偶氮杂芴功能材料的设计、合成及在有机光电器件中的应用

发布时间：2018-04-10 23:41

本文选题：杂芴 + 偶氮　；参考：《南京邮电大学》2015年硕士论文

【摘要】：杂芴类材料近年来在有机电子学领域应用非常广泛,然而杂芴小分子材料的多功能化、该类材料在其他领域的应用研究等问题仍需进一步的工作。本论文为拓宽杂芴类材料的多功能化,进一步研究其在有机电存储领域中的应用,并将杂芴类材料引入到其他应用领域,通过对杂芴类材料多功能化的分子设计、有机合成及表征、计算模拟、光物理性能、电化学性质及热分析性能的测试,系统分析了分子结构与材料性能的关系,为进一步发挥杂芴类材料的作用和下步突破奠定的一定基础。本论文具体研究内容概括如下:1.将偶氮官能团引入氧芴及硫芴分子,设计合成了四种单边偶氮修饰的杂芴类材料,表征了溶液状态及薄膜态下吸收光谱,测试了电化学性质,热力学性质,并将四种材料在有机电存储器件方面应用进行了研究,得到的有机电存储器件阈值电压在8-10 V,开关比为104左右,存储类型为WORM型。将溶液态下四种材料用紫外光激发后,研究了其吸收光谱的变化,证明了材料在紫外光激发下会发生顺反异构变化,为继续拓宽材料在智能材料及能源材料方面的应用奠定基础;2.将偶氮官能团先引入双碘偶氮联苯分子,再用不同二取代杂原子试剂进行合环,设计合成四种双边偶氮杂芴材料。一般来说,在单边硝化杂芴后,分子中苯环会被钝化,会难以得到双边偶氮杂芴材料,本路线不仅会解决这个问题,而且会避免硅芴等在硝化时被强酸破坏难以引入偶氮基团的问题;双边偶氮杂芴材料,不仅可以保持好的平面性,而且可以进一步延长π共轭结构。在大量合成摸索工作中,试验了不同溶剂、温度等条件对于合环的影响,得到了双边偶氮杂芴分子的重要中间体,通过计算模拟可知该材料不仅保持了很好的平面性,而且具有比单边取代偶氮更延展的π共轭结构;3.将偶氮官能团引入联苯材料,设计合成得到了五种单、双边偶氮联苯材料,制备的有机电存储器件阈值电压在4-6 V,开关比104左右;通过研究分子内引入强吸电子基团前后,制备的有机电存储器件特性变化,发现当向分子内引入强吸电子基团时,会显著降低器件的阈值电压,提高其开关比,揭示了在该体系材料中影响存储性能的因素。研究中不仅得到性能优良的WORM型存储器件;并且研究表征了材料在紫外光激发后的顺反异构变化,为继续拓宽材料在智能材料及能源材料等方面的应用奠定基础。
[Abstract]:In recent years, heterofluorene materials have been widely used in the field of organic electronics. However, the multi-functionalization of heterofluorene small molecular materials and the application of these materials in other fields still need further work.In order to broaden the multifunction of heterofluorene materials and further study its application in the field of electromechanical storage, this paper introduces the heterofluorene materials into other application fields, and designs the multifunctional molecular design of heterofluorene materials.Organic synthesis and characterization, calculation simulation, photophysical properties, electrochemical properties and thermal analysis properties were tested, and the relationship between molecular structure and material properties was systematically analyzed.For further play the role of heterofluorene materials and the next step of breakthrough laid a certain foundation.The specific contents of this thesis are summarized as follows: 1.Four kinds of one-sided azo modified heterofluorenes were designed and synthesized by introducing azo functional groups into oxyfluorene and thiofluorene molecules. The absorption spectra in solution and film state were characterized. The electrochemical and thermodynamic properties were measured.The application of four kinds of materials in electromechanical memory device is studied. The threshold voltage of electromechanical memory device is 8-10 V, the switching ratio is about 10 4, and the storage type is WORM type.The changes of absorption spectra of four kinds of materials in solution state were studied after excited by ultraviolet light. It is proved that the change of cis-trans isomerization occurs under ultraviolet light excitation.To continue to expand the application of materials in smart materials and energy materials lay a foundation for 2.The azo functional groups were first introduced into diiodiazobenzene molecules and then synthesized by using different disubstituted hetero-atomic reagents to design and synthesize four kinds of bilateral azofluorene materials.Generally speaking, after one-sided nitration of fluorene, benzene ring in the molecule will be passivated and it will be difficult to obtain bilateral azofluorene materials. This route will not only solve this problem.It can avoid the problem that silicofluorene is destroyed by strong acid and it is difficult to introduce azo group in nitration. The bilateral azofluorene material can not only maintain good planarity but also prolong 蟺 conjugated structure further.In a large number of synthetic and groping work, the effects of different solvents and temperature on the ring were tested, and an important intermediate of the bilateral azofluorene molecule was obtained. The results of calculation and simulation showed that the material not only maintained a good planarity.Moreover, the 蟺 -conjugate structure is more extensive than that of one-sided substituted azo.By introducing azo functional groups into biphenyl materials, five kinds of single and bilateral biphenyl materials were designed and synthesized. The threshold voltage of electromechanical storage devices was 4-6 V and the switching ratio was about 104.It is found that the threshold voltage and the switching ratio of the devices will be significantly reduced when the strong electron-absorbing groups are introduced into the molecules. The factors that affect the storage performance in the system are revealed.Not only WORM memory devices with excellent properties are obtained, but also the changes of cis-trans isomerism after UV excitation are studied and characterized, which lays a foundation for further broadening the applications of materials in smart materials and energy materials.
【学位授予单位】：南京邮电大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB34

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