【作者】 王芳；

【导师】 赖文勇；

【作者基本信息】 南京邮电大学 ， 信息材料， 2014， 硕士

【摘要】 近年来有机半导体材料由于具有制备成本低，种类和结构多样化，性能可通过结构设计来调制，易于制备大面积器件，以及可用于柔性电子器件等特点受到广泛关注。通过对有机分子的设计和结构的剪裁，来拓展材料的种类、调控材料的性质、改善器件的性能，以得到大量具有预期功能的材料。本文简单介绍了咔唑、吲哚单元的研究进展，对环状三聚吲哚和有机小分子太阳能电池材料研究现状进行了简单的论述。同时设计合成了一系列基于三聚吲哚可溶线性有机窄带系小分子的材料。为进一步拓展多聚吲哚材料的应用，我们进一步合成了四聚吲哚新材料，并初步研究了其在光电性质。具体内容如下：（1）通过Suzuki偶联的方法合成了一系列以三聚吲哚为端基，对称取代苯并噻二唑衍生物的窄带隙小分子材料。研究表明：这些小分子具有较好的溶解性，较宽的光谱吸收，较窄的光学带隙。TGA、DSC研究说明，这类小分子材料均具有较好的热稳定性，且表现出良好的无定形态有利于溶液加工处理。紫外可见吸收光谱，电化学以及理论计算研究发现，调节分子的共轭长度及烷基链的位置，能有效地拓宽了分子的吸收光谱，降低了共轭分子的带隙。线性分子的带隙从1.99调节到1.75eV。（2）为了进一步拓宽化合物的光谱吸收，降低分子能带隙。选取强吸电子能力，更长共轭长度的吡咯并吡咯二酮（DPP）、苯并噻吩为核（BDT），并引入噻吩和噻吩苯并噻二唑的作为桥连基团，逐步调节分子共轭长度，获得了一系较好溶解性，宽光谱吸收的线性有机小分子。这些小分子材料均具有较好的热稳定性并且是无定形态，有利于溶液加工处理。通过紫外吸收和电化学测试发现：这一系列化合物具有宽的吸收光谱和低的能带隙。其中以DPP为核的材料具有更宽的光谱吸收，噻吩苯噻唑集团的引入，更有利于化合物对可见光的吸收。成功的将线性分子的带隙从实验测试结果表明(TATBT)2DPP的带隙比(TATBT)2BDT更窄，这与理论计算的结果也相吻合。（3）以大平面具有很好的光热和化学稳定性的苝酰亚胺为核，三聚吲哚为封端，合成另一组以苝酰亚胺为核的窄带隙线性小分子，并引入噻吩基团，获得了两个性溶解非常好的有机共轭小分子。通过紫外吸收和电化学测试发现：这一系列化合物具有宽的吸收光谱和非常低的能带隙。噻吩基团的引入，化合物LUMO降低，HOMO值增加。整体能隙降低，这一结果与理论计算也相吻合。(4)通过环化反应得到另一个新的构筑单元-四聚吲哚（TTI）。并合成了芘和芴基封端的四取代和八取代衍生物。这一系列多臂结构大分子都具有较窄的光谱吸收和发射。电化学研究表明，当引入取代基个数增加时，化合物的HOMO能级增加，同时LUMO能级降低，即带隙变窄。芴取代衍生物的带隙比芘取代衍生物的带隙宽。与理论计算的结果相吻合。更多还原

【Abstract】 In recent years, organic semiconductor materials with low production cost, species andstructural diversity, performance can be modulated by structural design, preparation of synthesisprocess is simple, easily to be prepared and can be used for large-area flexible electronic devices,etc. have attracted widespread attention. Type of organic molecules by tailoring the design andstructure of the materials developed from the organic semiconductor material storage constraints,the nature of the regulation of the material to improve the performance of the device in order toobtain a large number of materials with intended function.This paper introduces the basic principles of organic electroluminescence, and the status quo ofthe development of small organic molecules indole solar cell material trimer a simple exposition.Meanwhile designed and synthesized a series of material soluble trimeric indole small organicmolecules narrowband lines and tetramer-based multi-substituted indole derivatives, and their light,thermal stability and electrochemical properties were studied based on the discussion. Details are asfollows:(1) Synthesis of a series of three carbazole-terminated poly-symmetrically substitutedbenzothiadiazole derivatives small molecule-based material through a narrowband Suzuki couplingmethod. Studies have shown that: These small molecules have a good solubility, a broad absorptionspectrum and a high thermal stability. Thermal gravimetric analysis (TGA) study shows that thesesmall molecular materials have better thermal stability. And is conducive to the solution ofamorphous processing. UV-visible absorption spectroscopy studies have found that by adjusting theposition of the conjugate molecules and the alkyl chain length, effectively broadening theabsorption spectrum of the molecules, reducing the bandgap conjugated molecules.Electrochemical measurements and theoretical calculations are consistent. Adjusting the band gapof linear molecules from1.99to1.75eV. Suggest that three carbazole and the possibility ofconstructing narrow-band materials.(2) To further broaden the absorption spectrum of the compound to the strong electron-donatinggroup and triindole or triazatruxene (TAT), diketopyrrolopyrrole, benzothiadiazole, and theintroduction of thiophene and benzo-thiadiazole-based electron-withdrawing groups, solubilityobtained a good linear series of small organic molecules. Thermal gravimetric analysis (TGA) studyshows that these small molecular materials have better thermal stability. And is conducive to the solution of amorphous processing. The electrochemical test by UV absorption and that: the series ofcompounds having a broad absorption spectrum and a low bandgap. Among DPP nuclear materialhas a wider spectral absorption, the introduction of thiophene benzothiazole group, more conduciveto visible light absorbing compounds. The electrochemical test results can be seen from the lowerlevel of this series LUMO small molecule materials conducive electron injection and transport. Theelectrochemical test results show,2BDT narrower (TATBT)2DPP bandgap ratio (TATBT)BDT, theresults of which are consistent with the theoretical calculations.(3) In large flat with good thermal and chemical stability of perylene nucleus, indole trimer(three and carbazole) was capped, and another group of narrow-band system of linear syntheticsmall molecules, thienyl and thiazolyl introduced group received two very good dissolution of smallorganic molecules. The electrochemical test by UV absorption and that: the series of compoundshaving a broad absorption spectrum and a very low bandgap. A thienyl group is introduced, thecompound LUMO lower HOMO value increases. Reduce overall energy gap, this result isconsistent with the theoretical calculations. Will be more strong electron-withdrawing ability of PDIunit fully to the energy gap of three and carbazole series materials by the beginning of1.99eV to1.36eV.(4) Obtained by cyclization of a new building blocks-indole tetramer. And a fluorenyl groupand pyrenyl synthesized capped four and eight-substituted substituted derivatives thereof. Thisseries of multi-arm structure of macromolecules having a narrow absorption and emission spectra.Electrochemical studies show that when the number of the substituent introduced increases, HOMOenergy level of the compound is increased, while reducing LUMO level, i.e., the band gap isnarrowed. Fluorene substituted pyrene derivatives substituted derivative than the band gap of wideband gap. The results agree with the theoretical calculations.更多还原