传输型电致发光聚合物的合成与表征

高分子发光材料除应具有优良发光性能外，还需具有优良电子传输性能和空穴传输性能。本论文以此为出发点，将具有优良空穴传输性能的芳胺类化合物和具有优良电子传输性能的噁二唑类化合物，通过无规共聚合调控发光基元和两类传输基元的含量，合成了系列的传输与发光一体化的即V类高分子发光材料，并探讨了聚合物本身的基本特性。同时，设计和制备了相应的单层结构器件和掺杂器件，考察了器件的器件性能。本论文主要工作内容及结果如下：1、成功的利用三类王芳胺类双醛：4，4'-二醛基-（4-辛氧基-苯基）-二苯胺（TPA双醛）、N，N'-二（4-辛氧基一苯基）-N，N'-二（4-甲醛基-苯基）-1，4-苯二胺（PDA双醛）和N，N，-二（4-辛氧基-苯基）-N，N，-二（4-甲醛基-苯基）-4，4' 联苯二胺（TPD双醛）和wittig麟盐无规共聚，得到三个系列双极传输高分子发光材料。2、聚合物主链中同时引入三芳胺类空穴传输基团和噁二唑电子传输基团，提高了器件性能。在TPA系列中，同时含有三芳胺和噁二唑全基团的聚合物比仅含有三芳胺基团聚合物的单层器件亮度及效率分别提高29和22倍，同时使器件的启动电压从9.3V下降到2．7V。在同样比较的情况下，在PDA系列中，聚合物的器件亮度及效率要提高近8倍，同时使器件的启动电压从5.3V下降到4.5V。在TPD系列中，聚合物的器件亮度及效率要提高44和38倍，同时使器件的启动电压从7.5V下降到5.7V。3、含有噁二唑基团聚合物分子的这种D-A体系所具有的分子内电荷转移性质，导致其荧光光谱和电致发光光谱红移。其中，TPA系列和TPD系列的电致发光光谱从绿光红移到了黄绿光，而PDA系列聚合物的电致发光光谱从黄绿光红移到了橙光。4、刚性的噁二唑基团的引入提高了聚合物的热稳定性，T以系列聚合物、PDA系列聚合物和TPD系列聚合物中含有噁二唑基团的聚合物的玻璃化转变温度在112-229℃之间，其热分解温度超过420℃。5、此三个系列聚合物中同时含有空穴和电子传输基元的双极分子溶液的紫外一可见吸收光谱和荧光光谱都有明显的溶剂化效应，表现出较强的分子内电荷转移特性。6、利用TPA系列聚合物中性能最好的聚合物TPA-OXD-PV1的良好电子和空穴传输性质，构造的单层掺杂器件，实现了橙色和红色发光。

High PL-efficiency ZnO nanocrystallites/PPV composite nanofibers

In this paper, we report for the first time on the synthesis of ZnO nanocrystallites in conjugated polymer (PPV) nanofibers by the coupling of the in situ/blend methods and electrospinning. These composite nanofibers were characterized by fluorescence microscopy, atomic force microscope (AFM), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectra, Fourier transform infrared (FT-IR) spectroscopy, and X-ray powder diffraction (XRD).

Morphology and crystalline transition of poly (3-butylthiophene) associated with its polymorphic modifications

Poly (3-butylthiophene) (P3BT) is a much less studied conjugated polymer despite its high crystallizability and thus excellent electrical property. In this work, morphology of P3BT at different crystalline polymorphs and solvent/thermal induced phase transition between form I and U modifications have been intensively investigated by using optical microscopy, electron microscopy, differential scanning calorimetry, and X-ray diffraction. It is shown that a direct deposition from carbon disulfide (CS2) at fast evaporation results in P3BT crystals in form I modification, giving typical whiskerlike morphology. In contrast, low evaporation rate from CS, leads to formation of form II crystals with spherulitic morphology, which is so far scarcely observed in polythiophene.

Single mode and multimodes lasing emission from MEH-PPV doped polystyrene thin films with surface ripples formed by vapour-induced phase separation

We report single mode and multimodes lasing emission from conjugated polymer poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) doped polystyrene ( PS) thin films with surface ripples. Surface ripples were formed by water vapour-induced phase separation. A single mode lasing emission at 606 nm with a line-width of less than 0.4 nm was obtained. The laser threshold was as low as 3.5 mu J pulse(-1). The side mode suppression ratio was 5.76 dB. The periodic changes of the refraction index in the MEH-PPV : PS blending film due to the phase separation should be attributed to the lasing actions.

Synthesis and Application of Thiadiazoloquinoxaline-Containing Chromophores as Dopants for Efficient Near-Infrared Organic Light-Emitting Diodes

series of a donor-acceptor-donor type of near-infrared (NIR) fluorescent chromophores based on [1,2,5]thiadiazolo[3,4-g]quinoxaline (TQ) as an electron acceptor and triphenylamine as an electron donor are synthesized and characterized. By introducing pendent phenyl groups or changing the pi-conjugation length in the TQ core, we tuned tile energy levels of these chromophores, resulting in the NIR emission in a range from 784 to 868 nm. High thermal stability and glass transition temperatures allow these chromophores to be used as dopant emitters, which can be processed by vapor deposition for the fabrication of organic light-emitting diodes (OLEDs) having the multilayered structure of ITO/MoO3/NPB/Alq(3):dopant emitter/BCP/Alq(3)/LiF/Al. The electroluminescence spectra of the devices based on these new chromophores cover a range from 748 to 870 nm. With 2 wt % of dopant 1, the LED device shows an exclusive NIR emission at 752 nm with the external quantum efficiency (EQE) as high as 1.12% over a wide range of current density (e.g., around 200 mA cm(-2)).

Novel blue light-emitting PPV-based copolymer containing triazole and carbazole units

A novel alternating conjugated copolymer containing triazole and carbazole units was synthesized by the Wittig reaction. The resulting bipolar conjugated polymer emits a pure light with good thermal stability, which is a promising candidate for polymer light emitting display.

Lasing behavior in DCM-doped PVK microcavity

A surface emitting microcavity was formed by sandwiching a polymer film containing PVK, Alq(3) and DCM between a distributed Bragg reflector (DBR) with a reflectivity of 99% and a silver film (300 nm). The lasing phenomenon was observed in DCM-doped PVK microcavity. The full width at half maximum (FWHM) was 0.6 nm with the peak wavelength at 603 nm. The threshold energy for lasing was estimated to be about 2.5 mu J per pulse. (C) 2000 Published by Elsevier Science S.A. All rights reserved.

Stimulated emission in the blue wavelength region from a copolymer containing PPV segment

The lasing properties of a soluble conjugated polymer, Poly[1,8-octanedioxy-2,6-dimethoxy-1,4-phenylene-1,2-ethenylene-1,2-phenylene-1,2-ethenylene-3,5-dimethoxy-1,4-phenylene] (CNMBC-Ph) in chloroform solution were investigated. The third harmonic radiation of a Nd:YAG laser was used as the pump light. The stimulated emission with a linewidth of 15 nm was observed in the blue wavelength region with the peak at 450 nm. The threshold pulse peak power was about 2.8 MW/cm(2). The energy conversion yield of the laser was estimated to be about 3.4%. The maximum peak power of the laser output pulse reached 40 kW. (C) 2000 Published by Elsevier Science S.A. All rights reserved.

Photoluminescent properties of dye-doped poly(N-vinyleabzole) (PVK) in microcavity

A surface emitting microcavity was formed by sandwiching a polymer film containing poly(N-vinyleabzole) (PVK). 8-hydroxyquinoline aluminium (Alq(3)) and 4-(Dicyanome thylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-Pyran(DCM) between a distributed Bragg reflector (DBR) with a reflectivity of 99% and a silver film. The sample was optically pumped with 250 ps pulses at 2 Hz repetition rate by a 355 nm line of the third harmonic of a mode-lock Nd:YAG laser. The lasing phenomenon was observed in DCM-doped PVK microcavity. The full width at half maximum (FWHM) was 3 nm with the peak wavelength at 602 nm. The threshold energy for lasing was estimated to be about 3 mu J. (C) 2000 Elsevier Science S.A. All rights reserved.

Synthesis and characterization of aromatic dianhydrides and polyesterimides derived from 4-hydroxyphthalic anhydride

4-Hydroxyphthalic anhydride, prepared from 4-chlorophthalic anhydride, was reacted with trimellitic anhydride monoacid chloride or arylene diacid chloride to give aromatic ester-containing dianhydrides (EDAs). These dianhydrides were characterized by element analysis, melt point, FTIR and H-1-NMR. A series of aromatic poly (amic ester acid)s was synthesized by polycondensation of these EDAs and various diamines in polar organic solvent. The inherent viscosity of poly (amic ester acid)s ranged from 0.55 to 0.89 dL/g, indicating the intermediate to higher molecular weight. Polyesterimides having glass transition temperatures between 184-219degreesC were produced by thermal imidization of corresponding poly (amic ester acid)s. These polymers were fairly resistant to organic solvent, but some of them were soluble in phenol solvents. Thermogravimetric analyses revealed that these polyesterimides were stable up to 400degreesC, and the 5% weight loss temperatures were recorded in the range of 432-483degreesC in air atmosphers and 451-490degreesC in nitrogen.

Stimulated emission in blue wavelength region from a copolymer

A dye laser based on the soluble conjugated polymer, Poly[1,8-octanedioxy-2,6-dimethoxy-1,4-phenylene-1,2-ethenylene-1, 4-phenylene-1,2-ethenylene-3,5-dimethoxy-1,4-phenylene], has been fabricated. The laser was pumped by light pulses from the third harmonic radiation of an Nd:YAG laser. The lasing was observed in the blue wavelength region with the peak at 450 nm. The threshold energy is about 19 mu J. The energy conversion yield of the laser is about 3.4%. The maximum peak power of the laser output pulse arrives at about 20 kW.

Design, fabrication and characterisation of components for microfluidic enzymatic biofuel cells

The concept of a biofuel cell takes inspiration from the natural capability of biological systems to catalyse the conversion of organic matter with a subsequent release of electrical energy. Enzymatic biofuel cells are intended to mimic the processes occurring in nature in a more controlled and efficient manner. Traditional fuel cells rely on the use of toxic catalysts and are often not easily miniaturizable making them unsuitable as implantable power sources. Biofuel cells however use highly selective protein catalysts and renewable fuels. As energy consumption becomes a global issue, they emerge as important tools for energy generation. The microfluidic platforms developed are intended to maximize the amount of electrical energy extracted from renewable fuels which are naturally abundant in the environment and in biological fluids. Combining microfabrication processes, chemical modification and biological surface patterning these devices are promising candidates for micro-power sources for future life science and electronic applications. This thesis considered four main aspects of a biofuel cell research. Firstly, concept of a miniature compartmentalized enzymatic biofuel cell utilizing simple fuels and operating in static conditions is verified and proves the feasibility of enzyme catalysis in energy conversion processes. Secondly, electrode and microfluidic channel study was performed through theoretical investigations of the flow and catalytic reactions which also improved understanding of the enzyme kinetics in the cell. Next, microfluidic devices were fabricated from cost-effective and disposable polymer materials, using the state-of-the-art micro-processing technologies. Integration of the individual components is difficult and multiple techniques to overcome these problems have been investigated. Electrochemical characterization of gold electrodes modified with Nanoporous Gold Structures is also performed. Finally, two strategies for enzyme patterning and encapsulation are discussed. Several protein catalysts have been effectively immobilized on the surface of commercial and microfabricated electrodes by electrochemically assisted deposition in sol-gel and poly-(o-phenylenediamine) polymer matrices and characterised with confirmed catalytic activity.

Multiphysics simulation of microwave curing in micro-electronics packaging applications

Purpose – This paper aims to present an open-ended microwave curing system for microelectronics components and a numerical analysis framework for virtual testing and prototyping of the system, enabling design of physical prototypes to be optimized, expediting the development process. Design/methodology/approach – An open-ended microwave oven system able to enhance the cure process for thermosetting polymer materials utilised in microelectronics applications is presented. The system is designed to be mounted on a precision placement machine enabling curing of individual components on a circuit board. The design of the system allows the heating pattern and heating rate to be carefully controlled optimising cure rate and cure quality. A multi-physics analysis approach has been adopted to form a numerical model capable of capturing the complex coupling that exists between physical processes. Electromagnetic analysis has been performed using a Yee finite-difference time-domain scheme, while an unstructured finite volume method has been utilized to perform thermophysical analysis. The two solvers are coupled using a sampling-based cross-mapping algorithm. Findings – The numerical results obtained demonstrate that the numerical model is able to obtain solutions for distribution of temperature, rate of cure, degree of cure and thermally induced stresses within an idealised polymer load heated by the proposed microwave system. Research limitations/implications – The work is limited by the absence of experimentally derived material property data and comparative experimental results. However, the model demonstrates that the proposed microwave system would seem to be a feasible method of expediting the cure rate of polymer materials. Originality/value – The findings of this paper will help to provide an understanding of the behaviour of thermosetting polymer materials during microwave cure processing.