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。     

新型联苯胺基窄带隙共轭聚合物的光学及电化学性能研究

随着化石燃料的日益枯竭,人类社会对能源的需求在不断增长。为了平衡能量应用需求并提升能量使用效率,开发高效能量转换材料与电化学储能材料成为当前研究的重要课题。导电聚合物基电极材料面临着相应储能器件能量密度、功率密度、循环性能不高的挑战,需进行结构改性提高电导率、改善界面性质。鉴于共轭高分子的电子结构、光学及电化学性质由共轭链骨架结构决定,对导电共轭聚合物进行结构修饰以提升其电荷传输性能和载流子迁移率,进而设计合成新型高迁移率导电聚合物基共轭聚合物是提高相应器件特性的关键所在。已有研究大多借助复杂的结构设计来实现提升迁移率,设计合成了结构简单,有助提升电荷迁移的新型窄带隙聚联苯胺基共轭聚合物聚物。通过光谱学及电化学方法对材料结构与性能进行了表征分析。采用核磁共振氢谱、红外光谱,X射线粉末衍射对单体及聚合物进行了结构表征,通过紫外光谱、紫外可见漫反射、循环伏安、计时电位、交流阻抗对其进行了光学及电化学性能测试。结果表明,成功制得具有预期结构的共轭聚合物,所得聚合物结晶性较佳,光学带隙Eopt_g为1.85 eV,HOMO及LUMO能级分别为-5.44和-3.59 eV,前者高于,后者则低于大部分文献值,呈现可同时促进p-型和n-型掺杂的结构特性,具备增强材料容纳电荷能力的性能优势。聚合物储能特性受化学结构、晶体结构及微观形貌综合影响。改善材料微观结构特性有助于提升其电子电导率,但层状致密块体形貌特征又使其离子电导率受限。电化学性能测试结果显示,聚合物具有一定电化学活性,具有较小的电荷转移阻抗,具备基本满足使离子顺利扩散的条件,0.05 A·g-1时的放电比电容达256.6 F·g-1。研究结果表明,制得的联苯胺基窄带隙共轭聚合物在光电转换、储能及微型电子器件中有广阔的应用前景。     

导电聚合物P3MT,P3BT,P3HT的低温物性研究

在导电聚合物的研究领域中,聚噻吩(PTh)是近来引起广泛注意的一种共轭聚合物.为了进一步了解其导电机制,本文对聚噻盼的一系列衍生物 P3MT,P3BT,P3HT 的低温电导,低温高压及低温热电势等基本物性做了系统的研究,并找出这些物性随取代基大小的变化规律.     

聚吡咯电化学掺杂过程的拉曼光谱研究

共轭导电聚合物经过掺杂,电导率可以提高十几个数量级,由绝缘体变为导体.但是,掺杂对聚合物链结构的影响方面,人们目前尚所知甚少.从实验的角度看,由于物性测量结果和材料的制备过程密切相关,往往不容易重复,有时还会出现一些令人困惑的假象.     

导电复合材料的研制

为了适应Z-pinch物理实验对新材料的要求，2003年来对导电复合材料进行了初步研制。由于导电聚合物结构的特殊性，导致了导电聚合物机械加工性能很差，聚吡咯是一种具有较好的热、化学氧化和光照稳定性导电聚合物，因此利用有机材料作为基体，吸附吡咯同时进行氧化聚合，可得到性能较好导电复合材料。在导电聚合物的研制过程中，主要涉及基体材料的选择、氧化剂的选择以及反应时间对复合材料的表面电阻的影响。     

含炔基有机硅共轭聚合物的光谱性能研究

应用荧光光谱、紫外光谱对不同结构的含炔基有机硅共轭聚合物的发光性能进行了表征和研究。探讨了聚合物主链上Si原子取代基的结构以及主链中炔基单元结构对其发光性能的影响,研究结果表明,聚合物可在219～260 nm处有紫外吸收,随着Si原子上取代基共轭性能的增强,以及主链中炔基数目的增多、链段共轭程度的增大,最大吸收波长红移。取代基的影响较小,主链共轭结构对吸收光谱的影响明显。不同主链结构的共轭聚合物在320～353 nm处发出一定强度的荧光。结果显示,聚合物主链共轭基团的结构对发射光谱具有明显的影响,随着主链中炔基数目的增多,最大发射波长显著向长波方向移动。由于此类聚合物的特殊结构使得他们具有良好的热学稳定性,因此这类聚合物具有潜在的光学应用价值。     

共轭聚合物单分子构象和能量转移特性研究

利用基于宽场显微光学系统的单分子散焦成像技术测量了不同构象poly[2,7-(9,9-dioctylfluorene)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole](PFO-DBT)共轭聚合物单分子的光物理与动力学特性.通过分析共轭聚合物单分子的荧光轨迹和对应的发射偶极取向变化识别共轭聚合物单分子发光单元,发现延伸构象下的单分子呈现多发色团发光特性,而折叠构象下的单分子保持高效链间能量转移,呈现单个发色团发光特性.共轭聚合物单分子构象对能量转移效率的影响可用于研究基于共轭聚合物的光电器件和分子器件.     

共轭聚合物中的量子限制效应和能量传递

在共混的两种共轭聚合物中,采用分子自级装技术制备了嵌段共轭聚合物量子线的异质结构,通过室温下吸收光谱、发光光谱和激姨光谱的研究证实了在这种嵌段共轭聚合物量子线的异质结构中存在很强的激子限制效应以及链内和链间的有效能量传递。     

有机聚合物受体给体复合体薄膜光伏电池性能研究

提出了用一种新的有机物－聚合物复合体薄膜制备受体给体聚合物光伏电池的思路,用于克服由于激子或极化子扩散范围短而熄灭造成的电荷分离与传输效率低的缺陷.在采用对称N,N′-二苯并咪唑3,4,9,10-四羧酸二亚酰胺和聚(2,5-二十五烷氧基对－苯撑乙烯)(ROPPV)为原材料制备成复合体薄膜,对其电学、光学及用其制作的光伏电池的性能进行了讨论.结果显示了导电聚合物－有机物复合体可代表一类新的有机半导体材料用于制造光伏电池 关键词： 有机光伏电池 有机染料 共轭聚合物 异质结     

非共轭聚合物PPV衍生物中烷氧基因对发光性质的影响

研究了3种非共轭PPV聚合物以及3种共轭PPV衍生物的吸收谱和发光光谱的特性。非共轭PPV聚合物上的侧链烷氧基团有着很强的供电子能力，对调节非共轭聚合物能带带隙有重要的影响，且离主链较近的碳原子对能带结构也有一定的影响。但当侧链上的碳原子数量很大，从7个小时一直变化到10小时，共轭PPV衍生物的吸收光谱和发光光谱变化较少，表明对能带结构影响小。     

导电高聚物的微波吸收机理的研究

本文以“导电孤岛”物理模型阐明界面极化率对导电高聚物电损耗的影响。通过物理模型的数学解析表明,导电高聚物中的“导电孤岛”是导电高聚物的介电损耗的主要来源,并发现“导电孤岛”所引起的介电损耗依赖于“导电孤岛”本身的电导率、介电常数以及它的体积分数。“导电孤岛”物理模型所揭示的介电特性与实验中所观祭到的微波吸收率和导电高聚物的室温电导率有关的实验事实相符合。 关键词：     

“Synthetic metals”: a novel role for organic polymers

Since the initial discovery in 1977, that polyacetylene (CH)_x, now commonly known as the prototype conducting polymer, could be p- or n-doped either chemically or electronically to the metallic state, the development of the field conducting polymers, “synthetic metals”, has continued to accelerate at an unexpectedly rapid rate and a variety of other conducting polymers and their derivatives have been discovered. Potential new science/technology has been developed by combining the now well established field of electronic polymers (intrinsically conducting polymers – “synthetic metals”, when doped) with the emerging field of nanoscience (one dimension <100 nm). A simple and inexpensive method is described for producing conducting patterns of electronic polymers on plastic and paper from computer-designed patterns. This method, “Line Patterning”, does not involve printing of the conducting polymers. The difference in hydrophobicity/hydrophilicity between a substrate and a line of regular toner printed on it by a non-modified, standard ofiice laser printer results in conducting polymer areas separated by insulating toner lines.     

不稳定晶格的能带计算

由于导电高分子是宽能带体系,紧束缚近似下的Su-Schrieffer-Heeger(缩写为SSH)模型存在一系列问题,需要加以改进才能满意地研究导电高分子的一维晶格的不稳定性。本工作将稳定晶格的Wannier函数方法加以推广,用来计算不稳定晶格的电子能带。数值结果表明,本方法的收敛性很快,取到三近邻时,能带的准确度可优于1％。同时能很精确地确定不稳定性所引起的二聚化。 关键词：     

Novel properties of nanoscale organic–inorganic systems and photonic crystals — conducting polymers in nanoscale periodic structures,microcavities and photonic crystals

Conducting polymer/C₆₀and C₆₀doped conducting polymer/C₆₀heterojunctions have been fabricated and found to exhibit remarkably enhanced photoresponse due to the highly effective photoinduced charge transfer at the interface. In conducting polymer/C₆₀alkali metal nanoscale composite systems, multiphase superconductivity has been clarified and explained by taking the coupling of nanoscale grains by Josephson junctions into consideration. As examples of intramolecular organic-inorganic combined systems, unique electrical and optical characteristics have been revealed in oligosilanylene oligophenylene polymers. Electroluminescence has been demonstrated in organic-inorganic junction devices such as conducting polymer/porous Si and conducting polymer/diamond junctions. Conducting, polymer-based nanoscale multilayer systems have been studied utilizing molecular self-assembly method and novel photosensitive characteristics have been revealed. \indent Novel optical and electrical properties of conducting polymers infiltrated in a photonic crystal, synthetic opal made of SiO₂spheres of several hundred nm in diameter, and also a conducting polymer replica have been revealed. A clear diffraction pattern was observed in a photonic crystal infiltrated with conducting polymers, and transmission spectra are dependent on various ambient conditions. Their photoluminescence (PL) spectra, spectral narrowing of PL and lasing characteristics at relatively low optical excitation have also been clarified. Novel conducting characteristics of conducting polymers in a photonic crystal that was prepared by pyrolysis of a polymer replica of opal have also been observed.     

Transparent conducting hybrid thin films fabricated by layer-by-layer assembly of single-wall carbon nanotubes and conducting polymers

The effect of conducting polymers on the performance of transparent conducting SWNT thin films fabricated by the layer-by-layer (LBL) assembly has been investigated. Transparent conducting SWNT thin films were fabricated by the LBL assembly in two ways, one using conducting polymers, PEDOT-PEG, and the other using non-conducting polymers, PAH, and their electrical and optical properties were compared. The sheet resistance of (PSS-SWNT/PEDOT-PEG) _n films is more than thrice lower than that of (PSS-SWNT/PAH) _n films for the same n while the decrease of optical transmittance due to the absorbance of PEDOT-PEG is fairly small (ca. 2?% at n=30). The conductivity ratio of the (PSS-SWNT/PEDOT-PEG)₃₀ is 3.3 times larger than that of the (PSS-SWNT/PAH)₃₀. These figures indicate that the performance of the transparent conducting SWNT thin films fabricated by the LBL assembly is highly improved by using conducting polymers instead of non-conducting ones.     

Conducting polymer based biomolecular electronic devices

Biomolecular electronics is rapidly evolving from physics, chemistry, biology, electronics and information technology. Organic materials such as proteins, pigments and conducting polymers have been considered as alternatives for carrying out the functions that are presently being performed by semiconductor silicon. Conducting polymers such as polypyrroles, polythiophenes and polyanilines have been projected for applications for a wide range of biomolecular electronic devices such as optical, electronic, drug-delivery, memory and biosensing devices. Our group has been actively working towards the application of conducting polymers to Schottky diodes, metal-insulator-semiconductor (MIS) devices and biosensors for the past 10 years. This paper is a review of some of the results obtained at our laboratory in the area of conducting polymer biomolecular electronics.     

Optical characterization of metallic aerosols

Airborne metallic particulates from industry and urban sources are highly conducting aerosols. The characterization of these pollutant particles is important for environment monitoring and protection. Because these metallic particulates are highly reflective, their effect on local weather or regional radiation budget may also need to be studied. In this work, light scattering characteristics of these metallic aerosols are studied using exact solutions on perfectly conducting spherical and cylindrical particles. It is found that for perfectly conducting spheres and cylinders, when scattering angle is larger than 90° the linear polarization degree of the scattered light is very close to zero. This light scattering characteristics of perfectly conducting particles is significantly different from that of other aerosols. When these perfectly conducting particles are immersed in an absorbing medium, this light scattering characteristics does not show significant change. Therefore, measuring the linear polarization of scattered lights at backward scattering angles can detect and distinguish metallic particulates from other aerosols. This result provides a great potential of metallic aerosol detection and monitoring for environmental protection.     

Charge carrier transport in conducting polymers on the metal side of the metal-insulator transition: A review

The advances achieved in the field of the synthesis of conducting polymer films and the results of experimental investigations of the mechanism of charge carrier transport in heavily doped conducting polymer films on the metal side of the metal-insulator transition have been considered. The samples studied belong to the last generation of conducting polymers with a low degree of structural disorder, which makes it possible to dope samples to a highly conducting state characterized by an increased stability. Apart from the study of the morphology, structure, and doping conditions, the mechanism of low-temperature transport in these polymers has been investigated in detail. The results of investigations of the transport at low temperatures (T < 1 K) have been described, and a phenomenological model of charge carrier transfer in these systems has been proposed. The polymers under investigation have been widely used as injecting and accumulating layers in light-emitting organic diodes and solar cells.     

功能聚合物:从薄膜器件到纳米器件

文章简要回顾了功能聚合物的发现和发展历程,着重介绍了其在发光二极管、太阳能电池、场效应晶体管、传感器件、纳米材料与器件中的应用。