【作者】 王泳；

【导师】 汪茫； 陈红征；

【作者基本信息】 浙江大学 ， 材料学， 2005， 硕士

【摘要】 酞菁类化合物因其独特的理化性能,在材料领域已被广泛采用,但其难熔、难溶性,制约了它的进一步研究和应用。因此,可溶性酞菁及其相关复合材料的制备与性能研究,具有重要的科学意义和应用前景。第一章综述了酞菁及其衍生物的合成、薄膜制备以及在材料领域的应用研究进展,并在此基础上提出了本论文的研究思路:以提高溶解性为目标,探寻一种简便、高效的合成取代酞菁的方法,并以共溶液法制备基于酞菁的有机半导体复合材料,研究复合材料结构与性能之间的关系。论文第二章论述了采用相转移催化反应合成了酯基取代酞菁铜。制备了不同取代基长度的酯基取代酞菁铜,通过对其溶液、薄膜的吸收光谱和X射线衍射谱的研究,发现取代基长度对酯基取代酞菁铜分子聚集状态产生显著的影响,导致其光电导性能的差异。制备了酯基取代酞菁铜LB膜,π-A曲线以及薄膜形态的变化表明,取代基长度对酯基取代酞菁铜成膜性具有重要影响,表现在以酯基取代酞菁铜LB膜为气敏层的气敏测试元件,对三甲基胺(TMA)、甲醇(CH3OH)气体的敏感性的差异。在第三章中,通过化学反应制备了十二酯基接枝纳米碳管,以改善碳管在有机溶剂中的分散性。以溶液共混法制备了酯基取代酞菁铜/纳米碳管复合材料,以该复合材料为载流子产生层制备双层感光体,其光敏性在全光谱范围比单一的酯基取代酞菁铜有了明显提高,当纳米碳管含量达到8%时,复合材料的光敏性达到最佳。由酯基取代酞菁铜到纳米碳管的分子间光致电荷转移作用,是光电导性能优化的主要原因。进一步采用LB膜技术,制备了酯基取代酞菁铜/修饰纳米碳管的复合薄膜,发现薄膜中的纳米碳管在一定程度上取向。与单纯的酯基取代酞菁铜LB膜相比,复合LB膜对还原性气体(三甲基胺)的气敏性有所下降。论文第四章论述了采用相转移催化反应对苝酐进行了化学改性,改善了其溶解性。以溶液共混法制备了酯基取代酞菁铜/酯基取代苝复合材料,并以其为载流子产生层制备双层感光体,其光电导性能优于单纯酯基取代酞菁。XRD测_一一—一一-一~粗要一—一_--一—试及复合薄膜的形貌研究表明,以醋基取代酞著铜为P型材料、以酷基取代花为N型材料的有机本体异质结结构,是复合材料光导性提高的主要原因。酉旨基取代酞蓄铜与酷基取代花在光谱吸收上存在互补性,是复合材料的光电导性能优化的另一原因。进一步采用LB膜技术,制备了醋基取代酞蓄铜酒旨基取代花复合膜。二一A曲线表明,两种材料的成膜性存在较大差异,分子结构的对称性是决定因素。与溶液浇铸复合膜相比,复合LB膜的形貌发生了很大变化,说明了成膜方式对薄膜结构有较大影响。关键词:酉旨基取代酞蓄铜,相转移催化,复合材料,光电导性能,LB膜,气敏性亩更多还原

【Abstract】 In Chapter 1, the recent progresses in synthesis, thin film fabrication and applications in the materials of phthalocyanine (Pc) and their derivatives were summarized, which followed by a proposal of the researching theme in this thesis: to improve the solubility in organic solvents, probing a simpler and more efficient method of synthesizing substituted Pc; fabricating organic semiconductor composite materials based on substituted Pc by simple solution blending method and studying the relationship between structure and properties of the composites further.Ester substituted CuPc were synthesized by the phase transfer catalyzed reaction in Chapter 2. Ester substituted CuPc with the deferent length of substituent group were synthesized by the same method. Because of the difference in the substituent group length of these compounds, the morphology and the congregation of the molecules in their casting films is different, leading to the different photoconductivities of them. The Langmuir-Blodgett (LB) film of ester substituted CuPc were fabricated subsequently. Changes in it - A curves and the morphology of LB films indicated that the difference in the substituent groups length of ester substituted CuPc led to the different film-forming characteristic of them. The gas sensing devices were fabricated by LB technology and the measured gases were tri-methyl-amine (TMA) andmethanol (CH3OH).In Chapter 3, the multi-wall carbon nanotubes (MWCNTs) bonded with dodecyl ester groups were obtained by chemical modification. The modified CNTs showed improved solubility in organic solvents. The ester substituted CuPc/ modified CNTs composite was fabricated by simple solution-blending method. The photo sensitivity of the dual-layer photoreceptor with ester substituted CuPc/ modified CNTs composite as charge generation material was higher than that with pristine ester substituted CuPc, and increased with increasing the content of modified CNTs in the composites. The optimal performance was obtained when the weight ratio of doped CNTs was 8%. The efficiency of charge carrier separation increased as well due to thephotoinduced charge transfer from ester substituted CuPc to modified CNTs, which might also contribute to the improved photosensitivity of the ester substituted CuPc/ modified CNTs composite. The hybrid LB film of ester substituted CuPc/ modified CNTs were fabricated subsequently. Because of the presence of ester substituted CuPc, the aggregation of modified CNTs was confined and the tropism of modified CNTs was obtained. After doping the modified CNTs, the sensitivities to TMA of ester substituted CuPc decreased.Ester substituted perylene were synthesized by the phase transfer catalyzed reaction in Chapter 4. The ester substituted CuPc/ ester substituted perylene composite was fabricated by solution-blending method. The photosensitivity of the dual-layer photoreceptor with ester substituted CuPc/ ester substituted perylene composite as charge generation material was higher than that with pristine ester substituted CuPc, and increased with increasing the content of ester substituted perylene in the composites. It was explained that, as demonstrated by XRD and the morphology of casting films, the bulk heteroj unction formed in the composites (ester substituted CuPc as P material and ester substituted perylene as N material). Furthermore, the adsorption spectra of ester substituted CuPc and ester substituted perylene were complementary, which might contribute to the improved efficiency of light adsorption. The hybrid LB film of ester substituted CuPc/ ester substituted perylene were fabricated subsequently. As shown in n - A curves, the degree of symmetry in molecule structure of two kinds of materials effected on their film-forming characteristic. In addition, the morphology of LB film changed greatly compared to that of casting film, indicating that the structure of composites film could be affacted by the fabrication method of thin film.更多还原