【作者】 李健；

【导师】 王世荣；

【作者基本信息】 天津大学 ， 应用化学， 2013， 硕士

【摘要】 有机场效应器件被广泛应用于传感器和大规模集成电路等领域，是目前光电领域的一大研究热点。在有机场效应器件中，有机半导体材料作为有源层材料，其性能的优劣直接影响着器件的性能。有机半导体材料根据载流子的不同可分为p型材料和n型材料。n型有机半导体材料在互补逻辑电路、p-n结和双极性晶体管等应用中起着十分重要的作用，但由于现有品种较少，限制了n型材料的发展与应用。酞菁化合物因其大环共轭体系以及良好的热稳定性，易于蒸镀成膜的特性，已被大量的应用在场效应晶体管中。本文通过向酞菁环引入氟取代基，降低酞菁分子的电子云密度，合成了具有n型半导体材料性质的四氟金属酞菁，并将其应用到有机场效应器件中。本文首先以4-硝基邻苯二甲酰亚胺为原料，经还原，重氮化和重氮盐热分解反应合成出了中间体4-氟邻苯二甲酰亚胺，并对该工艺路线进行了优化。在优化过工艺条件下，4-氟邻苯二甲酰亚胺的总收率为35.2%，纯度为97.2%。又以4-氟邻苯二甲酰亚胺为原料，与尿素和金属盐通过固相反应合成了5种四氟取代的金属酞菁化合物MPcF4（M=Fe、Co、Ni、Cu、Zn），收率分别为：44.7％、68.4％、72.0％、64.6％和54.4％。利用红外光谱和基质辅助激光解析飞行时间质谱对合成产物进行了结构表征，均验证了结构的正确性。研究了四氟金属酞菁的紫外、荧光、热性能、溶解性和场效应器件应用等性能，结果表明：五种金属酞菁在N,N’-二甲基甲酰胺溶剂（DMF）中紫外-可见吸收光谱最大吸收波长在657~672nm之间，NiPcF4和CuPcF4在DMF溶剂中均有聚集现象产生；溶液浓度的增大、溶剂极性的增大和氟取代基的引入，都会导致酞菁溶液的聚集现象更加明显；四氟金属酞菁在DMF溶剂中的荧光发射谱最大发射波长在598~672nm之间。随中心金属原子序数的增加，荧光发射光谱发生红移；四氟金属酞菁都有较高的分解温度，分解温度均在270℃以上，热稳定性良好；溶解性测试表明，四氟金属酞菁能微溶于吡啶、DMF和DMSO，但不溶于二氯甲烷和乙腈；将CuPcF4作为有源层材料应用到有机场效应器件中，器件显示了n沟道特性，说明CuPcF4能够作为n型半导体材料应用到场效应器件中， CuPcF4器件的迁移率和开关电流比分别为0.014cm2/V·s和100。更多还原

【Abstract】 Organic field-effect transistors(OFETs) have attracted a lot of attention due totheir wide application in the area of sensors and large scale integrated circuitscurrently. As the active layer of organic field-effect device, organic semiconductormaterials affect the property of organic field-effect device. Organic field effectmaterials are divided into two classes according to the type of carriers: p-type andn-type materials. N-type OFETs materials are important part of complementary logiccircuit, p-n junction diode and bipolar transistor, but less varieties astrict theirdevelopment and application. Metallophthalocyanines are widely used in field-effectdevices for their macrocyclic conjugated system, good thermal stability andevaporation into film easily. In this paper, F group is introduced to themetallophthalocyanine molecule to decrease the electron density. In this way, wesynthesized2,9,16,23-tetrafluoro metallophthalocyanines which can be used as n-typesemiconductor materials and applied the metal tetrafluorophthalocyanines to organicfield-effect devices.In this paper,4-fluorophthalimide was synthesized using4-nitrophthalimide asraw material by reduction, diazotization and decomposition reaction of diazoniumsalts and the synthetic process was optimized. Under optimum conditions, the totalyield of4-fluorophthalimide was35.2％and the purity was97.2％. The five kind ofmetal tetrafluorophthalocyanines MPcF4(M=Fe、Co、Ni、Cu、Zn) were synthesizedusing4-fluorophthalimide as raw material with carbamide and metal salts by solidstate reaction and the yield were44.7％,68.4％,72.0％,64.6％and54.4％,respectively. The structure of MPcF4were characterized by IR and MALDI-TOF-MS.The properties of UV-vis, fluorescence, thermal, solubility and field-effect devicewere studied and the results showed that the absorption maxima of UV-vis spectrumin DMF was in the range of657~672nm. NiPcF4and CuPcF4displayed aggregationbehavior in UV-vis spectrum. Introduction of F group and increasement ofconcentration and solvent polarity all led to aggregation; The emission maxima offluorescence spectrum in DMF was in the range of598~672nm. With the atomicnumber of central metal was improved, the fluorescence spectra displayed a trend ofred shift; The metal tetrafluorophthalocyanines all possess decomposition temperatureabove270℃indicating that they have a excellent thermal stability; All the metaltetrafluorophthalocyanines can be slightly soluble in pyridine, DMF and DMSO, but do not dissolve in CH2Cl2and acetonitrile; CuPcF4was applied in organic field-effectdevice and displayed n-channel performance, indicating that CuPcF4can be used asn-type semiconductor material in field-effect device. The field-effect mobility is0.014cm2/V·s and the ratio of switched-current is100.更多还原