新型共轭聚合物与齐聚物的设计合成与光电性能的研究

发布时间：2018-11-03 17:05

【摘要】：人口的增长和工业化发展,使得人类对能源的需要量越来越大。现在主要的能源-石化资源依照现在的消耗速度仅能维持几十年使用。为了解决发展与能源需求之间的矛盾,寻找新型,绿色,环保,可再生的能源成为一个亟须解决的世界问题。太阳能很早就开始为人类所利用,加上太阳能取之不尽,在能源危机出现的现在更是大受重视。现在太阳能利用的效率和途径限制了这个行业的发展,如何用尽可能低成本将太阳能转化为电能,是整个科技界共同努力解决的一个问题。与传统无机硅太阳能电池相比,有机太阳电池(organic solar cell,OSC)具有质轻,低成本,柔性,可实现印刷加工(roll-to-roll printing)和大面积而受到广泛关注。目前,文献报道的有机太阳能电池光电转化效率已经超过10%,但要真正实现大规模的商业应用还有很多问题需要解决。有机太阳能电池的效率和寿命问题,除了工艺的优化和革新,更多的是依靠新材料的合成和设计。聚合物近红外探测器是有机光电的另一个重要分支,相比传统无机近红外探测器材料(硅,铟砷化镓等)具有低成本,易于加工,宽的光响应范围,高灵敏度,可实现从紫外,可见光,近红外的大范围探测。在生物传感,夜间成像,环境监测方面有巨大实用价值。从材料设计合成角度来看,设计合成宽吸收光谱,结构简单,可溶液加工的新型聚合物近红外材料是这个领域的主要突破口。本论文通过吡啶噻二唑单元,氟代苯并噻二唑等具有化学优先选择性的杂环设计合成具有分子内局域规整性的有机太阳电池给体材料,并对光电性能的影响进行研究。第二章,我们根据weak donor srong aceptor设计思路出发,以9-亚甲基芴为电子给体,通过suzuki偶联与吡啶噻二唑,氟代苯并噻二唑,苯并噻二唑等不同吸电子强度的电子受体,合成了一系列局域规整的可溶液加工小分子太阳电池给体材料,并仔细对比不同吸电子单元对能级,光谱,光电性能的调控效应。第三章,聚合物的多分散性决定聚合物是由不同分子链长度,不同末端基分子组成的混合物。我们合成一系列基于二噻吩并噻咯和苯并噻二唑单元构筑的共轭齐聚物,共轭聚合物结构确定,可以作为模型化合物来研究同结构单元构筑的PSBTBT聚合物给体材料结构与性能关系。在这一系列不同共轭链长的共轭齐聚物中,随着共轭链长的增长,光谱红移,带隙变窄,摩尔吸收系数增大,光伏性能和形貌向有利方向发展。在第四章,我们利用第三章工作中的ADA中间体,与不同富电子能力的电子给体进行Stille聚合合成规整的D2-A-D1-A三元聚合物。相比传统的DA交替共聚物相比,可以通过D2单元对能级和光谱进行微调,同时D2和D1侧链的变化可以使聚合物在溶解性和π-π堆积上达到一个较好的平衡,其中PBDT-O-ADA器件效率4%,比同侧链的二噻吩并噻咯与苯并噻二唑聚合物效率提升。第五章,我们将第四章的ADA前驱体的D由二噻吩并噻咯替换成给电子能力更弱的苯并二噻吩单元,A单元换成吸电子能力更强的吡啶并噻二唑单元,这样更符合weak donor srong aceptor设计思路。同时通过Stille偶联与一些高效能的电子给体如噻吩并环戊二烯,苯并二噻吩,Indancenodithiophene聚合,优化光电性能,其中PBDTTEHPBP能量转化效率最好为4.96%.第六章,我们合成吡啶硒二唑和一种新杂环氟代苯并硒二唑单元,通过合成规整朝向ADA中间体与噻吩并环戊二烯单体共聚,合成两个近红外材料。其中,CDTPSE的光响应达到1100nm,在有机近红外探测器方面有巨大应用潜力。第七章,我们合成基于苯并二噻吩与氟代硒二唑为核的D2-A-D1-A规整聚合物,对比了苯并二噻吩不同侧链对光电性能的影响,并将其应用于有机太阳电池中。
[Abstract]:Population growth and industrialization have led to a growing demand for energy. Now the main energy-petrochemical resource can only be used for several decades, according to the current consumption rate. In order to solve the contradiction between development and energy demand, a new, green, environment-friendly and renewable energy source has become a world problem to be solved. Solar energy has long begun to be used by human beings, coupled with the inexhaustible solar energy, which is now more and more important in the energy crisis. The efficiency and path of solar energy now limits the industry's development, and how to convert solar energy into electrical energy with the lowest possible cost is a problem that can be solved through joint efforts across the globe. Compared with the traditional inorganic silicon solar cell, the organic solar cell (OSC) has the advantages of light weight, low cost and flexibility, and can realize the wide attention of roll-to-roll printing and large-area. At present, the photoelectric conversion efficiency of organic solar cells reported in the literature has exceeded 10%, but there are still many problems to be solved in order to realize large-scale commercial application. The efficiency and lifetime of the organic solar cell, in addition to the optimization and innovation of the process, is more dependent on the synthesis and design of new materials. the near infrared detector of the polymer is another important branch of organic photoelectric, Near-infrared range detection. and has great practical value in the aspects of biological sensing, night imaging and environmental monitoring. From the viewpoint of material design and synthesis, the new polymer near-infrared material with wide absorption spectrum, simple structure and solution processing is the main breakthrough in this field. In this paper, the organic solar cell material with local regularity in the molecule is synthesized by using a heterocyclic design with a chemical preferential selectivity, such as difluorobenzene diethylamine unit, fluorobenzene and diethylamine, etc., and the influence of the photoelectric property is studied. In the second chapter, based on the design thought of the weak Hellor srong acieptor, the electron donor of 9-methylene group is used as electron donor, and the electron acceptors with different electron absorption intensities such as difluorobenzene and difluorobenzene are coupled through suzbach. In this paper, a series of locally structured small molecule solar cell donor materials are synthesized, and the regulation effect of different electron withdrawing units on energy level, spectrum and photoelectric performance is carefully compared. In chapter three, the polydispersity of the polymer determines that the polymer is a mixture of different molecular chain lengths, different end-group molecules. The structure and properties of PSBBT polymer (PSBBT) polymer constructed by the same structural unit can be studied as a model compound. With the increase of chain length, the spectrum became red, the band gap became narrower, the molar absorption coefficient was increased, and the photovoltaic performance and morphology developed in favorable direction. In chapter 4, we use ADA intermediate in the third chapter to synthesize a regular D2-A-D1-A terpolymer with electron donor with different electron-rich ability. Compared with the traditional DA alternating copolymer, the energy level and the spectrum can be fine-tuned by D2 units, and meanwhile, the change of the D2 and D1 side chains can lead the polymer to achieve a better balance on the solubility and the carbon-acid accumulation, wherein the efficiency of the PBDT-O-DA device is 4 percent, which is higher than that of the diethylamine of the same side chain and improves the efficiency of the two-phase polymerization of benzene and benzene. In the fifth chapter, we replace the D of the ADA precursor in chapter 4 with the benzidine which is weaker in the electron capacity, and replace it with a two-way unit, which is more suitable for the design idea of the weak writer. At the same time, the photoelectric properties are optimized by Stille coupling and some high-performance electron donor such as trimethylamine and cyclopentadiene, benzene and dibenzidine, and the efficiency of PBDTEHPBP energy conversion is preferably 4.96%. In chapter 6, we synthesized two kinds of near-infrared materials by synthesizing Se _ 2O _ 2 and a new heterocyclic fluorine-substituted benzene and selenium-diethylamine unit. Among them, the light response of CDTPSE reaches 1100nm, and it has great potential for application in organic near infrared detector. In chapter 7, we synthesized the D2-A-D1-A structured polymer based on benzene and diethylamine as the core, compared the influence of different side chains on the photoelectric properties and applied it to the organic solar cell.
【学位授予单位】：华南理工大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TM914.4;O631

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