含芳基胺给体单元的可溶性D-A-D方酸菁衍生物的光电性能研究及在太阳能电池中的应用

发布时间：2018-02-28 17:17

本文关键词： 可溶性方酸菁衍生物光电性能太阳能电池　出处：《太原理工大学》2017年硕士论文　论文类型：学位论文

【摘要】：1965年,方酸菁衍生物被首次合成,至今已经历了五十多年的发展,由于其具有合成路线简单、能隙可调、良好的稳定性和卓越的光电性能而备受青睐,现已应用至包括有机光伏在内的多个领域。方酸菁衍生物在可见光及近红外区域有较强的吸收,摩尔吸收系数(ε)达到了105 L/(mol·cm),这归因于方酸菁衍生物分子中两端富含电子的给体和中心缺电子的受体四元环之间强烈的“给体-受体-给体”(D-A-D)电子转移相互作用。方酸菁衍生物的性能主要受富电子亲核试剂种类的影响,其中最常见的一类亲核试剂是N,N-二烷基(R)芳基胺,本论文首先:采用具有不同溶解性的烷基基团R,如R为异丁基、己基及乙基等,作为N,N-二烷基(R)芳基胺中N的取代基团;用羟基、甲基等可通过改变分子内与分子间相互作用进而影响吸收特性的取代基团修饰芳基来合成一系列N,N-二烷基(R)芳基胺为给体单元的D-A-D方酸菁衍生物,从而为进一步优化分子结构提供实验依据。综合以上实验结果,为了进一步改善其吸收及溶解特性,再引入给电子能力更强的噻吩基团在N的另一取代位置,合成目标产物,即以N-烷基-N-噻吩基芳香胺为给体单元的D-A-D方酸菁衍生物。通过氢谱、碳谱、红外光谱、元素分析等手段对其结构进行了表征,并研究了其光电性质、稳定性、溶解性、分子的聚集态等性质,以及作为给体材料在本体异质结太阳能电池中光伏性能。具体工作概括如下:选取含N,N-二取代烷基(R)的芳基胺为给体基团与方酸进行缩合反应分别合成了SQ1、SQ2和SQ3(SQ1、SQ2和SQ3中R分别为异丁基、己基及乙基)。通过核磁、红外光谱、元素分析确定了其分子结构。首先研究了三种衍生物的溶解性,这三种衍生物在1 m L氯苯中分别能溶解4 mg、95 mg、5 mg,其中SQ2通过己基的引入改善溶解性的效果很显著。随后,详细研究了在不同溶剂中溶液和薄膜状态下的紫外可见吸收光谱。与薄膜状态下的SQ1相比,SQ3紫外可见吸收明显红移并拓宽,并且在薄膜状态最大吸收波长可达到729 nm,吸收红移32 nm,SQ3将甲基修饰的芳香胺取代羟基修饰的芳香胺,其吸收光谱发生了明显的红移。研究表明:SQ1和SQ3的薄膜状态下J-聚集形态显著,SQ2薄膜中H-聚集和J-聚集都较为明显,并且其聚集形态受溶剂类型、与PC_(61)BM混合比例的影响。在对比SQ2与SQ3实验结果的基础上,进一步设计以N-己基且甲基修饰的芳基胺为母体基团,并引入了给电子能力更强的噻吩基团在N的另一取代位置,分别合成了SQ4a和SQ5a,其中SQ4a和SQ5a的区别在于噻吩的接入位置分别为2位与3位。为了进一步研究苯环上甲基的存在对于分子结构与性能的影响,又设计、合成了不含甲基的对比分子SQ4b和SQ5b。首先,研究了他们的溶解性,在1 m L氯苯中SQ4a、SQ4b、SQ5a和SQ5b分别能溶解25 mg、18 mg、40 mg和7 mg。进而,详细研究了溶液和薄膜状态下的紫外可见吸收光谱,SQ4a和SQ5a薄膜状态的最大吸收峰达到了700 nm左右,SQ4b和SQ5b薄膜状态的最大吸收峰分别在640 nm和670 nm。这四种材料在薄膜状态下同时存在两种聚集状态——H-聚集和J-聚集,当溶剂不同、与PC_(61)BM掺杂比不同时,对它们薄膜状态下的聚集形态有一定的影响。结果显示:当具有给电子能力基团CH_3引入给体单元中时,取代基的诱导效应作用明显,相较于没有引入CH_3基团的方酸菁衍生物吸收光谱发生明显红移。并且,当引入CH_3时,增强了分子间的耦合作用以及分子间的氢键作用,都有利于J-聚集状态的形成,不论是高沸点溶剂还是低沸点溶剂,J-聚集行为都比较显著。
[Abstract]:In 1965, squaraine derivatives were synthesized for the first time, has experienced more than 50 years of development, because of its simple synthetic route, the energy gap is adjustable, good stability and excellent photoelectric properties and favored, has been used to include organic photovoltaic, many fields. Squaraine derivatives have strong absorption in the visible and near infrared region, the molar absorption coefficient (E) reached 105 L/ (mol - cm), which is attributed to the molecular squaraine derivatives in both electron rich donor and receptor deficiency between the four membered ring center electron strong "donor acceptor donor" (D-A-D) electron transfer the interaction of squaraine derivatives. The performance is mainly affected by the electron rich nucleophilic species, one of the most common type of nucleophilic reagent is N, N- two alkyl aryl amine (R), this paper using R alkyl groups with different solubility, such as R is isobutyl, f Base and ethyl, as N, N- (R) two alkyl substituted aryl amine N with hydroxyl methyl, etc.; can change the intra and inter molecular interactions and effects of substituent aryl group to synthesize a series of N absorption characteristics of N- two (R), alkyl aryl amine for unit D-A-D squaraine derivatives, so as to provide experimental basis for further optimization of the molecular structure. Based on the above results, in order to further improve its absorption and solubility, and thiophene introduced to electronic stronger ability in another to replace the position of N, synthesis of the target product, namely N- -N- alkyl thiophene aromatic amine as to the unit D-A-D squaraine derivatives. By 1H NMR, 13C NMR, IR spectra and structure were characterized by elemental analysis, and study its optical properties, stability, solubility and aggregation properties of molecules, as well as donor materials in Bulk heterojunction photovoltaic solar cell performance. The specific work is summarized as follows: two containing N, N- substituted alkyl aryl amine (R) as the donor group and squaric acid were synthesized by the condensation reaction of SQ1, SQ2 and SQ3 (SQ1, SQ2 and SQ3 R respectively, isobutyl and ethyl hexyl). By NMR, IR, elemental analysis, its molecular structure was confirmed. First studied the solubility of three kinds of derivatives, these three kinds of derivatives can be dissolved in 4 mg, 95 mg and 5 mg respectively in 1 m L SQ2 by chlorobenzene, hexyl introduced to improve the solubility of the effect is very significant. Then, detailed study the UV solution in different solvents and films under visible absorption spectra. Compared with films under the condition of SQ1, SQ3 and UV Vis absorption red shifted and widen, and can reach 729 nm at the maximum absorption wavelength of the film state, absorption red shift 32 nm, SQ3 will replace the methyl modified aromatic amine Hydroxyl modified aromatic amine, the obvious red shift in the absorption spectrum. Research shows that the film state SQ1 and SQ3 under J- morphology of SQ2 thin films significantly, H- aggregation and aggregation of J- are more obvious, and the aggregation morphology by solvent type, and PC_ (61) BM mixing ratio. The influence of the foundation comparison of SQ2 and SQ3 on the experimental results, further design using aryl amine hexyl methyl N- and modified as the parent group, and the introduction of thiophene moiety to electronic stronger ability in another place of N, SQ4a and SQ5a were synthesized, the difference between SQ4a and SQ5a in thiophene access location respectively. 2 and 3. In order to further study, methyl benzene ring for the molecular structure and properties of the design, synthesis of not containing methyl contrast molecules SQ4b and SQ5b. first, studied their solubility in 1 m L, SQ4a, SQ4b and SQ5b SQ5a in chlorobenzene, divided Don't be dissolved in 25 mg, 18 mg, 40 mg and 7 mg., and then, a detailed study of the solution and film state ultraviolet visible absorption spectra, the maximum absorption peak of SQ4a and SQ5a thin film reached about 700 nm, the maximum absorption peak of SQ4b and SQ5b film state respectively in 640 nm and 670 nm. four in the condition of thin film materials have two kinds of aggregation H- aggregation and J- aggregation, when different solvents and PC_ (61) BM doping ratio is not the same, have certain effects on the morphology of their film state. The results showed that when having electron donating group CH_3 into the donor unit in effect of substituent induced effect, obviously, compared with the CH_3 group without introducing squaraine derivative absorption spectra is obviously red shifted. And, when the introduction of CH_3, enhance the hydrogen bonding interaction between molecules and between molecules, which help to form the aggregation state of J- The aggregation behavior of J- is significant both at high boiling point solvent or low boiling point solvent.

【学位授予单位】：太原理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TM914.4

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