Band‐gap engineering of polythiophenes via dithienophosphole doping

A series of polythiophenes doped with dithieno[3,2‐b:2′,3′‐d]phosphole units at varying levels (0–17%) were synthesized and characterized. Polymer work up provided two series of polymers from chloroform (C) and hexanes (H) for each doping level, respectively. Systematic structure–property studies revealed that the C‐series polymers generally had higher molecular weights than the H‐series, but also slightly higher relative dithienophosphole concentrations, both having a significant impact on the photophysical and electrochemical properties of the polymers. Furthermore, the presence of the dithienophosphole units also stabilizes the LUMO levels, whereas the HOMO levels remain dominated by the thiophene units, resulting in desirable electronics for an interaction with acceptor materials, such as 1‐(3‐methoxycarbonyl)propyl‐1‐phenyl[6,6]C₆₁. Importantly, increasing amount of dithienophosphole doping results in increased conductivities for the polymers in their oxidized state, while concurrently significantly stabilizing the neutral polythiophenes toward oxidation under environmental conditions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Solution processable high band gap hosts based on carbazole functionalized cyclic phosphazene cores for application in organic light‐emitting diodes

A new class of solution processable dendrimers based on cyclic phosphazene (CP) cores have been prepared and used as host materials for blue and green organic light emitting diodes (OLEDs). The dendrimers are prepared in high yield from minimal step reactions, are soluble in common solvents for solution processing, are amorphous, and have excellent thermal properties necessary for application in OLEDs. OLED efficiencies of 10.3 cd/A (4.2 lm/W) and 35.3 cd/A (33.5 lm/W) were achieved using commercially available FIrpic and Ir(mppy)₃ as blue and green phosphorescent emitters, respectively. These efficiencies were 2× higher than control devices prepared using poly(N‐vinylcarbazole), the most commonly used host material in solution processed phosphorescent OLEDs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Effect of chemical modifications on the electronic structure of poly(3‐hexylthiophene)

The widespread use of poly(3‐hexylthiophene) (P3HT) in the active layers of organic solar cells indicates that it possesses chemical stability and solubility suitable for such an application. However, it would be desirable to have a material that can maintain these properties but with a smaller bandgap, which would lead to more efficient energy harvesting of the solar spectrum. Fifteen P3HT derivatives were studied using the Density Functional Theory. The conclusion is that it is possible to obtain compounds with significantly smaller bandgaps and with solubility and stability similar to that of P3HT, mostly through the binding of oxygen atoms or conjugated organic groups to the thiophenic ring. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys., 2013     

Lateral Inhomogeneity in the Electronic Structure of a Conjugated Poly(3‐hexylthiophene) Thin Film

How annealing influences the morphology of a highly regioregular poly(3‐hexylthiophene) (RR‐P3HT) film at the substrate interface as well as the lateral inhomogeneity in the electronic structure of the film are elucidated. Whereas previous studies have reported that high‐molecular‐weight (MW) RR‐P3HT films tend to show low crystallinity even after annealing, it is found that high‐MW RR‐P3HT does show high crystallinity after annealing at high temperature for a long time. Photoemission electron microscopy (PEEM), X‐ray photoemission spectroscopy, and ultraviolet photoemission spectroscopy results clearly resolve a considerable lateral inhomogeneity in the morphology of RR‐P3HT film, which results in a variation of the electronic structure depending on the local crystallinity. The PEEM results show how annealing facilitates crystal growth in a high‐MW RR‐P3HT film.     

导电聚苯胺／MnO2空气阴极氧还原动力学

采用动电位扫描、交流阻抗技术研究了导电聚苯胺/MnO2复合阴极上氧还原反应动力学.动电位扫描表明氧在该复合阴极上还原的极化曲线服从Butler-Volmer公式,表观标准活化能为184.9 kJ/mol,反应为电化学步骤控制;交流阻抗谱观察到氧阴极还原由3个明显的线圈组成,表明氧阴极还原分3步进行,第1个圆弧随过电位的增大而显著减小,表明第1步电荷转移过程的确为氧还原反应的速率控制步骤;导电聚苯胺的高比表面积与MnO2的多微毛细管结构使氧在该复合电极上还原变得容易.     

具有共轭结构的导电聚合物及其应用

具有共轭结构的导电聚合物在微电子学和光电子领域有着广泛的应用前景。文章简要介绍了这类聚合物材料的主要合成方法、导电机理及其应用概况，并对目前该领域的研究进展作了扼要评述。     

Synthesis of achiral PEG‐PANI rod‐coil block copolymers and their helical superstructures

Poly(ethylene glycol) (PEG) was modified with aniline groups at both the end, and then PEG‐PANI rod‐coil block polymers have been synthesized by polymerization of the aniline with the aniline‐modified PEG. FTIR, NMR, and elemental analysis provided the chemical strucutre of the as‐prepared polymers. The achiral rod‐coil copolymer could form different superstructures by means of self‐assembly when adding diethyl ether into its THF solution and the length of PANI segments is a key factor to the superstructures. AFM measurements revealed that they form spring‐like helical superstructures from the short PANI‐containing copolymers while these form fibrous helical superstructures from the longer PANI‐containing copolymer. A possible mechanism of the helical superstructures is suggested in this article and the driving force is believed the π–π stacking of the rigid segment of the copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 12–20, 2008     

Properties of proton-conducting Nafion-type membranes with Nanometer-thick polyaniline surface layers

The study is directed to the improving of proton-conducting Nafion-type membranes for using in fuel cells with direct oxidation of liquid fuels. Nanometer-thick layer of polyaniline (in its conducting emerald-dine form) was deposited onto the membrane surface by in situ polymerization. The structure of the polyaniline layer is studied, as well as the properties of thus modified membranes (electronic and proton conduction, permeability for methanol, thermal stability). A method of platinum catalyst deposition onto the Nafion-modifying polyaniline layer is developed.     

Highly conductive soluble terpolymers of aniline,toluidine, and o‐aminobenzoic acid/m‐aminobenzenesulfonic acid

Two series of terpolymers, one of o‐/m‐toluidine and aniline with o‐aminobenzoic acid and the other of o‐/m‐toluidine and aniline with m‐aminobenzenesulfonic acid, have been synthesized by oxidative polymerization via an emulsion method with ammonium persulfate as the oxidant and HCl as the external dopant. The terpolymers exhibit excellent solubility and retain the high conductivity (∼1 S cm⁻¹) characteristic of the unsubstituted homopolymer, polyaniline. The terpolymers also possess higher thermal stability than polyaniline. This can be attributed to the presence of internal doping groups and substituents, which introduce flexibility to the otherwise rigid polyaniline backbone. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3040–3048, 2005