酞菁类n型半导体材料的合成及性质表征

发布时间：2018-06-05 10:46

  本文选题：酞菁 + 亚酞菁　； 参考：《天津理工大学》2017年硕士论文

【摘要】：有机场效应晶体管(Organic field-effect transistor,OFET)由于其质轻、低成本、制备工艺简单和大规模集成等优势,逐渐成为有机光电领域的研究热点。有机半导体材料是OFETs的重要组成部分,它直接影响OFETs载流子迁移率。到现今为止,研究较多的有机半导体材料其材型总体上都是p型,而n型则只占一小部分,另外n型材料又是制备双极性场效应晶体管、p-n结以及互补逻辑电路的不可或缺的组成成分,因此,开发n型材料对于OFETs器件的研究具有非常重要的价值。酞菁以及亚酞菁类化合物拥有多π电子共轭体系、很好的热稳定性能以及真空蒸镀成膜等特点,是制造OFETs器件的良好有机半导体材料。本文通过将氟原子取代基引入到化合物分子中,将p型材料转变成n型材料,并将它们应用到OFETs中。本文首先是用四氟邻苯二甲酸酐作原料,依次经过亚胺化、酰胺化和脱水反应得到原料3,4,5,6-四氟邻苯二甲腈,然后用3,4,5,6-四氟邻苯二腈作原料制得了3种全氟金属酞菁MPcF16(M=Cu,Zn,VO),其收率分别为52.46%,48.00%,14.90%;又用3,4,5,6-四氟邻苯二甲腈作原料制得了3种全氟硼亚酞菁X-BsubPcF12(X=Br,Cl,F),其收率分别为30.01%,33.98%,28.57%;再用邻苯二甲腈作原料制得了3种硼亚酞菁X-Bsubpc(X=Br,Cl,F),其产率分别是42.01%,38.97%,10.43%。利用红外光谱、核磁共振以及质谱等手段对合成的物质进行结构表征。利用紫外-可见光谱、荧光光谱手段测定它们的光学性质;通过热重分析来判定它们的热稳定性能;利用循环伏安(CV)曲线对它们进行电化学性能分析。化合物的光物理性能测定结果显示:全氟金属酞菁化合物MPcF16(M=Cu,Zn,VO)在溶剂邻二氯苯(DCB)、N,N-二甲基甲酰胺(DMF)、四氢呋喃(THF)中的紫外最大吸收波长均在665~720 nm之间;全氟硼亚酞菁化合物X-BsubPcF12(X=Br,Cl,F)在甲苯(Toluene),氯仿(TCM),二氯甲烷(DCM)以及邻二氯苯等溶剂中的紫外最大吸收波长均位于570~580 nm之间;硼亚酞菁X-Bsubpc(X=Br,Cl,F)在Toluene,TCM,DCM等溶剂中的紫外最大吸收波长均位于560~570 nm之间。合成物质的电化学性能测定结果表明:全氟金属酞菁化合物MPcF16(M=Cu,Zn,VO)的LUMO能级值介于-4.57~-4.50 eV之间;全氟硼亚酞菁化合物X-BsubPcF12(X=Br,Cl,F)的LUMO能级值介于-4.08~-4.05eV之间;硼亚酞菁化合物X-BsubPc(X=Br,Cl,F)的LUMO能级值介于-4.03~-4.00 eV之间。所合成物质的热稳定性能测定结果显示:全氟金属酞菁化合物MPcF16(M=Cu,Zn,VO)其热分解温度(Td)均在380℃以上;全氟硼亚酞菁化合物X-BsubPcF12(X=Br,Cl,F)的Td都在360℃以上;硼亚酞菁X-BsubPc(X=Br,Cl,F)的Td均在280℃以上,说明它们也具有良好的热稳定性能。选取全氟酞菁锌ZnPcF16作为有源层应用于OFETs,器件显示出了n-沟道特性,其器件迁移率是1.3×10-2 cm2/V s。
[Abstract]:Due to its advantages of light weight, low cost, simple preparation process and large scale integration, organic field-effect transistors have gradually become the research hotspot in the field of organic photoelectricity. Organic semiconductor material is an important part of OFETs, which directly affects the carrier mobility of OFETs. Up to now, most of the organic semiconductor materials studied are p-type in general, and n-type in a small part. In addition, n-type material is an indispensable component in the fabrication of bipolar field-effect transistors and complementary logic circuits. Therefore, the development of n-type materials is of great value for the research of OFETs devices. Phthalocyanines and phthalocyanines have many 蟺 electron conjugation systems, good thermal stability and vacuum evaporation film, etc. They are good organic semiconductor materials for manufacturing OFETs devices. In this paper, fluorine atom substituents are introduced into compound molecules, p-type materials are transformed into n-type materials, and they are applied to OFETs. In this paper, first of all, using Tetrafluoro phthalic anhydride as raw material, the raw material was synthesized by imidization, amidation and dehydration. Then three kinds of perfluorinated metal phthalocyanine MPcF16 MCuCuZN were prepared from 3H 4N 4N 5N 6- tetrafluoro phthalonitrile in 52.46m 48.00 and 14.900.Three kinds of perfluoroborophthalocyanine X-BsubPcF12X BrClFN were prepared by using 3O4O4O4O4F5F6 tetrafluoro phthalonitrile as raw material, and the yields of them were 30.01n 33.9828.577.The yield of the three perfluorobenzocyanine phthalocyanines MPcF16 / MCuCuO4 was 30.01or 33.9828.570.Three perfluorobenzene phthalocyanines were used as raw materials. Three kinds of boron phthalocyanine X-BsubpcCX (BrC1-Cl-FN) were prepared from nitrile, and their yields were 42.01 and 38.97 and 10.43, respectively. The synthesized materials were characterized by IR, NMR and MS. Their optical properties were determined by UV-Vis and fluorescence spectra, their thermal stability was determined by thermogravimetric analysis, and their electrochemical properties were analyzed by cyclic voltammetry (CV) curves. The photophysical properties of perfluorinated metal phthalocyanine compounds (MPcF16 / MCuCuOZnVOO) were determined. The UV maximum absorption wavelengths of perfluorinated metal phthalocyanine compounds (MPcF16 / MCuCuOZnVOO) in the solvent of o-dichlorobenzene (DCB), N-dimethylformamide (DMF), tetrahydrofuran (THF), are between 665nm and 720nm. The UV maximum absorption wavelengths of perfluorinated boron phthalocyanine compound X-BsubPcF12XHBrCClF in toluene, chloroform, dichloromethane, dichloromethane (DCM) and o-dichlorobenzene are between 570nm and 580nm, and the maximum UV absorption wavelengths of boron phthalocyanine X-BsubpcXBrClClCF in solvents such as Tolueneine TCM-DCM are between 560nm and 570nm. The electrochemical properties of the synthesized compounds showed that the LUMO energy level of perfluorinated metal phthalocyanine compound MPcF16MCuCuZN was between -4.57 and 4.50 EV, and the LUMO energy level of perfluorinated boron phthalocyanine compound X-BsubPcF12XOBHBr-Cl-F) was between -4.08 and 4.05 EV, and the LUMO energy level of perfluorinated metal phthalocyanine compound (MPcF16) was between -4.08 and 4.05 EV. The LUMO energy level of boron phthalocyanine compound X-BsubPcC (X-BsubPcC) is between -4.03 and 4.00 EV, and the LUMO energy level is between -4.03 and 4.00 EV. The results of thermal stability test showed that the thermal decomposition temperature of the perfluorinated metal phthalocyanine compound MPcF16MCuCuCuZnVOO was above 380 鈩，

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