本文關(guān)鍵詞： 可溶性 方酸菁衍生物 光電性能 太陽能電池　出處：《太原理工大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：1965年,方酸菁衍生物被首次合成,至今已經(jīng)歷了五十多年的發(fā)展,由于其具有合成路線簡單、能隙可調(diào)、良好的穩(wěn)定性和卓越的光電性能而備受青睞,現(xiàn)已應(yīng)用至包括有機(jī)光伏在內(nèi)的多個領(lǐng)域。方酸菁衍生物在可見光及近紅外區(qū)域有較強(qiáng)的吸收,摩爾吸收系數(shù)(ε)達(dá)到了105 L/(mol·cm),這歸因于方酸菁衍生物分子中兩端富含電子的給體和中心缺電子的受體四元環(huán)之間強(qiáng)烈的“給體-受體-給體”(D-A-D)電子轉(zhuǎn)移相互作用。方酸菁衍生物的性能主要受富電子親核試劑種類的影響,其中最常見的一類親核試劑是N,N-二烷基(R)芳基胺,本論文首先:采用具有不同溶解性的烷基基團(tuán)R,如R為異丁基、己基及乙基等,作為N,N-二烷基(R)芳基胺中N的取代基團(tuán);用羥基、甲基等可通過改變分子內(nèi)與分子間相互作用進(jìn)而影響吸收特性的取代基團(tuán)修飾芳基來合成一系列N,N-二烷基(R)芳基胺為給體單元的D-A-D方酸菁衍生物,從而為進(jìn)一步優(yōu)化分子結(jié)構(gòu)提供實驗依據(jù)。綜合以上實驗結(jié)果,為了進(jìn)一步改善其吸收及溶解特性,再引入給電子能力更強(qiáng)的噻吩基團(tuán)在N的另一取代位置,合成目標(biāo)產(chǎn)物,即以N-烷基-N-噻吩基芳香胺為給體單元的D-A-D方酸菁衍生物。通過氫譜、碳譜、紅外光譜、元素分析等手段對其結(jié)構(gòu)進(jìn)行了表征,并研究了其光電性質(zhì)、穩(wěn)定性、溶解性、分子的聚集態(tài)等性質(zhì),以及作為給體材料在本體異質(zhì)結(jié)太陽能電池中光伏性能。具體工作概括如下:選取含N,N-二取代烷基(R)的芳基胺為給體基團(tuán)與方酸進(jìn)行縮合反應(yīng)分別合成了SQ1、SQ2和SQ3(SQ1、SQ2和SQ3中R分別為異丁基、己基及乙基)。通過核磁、紅外光譜、元素分析確定了其分子結(jié)構(gòu)。首先研究了三種衍生物的溶解性,這三種衍生物在1 m L氯苯中分別能溶解4 mg、95 mg、5 mg,其中SQ2通過己基的引入改善溶解性的效果很顯著。隨后,詳細(xì)研究了在不同溶劑中溶液和薄膜狀態(tài)下的紫外可見吸收光譜。與薄膜狀態(tài)下的SQ1相比,SQ3紫外可見吸收明顯紅移并拓寬,并且在薄膜狀態(tài)最大吸收波長可達(dá)到729 nm,吸收紅移32 nm,SQ3將甲基修飾的芳香胺取代羥基修飾的芳香胺,其吸收光譜發(fā)生了明顯的紅移。研究表明:SQ1和SQ3的薄膜狀態(tài)下J-聚集形態(tài)顯著,SQ2薄膜中H-聚集和J-聚集都較為明顯,并且其聚集形態(tài)受溶劑類型、與PC_(61)BM混合比例的影響。在對比SQ2與SQ3實驗結(jié)果的基礎(chǔ)上,進(jìn)一步設(shè)計以N-己基且甲基修飾的芳基胺為母體基團(tuán),并引入了給電子能力更強(qiáng)的噻吩基團(tuán)在N的另一取代位置,分別合成了SQ4a和SQ5a,其中SQ4a和SQ5a的區(qū)別在于噻吩的接入位置分別為2位與3位。為了進(jìn)一步研究苯環(huán)上甲基的存在對于分子結(jié)構(gòu)與性能的影響,又設(shè)計、合成了不含甲基的對比分子SQ4b和SQ5b。首先,研究了他們的溶解性,在1 m L氯苯中SQ4a、SQ4b、SQ5a和SQ5b分別能溶解25 mg、18 mg、40 mg和7 mg。進(jìn)而,詳細(xì)研究了溶液和薄膜狀態(tài)下的紫外可見吸收光譜,SQ4a和SQ5a薄膜狀態(tài)的最大吸收峰達(dá)到了700 nm左右,SQ4b和SQ5b薄膜狀態(tài)的最大吸收峰分別在640 nm和670 nm。這四種材料在薄膜狀態(tài)下同時存在兩種聚集狀態(tài)——H-聚集和J-聚集,當(dāng)溶劑不同、與PC_(61)BM摻雜比不同時,對它們薄膜狀態(tài)下的聚集形態(tài)有一定的影響。結(jié)果顯示:當(dāng)具有給電子能力基團(tuán)CH_3引入給體單元中時,取代基的誘導(dǎo)效應(yīng)作用明顯,相較于沒有引入CH_3基團(tuán)的方酸菁衍生物吸收光譜發(fā)生明顯紅移。并且,當(dāng)引入CH_3時,增強(qiáng)了分子間的耦合作用以及分子間的氫鍵作用,都有利于J-聚集狀態(tài)的形成,不論是高沸點溶劑還是低沸點溶劑,J-聚集行為都比較顯著。
[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.

【學(xué)位授予單位】：太原理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TM914.4

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本文編號：1548237