【作者】 叶坚；

【导师】 陈红征；

【作者基本信息】 浙江大学 ， 高分子化学与物理， 2003， 硕士

【摘要】 有机半导体光电器件由于其诱人的应用前景和巨大的市场正日益引起人们的广泛关注和研究兴趣，其中唯一已进行大规模产业化的有机半导体光电器件是有机光导鼓(OPC)。目前双层OPC鼓的研究技术和制备工艺已经成熟，各大公司为利益所驱去，纷纷把研究的重点转移到了低成本的单层OPC鼓上。本论文旨在开发新一类高性能的有机单层光电导体，探索其凝聚态结构与光电导性能之间的关系，丰富有机半导体理论体系。 论文第一章首先评述了电子照相技术的发展历史和发展趋势，同时介绍了有机光电导材料的种类和光电导体的结构，提出可通过复合、纳米化和研制新型的电子传输材料三种手段来制备高性能有机单层光电导体。综述了酞菁类纳米光电导材料的制备方法，发现纳米光电导材料优异的光电性能来源于材料的量子尺寸效应。本章还重点综述了有机电子传输材料研究的最新进展，总结和比较了有机材料载流子迁移率的测试方法，并提出了设计高性能有机电子传输材料的若干原则。 在论文的第二章，我们研究了氯化酞菁铟／酞菁氧钛(InClPc／TiOPc)载流子发生材料的复合体系的光电导性能。结果表明，共混复合后，其光电导性能表现出负效应，并发现酞菁中心金属与其相连的氮原子之间的部分电荷转移是引起复合体系光电导性能变化的根本原因，同时复合体系中的电子空穴对的分离效率是影响光电性能的一个重要因素。InClPc／TiOPc复合体系光电导性能的研究支持了“电荷逐步转移”的理论模型。 在论文的第三章，我们研究了有机电子传输材料2，4，7-三硝基芴酮(TNF)对有机单层光电导体(TiOPc／BAH／PC体系)光敏性能的影响，发现少量的TNF(TNF／BAH≤0.005)可使得单层有机光电导体的光敏性能大幅度增强，并探索了其影响因素和微观机理。通过对DSC、紫外可见光谱和循环伏安特性的综合研究，发现随着TNF浓度的增加，TNF和BAH之间形成了电荷转移络合物，从而导致光电导体光敏性能的下降。本章从电荷传输材料复合的角度研究了这种光敏性增强效应和电荷转移络合物的形成，为设计和开发新型的有机光电导体提供了一种新途径。 在论文的第四章，我们采用新型的络合物溶解法进行InCIPC有机半导体纳米微粒的制备，用聚合物聚乙烯咋哇（PVK）将其包裹，并对其进行了表征。络合物溶解法的机理是电子给体受体络合物的形成；紫外吸收光谱表明纳米微粒的两个吸收峰较之本体材料发生了显著的蓝移；PVK包覆的纳米微粒固体粉木的衍射峰明显变宽；对纳米微粒光电导性能的研究发现比本体微晶的光敏性有了很大的提高。 论文的最后一章中，我们合成了具有较好的电子传输性能的化合物＊’一二苯基四竣酸花酚亚胺（DDP）；研究了其溶解性、热稳定性、晶体结构、红外光谱、紫外吸收光谱和蒸镀薄膜的属性，并用量子化学计算方法模拟其单分子的空间构型；载流子迁移率测试的结果约为IX10“、m’／V”’·s“’。本章的研究旨在对有机电子传输材料进行初步的探索，为今后新型的高迁移率有机电子传输材料的合成和表征，以及应用等方面积累经验。 综上所述，我们分别从载流子光生材料的复合化和纳米化、电荷传输材料的复合化和新型化等四个角度出发研制高性能的有机单层光电导体，初步揭示了有机光电材料的凝聚态结构、激发态结构以及光电性能之间的关联，为有机半导体理论的深入研究和单层光导鼓的产业化提供了数据积累。更多还原

【Abstract】 Recently organic optoelectronic devices have attracted intensive interest among scientists and technologists because of their huge market and intriguing potential applications. Among these devices, organic photoconductor (OPC) drum is the only one who has been put into market in large scale. At present, because scientific research and fabrication techniques of double-layered OPC drum are considerable mature, more and more attention has been paid to single-layered OPC drum for its simple structure and low cost. In the thesis, we aim to design a new kind of single-layered photoconductor with high performance, to study the relationship between aggregate state structure and photoconductivity, and to enrich organic semiconductive theory system.In the first chapter of the dissertation, we review the development history and the trend of xerography technology, present a series of organic semiconductive materials and their device structures, and bring forward three ways to prepare single-layered photoconductor with high performance by dimixing, preparing nanomaterials, and synthesizing new organic electron transport materials. The methods used to prepare nanostructure phthalocyanines are introduced. It is found that the quantum scale effect in organic nanostructures is the real reason for the unique photoconductive properties. The recent development of organic electron transport materials are reviewed as well. Several technologies for charge carrier mobility measurement are summarized and compared, and a series of basic principles for designing high-performance organic electron transport materials are suggested as well.In the second chapter, a single-layered photoconductor was made incorporating oxotitanium phthalocyanine/ chloroindium phthalocyanine (InClPc/TiOPc) composite as charge generation material (COM) into polymer matrix. The negative photoconductivity effect was found in the dimixing phthalocyanine composites. The experiment results indicated that the negative photoconductivity effects were closely related with the partial charge transfer from the center metals to phthalocyanine rings, and the separation efficiency of photocarriers was a key factor to thephotoconductivity.In the third chapter, the organic single-layered photoreceptors were prepared, which consisted of polycarbonate matrix containing dispersed N,N’-diethyl-4-aminobenzaldehyde-l-phenyl-l’-(a-naphthyl)-hydrazone (BAH) and 2,4,7-trinitryl-fluorenone (TNF) as bipolar charge transport materials (CTM), as well as TiOPc as charge generation material (COM). The influence of organic electron transport material on the photosensitivity in the photoreceptors was investigated. It was found that small amount of TNF (TNF/BAH<0.005) could improve the photosensitivity of photoreceptors greatly, i.e., the enhanced photoconductive effect, but the further increase of TNF concentration would lead to the decline of the photosensitivity. DSC, UV-Vis and cyclic voltammograms studies showed that the enhanced photoconductivity might be resulted from the improvement of the separation efficiency of charge-carrier pairs, and that the decline of photosensitivity was due to the formation of the charge transfer complex of TNF-BAH. The enhanced photoconductive effect from small amount of TNF facilitates the preparations of new organic photoconductive devices under the drive of low fields.In the fourth chapter, InClPc nanoparticles embedded in poly(N-vinylcarbzaole) (PVK) were prepared successfully by dissolving InClPc in aprotic organic solvent/Lewis acid with great concentration for the formation of electron donor-acceptor complexes, i.e., the method of complexation-mediated solubilization. The fabricated InClPc nanoparticles were characterized by means of UV/Vis absorption, X-ray diffraction pattern, and TEM. The results showed that InClPc nanoparticles were ball-shaped with a size of 25-50 run, that their diffraction peaks become broader, and that the blue-shift in UV/VIS absorption was also observed. The photoconductivity of InClPc nanoparticles in single-更多还原