a unique way to combine deposition of the metallic nanoparticles with that of functional oxides to produce such films.     

Research progress on hybrid organic–inorganic perovskites for photo-applications

Hybrid organic–inorganic perovskite materials have attracted significant attention of most researchers in recently years, which is ascribed to the superior photoelectric properties, such as the suitable band gaps for harvesting sunlight, and exhibit high optical adsorption, high charge-carrier lifetimes and long diffusion lengths. The photodetectors, light-emitting diodes, solar cells and photocatalysts represent the remarkable applications for the hybrid organic–inorganic perovskite materials. Herein, we review the recent progress of hybrid organic–inorganic perovskite-based photodetectors, light-emitting diodes, solar cells and photocatalysts. The challenges and outlook for the hybrid organic–inorganic perovskite-based photodetectors, light-emitting diodes, solar cells and photocatalysts are considered.     

金属有机电致磷光材料研究进展

综述了近几年来用于有机发光二极管中的金属有机电致磷光材料的研究进展, 重点评述了重金属铱配合物、稀土元素配合物和含金属配合物的聚合物磷光材料近年来的研究进展, 展望了金属有机配合物电致磷光材料的发展前景.     

Measuring internal electric fields in organic light-emitting diodes using electroabsorption spectroscopy

A widely applicable electroabsorption technique to measure internal electric fields in organic light-emitting diodes is presented. The technique exploits the change in the a.c. electroabsorption response in the presence of a d.c. electric field. The electroabsorption signal is modulated at the fundamental frequency of the a.c. test signal, in addition to the usual modulation at the second harmonic frequency, when a d.c. bias is present. In metal/organic film/metal devices employing different metal contacts there is a built-in electric field in the organic film caused by the difference in work function between the two contacts. The electroabsorption response at the fundamental frequency of the applied a.c. bias is measured as a function of an external d.c. bias. The electroabsorption signal is nulled when the applied d.c. bias cancels the built-in electric field established by the different metals. We apply this technique to measure changes in metal–polymer Schottky barrier heights as a function of the contact metal. In metal/multiple organic films/metal structures the electroabsorption signals from the constituent organic films are identified spectroscopically and measured at both the fundamental and second harmonic frequency of the a.c. test signal. The amplitudes of the electroabsorption responses are then used to determine the a.c. and d.c. electric fields present in the organic layers. We apply this technique to determine the d.c. electric field distribution within a multi-layer organic light-emitting diode. These results highlight the general applicability of electroabsorption methods to probe internal electric fields in organic light-emitting diodes. © 1997 John Wiley & Sons, Ltd.     

Evaporated thin films of insulating poly-(tetrabromo-p-phenylenediselenide)

It has been shown that thin insulating film at the interface transparent conductive oxide/organic electroluminescent film could improve the performance of organic electroluminescent diodes (OLED). Such insulating film can be inorganic or organic. Poly-(tetrabromo-p-phenylenediselenide) (PBrPDSe) has been proved to be an efficient insulating film in OLED. The properties of these evaporated PBrPDSe thin films have been systematically studied by IR absorption, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, electron spin resonance and optical transmission measurements. It is shown that, when the deposition temperature is kept below the decomposition temperature of the polymer, tetrabromo-p-phenylenediselenide molecule is preserved during the deposition process. However the polymer, which is insoluble in powder form, becomes soluble after deposition. It can be concluded that films are mainly composed of oligomers of tetrabromo-p-phenylenediselenide.The electrical properties of SnO₂/PBrPDSe/Al thin films structures have been studied. The current-voltage characteristics exhibit a rectifying behaviour with a forward direction corresponding to a positive bias of the transparent conductive oxide film, the SnO₂.     

Blue-light-emitting and hole-transporting molecular materials based on amorphous triphenylamine-functionalized twisted binaphthyl

Two stable blue-light-emitting molecular materials containing twisted binaphthyl and peripheral triphenylamine groups were synthesized by Suzuki and Heck cross-coupling reactions. Both compounds exhibit excellent thermal and morphologic stabilities, high glass transition temperatures and good fluorescence quantum yield in films. They serve as both hole-transporting and blue emission materials in organic light-emitting diodes with good external quantum efficiencies.     

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。     

PURIFIED POLAR POLYFLUORENE FOR LIGHT-EMITTING DIODES AND LIGHT-EMITTING ELECTROCHEMICAL CELLS

Conjugated ployfluorene with 2-(2-(2-methoxyethoxy)ethoxy)ethyl groups(EO-PF)is prepared by the palladiumcatalyzed Suzuki coupling reaction.The polymer is purified carefully by a simple chemical procedure.The inductively coupled plasma(ICP)test shows palladium-catalyst in the polymer can be removed by this procedure.The thermal properties,electrochemical properties,UV-Vis absorption properties,photoluminescence properties and electroluminescent properties of the polymer without(EO-PF1)or with purification(EO-PF2)are studied.EO-PF2 shows better PL CIE coordinates in THF solutions as blue light-emitting materials and better photoluminescence stability in thin solid films. Polymer light emitting diodes and electrochemical cells based on EO-PF2 exhibit somewhat improved optoelectronic performance than control devices of EO-PF1.     

Heterolayer light-emitting diodes based on poly-phenylene vinylene

In order to enhance the quantum efficiency of poly-p-phenylene vinylene (PPV) light-emitting diodes (LEDs), we have fabricated metal/insulator/polymer (MIP) LEDs and heterolayer LEDs based on PPV and oxadiazole polymers. The current–voltage (I–V) characteristics and electroluminescence (EL) intensity of the MIP structures display a pronounced dependence of the insulator thickness and we detect an increase in the quantum efficiency of more than a factor of 30 at an AlO_x layer thickness of 3–6 nm. The device characteristics are qualitatively understood within inorganic metal insulator semi-conductor (MIS) theory and can be explained by a voltage-dependent barrier for minority carrier injection in connection with a hole-blocking barrier at the PPV/insulator interface. Our oxadiazole polymers used in the heterolayer polymeric devices are characterized by a high thermal stability and excellent film-forming properties. These materials act as efficient hole-blocking, electron transport and injection layers in PPV-based LEDs and we measure a significantly improved device performance with external quantum efficiencies of more than 0.5%. Temperature-dependent investigations point to a relatively balanced charge carrier injection and reveal the influence of space charge limited currents on the device performance at low temperature. © 1997 John Wiley & Sons, Ltd.     

喷墨打印聚合物薄膜均匀性调控研究进展

聚合物发光显示材料具有发光颜色在全可见光区可调、可溶液简单加工及适用于柔性大面积基底的特点,成为目前研究的热点。 在聚合物发光薄膜图案化技术中,喷墨打印因为具有加工过程简单高效、适用于溶液方式加工、柔性的加工过程等特点而被认为是最具有应用潜力的技术。 高质量聚合物薄膜的制备是高精度发光显示器件制作的关键,但喷墨打印液滴在干燥过程中通常伴随着“咖啡环”现象,造成薄膜不均匀沉积。 因此,消除“咖啡环”现象,实现聚合物薄膜的均匀沉积,是喷墨打印高性能器件的重要研究方向。 本文主要论述了“咖啡环”效应的产生机理,如何抑制喷墨打印聚合物薄膜加工过程中的“咖啡环”效应,最终实现聚合物薄膜均匀性调控。     

New n-type organic semiconductors: synthesis, single crystal structures, cyclic voltammetry, photophysics, electron transport, and electroluminescence of a series of diphenylanthrazolines

The synthesis, properties, and electroluminescent device applications of a series of five new diphenylanthrazoline molecules 1a-1e are reported. Compounds 1b, 1c, and 1d crystallized in the monoclinic system with the space groups P2(1)/c, C2/c, and P2(1)/c, respectively, revealing highly planar molecules. Diphenylanthrazolines 1a-1e have a formal reduction potential in the range -1.39 to -1.58 V (versus SCE) and estimated electron affinities (LUMO levels) of 2.90-3.10 eV. Compounds 1a-1e emit blue light with fluorescence quantum yields of 58-76% in dilute solution, whereas they emit yellow-green light as thin films. The diphenylanthrazoline molecules as the emissive layers in light-emitting diodes gave yellow light with a maximum brightness of 133 cd/m(2) and an external quantum efficiency of up to 0.07% in ambient air. Bilayer light-emitting diodes using compounds 1a-1e as the electron-transport layer and poly(2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene) as the emissive layer had a maximum external efficiency of 3.1% and 2.0 lm/W and a brightness of up to 965 cd/m(2) in ambient air. These results represent enhancements of up to 50 times in external quantum efficiency and 17 times in brightness when using 1a-1e as the electron-transport materials in polymer light-emitting diodes. These results demonstrate that the new diphenylanthrazolines are promising n-type semiconductors for organic electronics.     

Recent Advances and Optoelectronic Applications of Lead-Free Halide Double Perovskites

Organic–inorganic metal halide perovskites (most notably CH₃NH₃PbI₃) have demonstrated remarkable physical attributes for photovoltaic and diverse optoelectronic applications, whereas concerns about toxicity owing to the use of lead in the chemical composition still motivate further exploration of new, nontoxic candidates. Lead-free halide double perovskites (HDPs), designed by the rational chemical substitution of Pb²⁺ with other nontoxic candidate elements, have recently attracted interest as a fascinating alternative to their Pb-based counterparts. Herein, recent advances in crystal structures, physical properties, and versatile optoelectronic applications of lead-free HDPs, such as solar cells, photodetectors, X-ray detectors, and light-emitting diodes, are reviewed. Perspectives to improve the physical and photoelectric properties of existing HDP materials are also discussed and will favor future development of new, lead-free HDP candidates.     

Achieving saturated red photoluminescence and electroluminescence with readily synthesized maleimide-arylamine copolymers

Maleimide-based red fluorescent copolymers were easily synthesized from palladium catalyzed polycondensation of N-alkyl-3,4-bis(4-bromophenyl)maleimide with commercially available or readily prepared secondary aryldiamines. The copolymers were characterized by gel permeation chromatography, differential scanning calorimetry, cyclic voltammetry, UV-vis absorption, and fluorescence spectroscopy. They showed brilliant red fluorescence in solution (toluene) with emission maximum in the range of 617-638 nm, although severely red-shifted in thin films. With judicious selection of aryldiamine monomers, the red-shifting of the thin film fluorescence can be largely diminished. The structure and property (molecular weight, glass transition temperature, and fluorescence) relationships were analyzed and deciphered as well. A light-emitting device has been fabricated with maleimide-arylamine copolymer in demonstrating the potentials for saturated red polymer light-emitting diodes (PLEDs).     

White and Red Organic Light Emitting Materials

Derivatives of 2,3-(1,4-dialkoxyaceno)norbornadiene underwent ring-opening metathesis polymerization (ROMP) upon the catalysis of a ruthenium complex to afford the corresponding polymers. The polymeric materials containing anthracene chromophores emit white electro-luminescence, which can be fabricated into light-emitting diodes (LED). The broad emission band is composed of a blue emission from anthracene and a red emission from aggregates. A single layer device, ITO/polymer/Ca/Al, can be turned on at 7V and exhibits maximum intensity 427 cd/m2 at 15 V. A double layer device, ITO/polymer/TPBI/Mg:Ag (TPBI = (2,2′,2"-(1,3,5-benzenetriyl)-tris(1-phenyl-1H-benzimidazole)) displayed blue light with turn-on voltage 6 V and maximal intensity 930 cd/m2 at 15 V.Derivatives of bisindolylmaleimide were found to form amorphous solid films which exhibit intensive red luminescence. The property of forming glasses can be ascribed to the nonplanar geometry of these molecules. LED devices were fabricated by a layer of pure dye sandwiched between two charge transporting films. The yellow emission spectrum of the devices utilizing Alq (tris(8-hydoxyquinolinato)aluminum) contains a green component from Alq. Pure red emissions can be achieved by replacing Alq with TPBI. Typical devices can be turned on at ～3 V with maximal intensity 2000 cd/m2. White color devices are under current investigation, in which the green Alq layer is replaced by its blue derivative (bis(2-methyl-8-hydoxyquinolinato)(phenolato)aluminum).     

MOCVD-derived highly transparent, conductive zinc- and tin-doped indium oxide thin films: precursor synthesis, metastable phase film growth and characterization, and application as anodes in polymer light-emitting diodes

Four diamine adducts of bis(hexafluoroacetylacetonato)zinc [Zn(hfa)(2).(diamine)] can be synthesized in a single-step reaction. Single crystal X-ray diffraction studies reveal monomeric, six-coordinate structures. The thermal stabilities and vapor phase transport properties of these new complexes are considerably greater than those of conventional solid zinc metal-organic chemical vapor deposition (MOCVD) precursors. One of the complexes in the series, bis(1,1,1,5,5,5-hexafluoro-2,4-pentadionato)(N,N'-diethylethylenediamine)zinc, is particularly effective in the growth of thin films of the transparent conducting oxide Zn-In-Sn-O (ZITO) because of its superior volatility and low melting point of 64 degrees C. ZITO thin films with In contents ranging from 40 to 70 cation % (a metastable phase) were grown by low-pressure MOCVD. These films exhibit conductivity as high as 2900 S/cm and optical transparency comparable to or greater than that of commercial Sn-doped indium oxide (ITO) films. ZITO films with the nominal composition of ZnIn(2.0)Sn(1.5)O(z)() were used in fabrication of polymer light-emitting diodes. These devices exhibit light outputs and current efficiencies almost 70% greater than those of ITO-based control devices.     

Advances in the field of π-conjugated 2,2':6',2"-terpyridines

This critical review summarizes the research progress made in the field of π-conjugated terpyridines within the last decade. Supramolecular materials based on metal ion complexes of 2,2':6',2"-terpyridine derivatives have found manifold potential applications-from opto-electronic devices to life science. In this contribution, synthetic strategies towards π-conjugated terpyridines and their incorporation into advanced supramolecular architectures are evaluated. Applications as photoactive species in, e.g., photovoltaic devices, polymer light-emitting diodes (PLEDSs) and nanotechnology are discussed comprehensively (523 references).     

白光聚合物和聚合物白光器件

有机/聚合物电致发光器件(O/PLEDs)具有低能耗、宽视角、色彩丰富、快速响应、绿色环保以及可制备柔性屏等诸多优异特性,被业界公认为是21世纪最具潜质和最具发展前景的高技术领域之一.白光聚合物电致发光器件(WPLEDs)具有可通过湿法加工技术(如旋涂、丝网印刷、喷墨打印)大大降低器件的制作成本等优点,在显示和照明领域有着极大的应用前景,而受到人们广泛的关注.本文就国内在白光聚合物和聚合物白光器件方面的的研究现状,从聚合物白光器件和制备单一白光聚合物两个方面进行阐述,并介绍这一领域的发展前景和目前亟待解决的一些问题.     

蓝色有机电致发光材料及器件的研究进展

有机电致发光器件因在全彩平板显示和固态照明领域中具有广阔的应用前景, 而受到人们的广泛关注。 时至今日, 与现有的红色和绿色有机电致发光材料和器件相比, 具有优越综合性能的蓝色有机电致发光材料和器件却始终匮乏。 相对而言, 蓝光材料具有较宽的能隙, 因而很难获得低电压、高效率和良好稳定性的深蓝光器件。 通常, 白色有机电致发光器件可以通过混合三基色或者两种颜色的方法获得。 但是无论哪种方法, 蓝光材料均是必不可少的。 另外, 还可以通过能量传递将蓝光转化为红光和绿光。 因此, 研发出具有优越综合性能的蓝光材料对有机电致发光器件的推广及应用十分关键。 本文综述了近年来蓝色荧光材料、蓝色磷光材料的研究进展以及蓝光材料在蓝色和白色有机电致发光器件中的应用, 并结合现有工作, 对蓝色有机电致发光材料的研究和应用前景进行展望。     

Tuning the optical properties of mesoporous TiO2 films by nanoscale engineering

The optical properties of spin-coated titanium dioxide films have been tuned by introducing mesoscale pores into the inorganic matrix. Differently sized pores were templated using Pluronic triblock copolymers as surfactants in the sol-gel precursor solutions and adjusted by varying the process parameters, such as the polymer concentration, annealing temperature, and time. The change in refractive index observed for different mesoporous anatase films annealed at 350, 400, or 450 °C directly correlates with changes in the pore size. Additionally, the index of refraction is influenced by the film thickness and the density of pores within the films. The band gap of these films is blue-shifted, presumably due to stress the introduction of pores exerts on the inorganic matrix. This study focused on elucidating the effect different templating materials (Pluronic F127 and P123) have on the pore size of the final mesoporous titania film and on understanding the relation of varying the polymer concentration (taking P123 as an example) in the sol-gel solution to the pore density and size in the resultant titania film. Titania thin film samples or corresponding titanium dioxide powders were characterized by X-ray diffraction, cross-section transmission electron microscopy, nitrogen adsorption, ellipsometery, UV/vis spectrometry, and other techniques to understand the interplay between mesoporosity and optical properties.