CN110003245B - 一类烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭化合物及其制备方法与应用 - Google Patents
一类烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭化合物及其制备方法与应用 Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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Abstract
本发明属于有机光电材料技术领域,具体涉及一类烷基/硫烷基氮杂芳环末端的D(A‑Ar)2型共轭化合物及其制备方法和应用。以3,3'‑二氟‑2,2'‑双噻吩给体单元为中心核,通过烷基化反应、亲电取代上溴反应和stille偶联反应,获得D(A‑Ar)2型结构的共轭有机小分子光伏给体材料。本发明所涉及的D(A‑Ar)2型共轭化合物具有良好的溶解性和稳定性,具有宽的光谱吸收范围,强的吸光能力和合适的电化学能级,有望用于有机太阳能电池的给体材料。其与以富勒烯PC71BM为受体的单层器件本体异质结太阳能电池的最大能量转化效率和短路电流分别高达8.91%和16.75mA cm‑2。
Description
技术领域
本发明属于有机光电材料技术领域,特别涉及一类烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭化合物及其制备方法与应用。
背景技术
随着全球人口的急剧增长和经济的迅速发展,曾经作为重要的天然能源的化石燃料存储量急剧减少,在不久的将来将消耗殆尽,并且过分使用化石燃料还引发了不可扭转的环境问题,雾霾天气出现频率越来越高。除水能、风能、地热能等之外,太阳能是最重要的可再生能源,研究表明每年太阳光到地球的能量超过人类目前消耗总能量的几千倍,可谓是取之不尽,用之不竭。自然界中的生物通过光合作用,可以将太阳能转化为化学能。而电能作为科学技术发展、国民经济飞跃的主要动力,在人类生活中起着不可或缺的作用。因此,人类迫切地需要将太阳能转化为电能来替代传统能源。早在19世纪法国的物理学家Becquerel就发现,半导体在受到光照时会产生电动势,这种现象在物理学上称为光生伏特效应(photovoltaic effect)。1954年,美国的贝尔研究所成功地研制出第一块硅太阳能电池,光电转化效率达到6%,标志着人工器件将太阳能转化为电能成为现实。通过几十年来的发展,不同材料的太阳能电池技术日益成熟,并且各有特色。太阳能电池根据所用材料的不同可分为:硅太阳能电池(silicon solar cells)、无机盐太阳能电池(inorganic solarcells)、染料敏化太阳能电池(dye sensitized solar cell,简称DSSC)、有机太阳能电池(organic solar cells,简称 OSCs)和钙钛矿太阳能电池(pervoskite solar cells)等。目前实现产业化的太阳能电池主要是硅太阳能电池,在实验室里最高的转换效率达到了26%,接近理论效率29%的上限。但由于硅单晶加工工艺复杂,制作太阳能电池成本高昂,能耗大,阻碍了其进一步的推广。
无机盐太阳能电池材料如砷化镓、硫化镉、铜铟硒等,光电转换效率较高,材料价格虽然昂贵但是成本相比单晶硅较低。然而,这类太阳能电池的缺点是有剧毒,会对环境造成严重的污染,并且铟和硒都是比较稀有的元素,来源受到限制,这些因素阻碍了其实际应用。染料敏化太阳能电池和钙钛矿太阳能电池制备成本较低,光电转换效率比较理想,尤其是钙钛矿太阳能电池,其效率已超过20%。但是它们目前存在对环境易造成污染、器件寿命短、稳定性低、较难进行柔性器件制备等缺点。有机太阳能电池的材料来源广泛、低成本、分子易调控、重量轻、柔韧性好、可以进行大面积的柔性制备。因此,有机太阳能电池具有长远发展的潜力,为解决未来全球的能源问题提供了一种新的选择。
目前为止,有机太阳能电池主要包括本体异质结有机太阳能电池(BHJ-OSC) 和染料敏化太阳能电池(DSSC)两个研究方向。其中,本体异质结有机太阳能电池(BHJ-OSC)又分为聚合物有机太阳能电池材料(BHJ-PSC)和小分子有机太阳能电池材料(BHJ-SMOSC),基于聚合物有机太阳能电池材料(BHJ-PSC)串联器件的光电转化最高效率(PCE)达到了17.3%,基于有机小分子三元器件最高效率的BHJ-SMOSC的PCE达到了13.6%,单层器件光电转化效率PCE最高达到了11.5%。由于BHJ-OSC与DSSC相比,生产工艺更简单、器件更趋稳定,所以获得了越来越多研究者的青睐。有机小分子光伏材料,与聚合物光伏材料相比,分子结构与器件性能之间的关系更加明确和可靠,因此,BHJ-SMOSC具有很大的发展潜力,吸引了更多科学家去进一步研究和发掘。
目前有机小分子材料的光电转换效率整体上还低于聚合物材料,有限的小分子供体材料的设计原则已经严重阻碍了高效率有机小分子太阳能电池的发展,如何通过分子结构的设计获得高效光电转换效率的有机小分子光伏材料存在着巨大的挑战。本工作不仅提供了一类新颖高性能的有机太阳能电池的小分子给体材料,而且提供了高效率有机小分子材料的构筑方式和研究思路。
发明内容:
本发明提供了一类烷基/硫烷基氮杂芳环末端的D(A-Ar)2型结构有机小分子光伏材料,该类材料的特点是以3,3'-二氟-2,2'-双噻吩给体单元(D),吡咯并吡咯二酮衍生物(A)为受体单元(A),并分别以2-烷基噻唑、2-烷基锡唑、2-硫烷基噻唑或2-硫烷基锡唑作为末端单元(Ar)。构筑D(A-Ar)2结构的线性小分子光伏供体材料,旨在实现宽吸收,强吸收和高迁移率有机光伏供体材料的分子构筑,将其用于制作有机小分子光伏器件(OSCs),实现了D(A-Ar)2型结构光伏材料的较高转换效率。
D(A-Ar)2型共轭化合物结构式为式I所示:
其中,A为拉电子桥联基团;D为中心给电子基团;X=O、S、Se或者Te; Y=O或S,R1独立的为C6~C8烷基;
该类材料的特点是以烷基/硫烷基芳杂稠环为末端单元。
其中,吸电子桥联基团A可选用下列结构之一,R独立地为C6~C12烷基;
所述具有吸电子性质桥联受体A单元为苯并噻二唑、单氟苯并噻二唑、双氟苯并噻二唑、双噻吩苯并噻二唑、双噻吩单氟苯并噻二唑、苯并噁二唑、单氟苯并噁二唑、双氟苯并噁二唑、双噻吩苯并噁二唑、双噻吩单氟苯并噁二唑、苯并三氮唑、单氟苯并三氮唑、双氟苯并三氮唑、双噻吩苯并三氮唑、双噻吩单氟苯并三氮唑、噻吩吡咯并吡咯二酮、噻唑吡咯并吡咯二酮、吡啶吡咯并吡咯二酮、苯基吡咯并吡咯二酮、苯基异靛蓝、噻吩基异靛蓝、噻唑基异靛蓝、噻吩[3,4-b]并-3-氟-噻吩酯、噻吩[3,4-b]并-3-氟-噻吩酮、噻吩[3,4-b]并-3-氟-噻吩酮、噻吩[3,4-b]并-3-噻吩酮、噻吩[3,4-b]并吡咯二酮、双噻吩-噻吩[3,4-b]并吡咯二酮、双噻吩[4,5-b]并吡啶酮并苯、双噻吩[3,4-b]并环己基二酮。
中心给电子基团D可选用下列结构之一,R独立地为C6~C12烷基;
D为功能化稠环给体单元,所述D共轭单元为苯、萘、蒽、菲、噻吩、烷基联噻吩、烷基三联噻吩、烷基噻吩并噻吩、三芳胺、烷基苯并二噻吩、烷基引达省、茚并噻吩、芴、咔唑、双噻吩芴、双噻吩咔唑、苯并[b]噻唑硅芴、烷基锡吩并锡吩、双锡吩芴和烷基苯并[b]二锡唑。
末端芳杂稠环(Ar)为烷基/硫烷基功能化稠环给体单元,可选用下列结构之一,R1独立地为C6~C12烷基;
Ar为芳杂稠环单元,所述Ar共轭单元为2-烷基恶唑、2-硫烷基恶唑、2- 烷基噻唑、2-硫烷基噻唑、2-烷基锡唑、2-硫烷基锡唑、2-烷基碲唑和2-硫烷基碲唑。
上述D(A-Ar)2型共轭化合物(有机小分子光伏材料),优选为:
以3,3'-二氟-2,2'-双噻吩(DFT)为给电子基团,吡咯并吡咯二酮衍生物(TDPP)为拉电子基团,2-辛基噻唑(TZ)为末端单元的D(A-Ar)2型小分子光伏材料DFT(TDPP-TZ)2。
或以3,3'-二氟-2,2'-双噻吩(DFT)为推电子基团,吡咯并吡咯二酮衍生物(TDPP)为拉电子基团,2-硫辛基噻唑(TZS)为末端单元的D(A-Ar)2型小分子光伏材料DFT(TDPP-TZS)2。
基于烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭化合物的制备方法为:
将带有R1或SR1的氮杂芳环(Ar)锡试剂与吸电子桥联基团A单元(摩尔比为 2~3:1)在Pd(PPh3)4(10%mol)催化条件下于甲苯溶剂中进行Stille偶联反应,制备得到相应的一侧含溴、一侧含烷基/硫烷基氮杂芳环(Ar)的化合物。
将所得到相应的一侧含溴、一侧含烷基/硫烷基氮杂芳环(Ar)与给电子基团D (摩尔比为2~2.5:1)在Pd(PPh3)4(10%mol)催化条件下于甲苯溶剂中再进行Stille 偶联反应,进行脱氧处理,氮气保护下加热回流反应12小时,获得含烷基/硫烷基氮杂芳环(Ar)为末端的D(A-Ar)2型线性小分子共轭化合物。A单元指的是上述所述吸电子桥联基团中的一种,D单元指的是上述所述功能化稠环给体单元种的一种。
本发明的D(A-Ar)2型小分子光伏材料的主要优点在于:
(1)合成的基于烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭分子具有良好的溶解性,能溶于大部分有机溶剂,如二氯甲烷、氯仿、四氢呋喃和氯苯等。
(2)由于平面型的分子结构,合成的基于烷基/硫烷基氮杂芳环末端的 D(A-Ar)2型小分子材料具有较高的载流子迁移率。
(3)合成的基于烷基/硫烷基氮杂芳环末端的共轭分子D(A-Ar)2具有较强的分子间相互作用,较紧密的π-π堆积作用。
(4)合成的基于烷基/硫烷基氮杂芳环末端的D(A-Ar)2共轭分子中给-受体相互作用的存在,形成较强的ICT作用,增强了电荷传输性能。
(5)合成的基于烷基/硫烷基氮杂芳环末端的D(A-Ar)2共轭分子,由于末端烷基和硫烷基链的引入,易于调节溶解性,使共轭分子具有更好的成膜性。
(6)合成的基于烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭分子具有合适的电化学能级,适合用于电子给体材料。
(7)合成的基于烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭分子作为电子受体材料在有机太阳能电池中获得较高的能量转换效率。
本发明制得的D(A-Ar)2型共轭化合物具有高的空穴迁移率,可与PC71BM 共混,制作小分子光伏器件;其中,D(A-Ar)2型共轭化合物与PC71BM共混质量比为1:1。
具体为:将D(A-Ar)2型共轭化合物作为活性层应用于有机太阳能电池、有机场效应晶体管或有机电致发光二极管等器件中。
所述的小分子光伏器件的阳极修饰层为聚二氧乙基噻吩(PEDOT)涂层。
所述的有机小分子光伏器件包括氧化锡铟导电玻璃衬底层(ITO),阳极层,其中阳极修饰层为聚二氧乙基噻吩(PEDOT,30nm)涂层;阴极为Ca(10nm)/Al (100nm)的沉积层;活化层材料为本发明所述的D(A-Ar)2分子与PC71BM。
所述活性层的厚度介于20纳米~1000纳米之间。
所述的活性层是通过溶液加工法实现,包括旋涂、刷涂、喷涂、浸涂、辊涂、丝网印刷、印刷或喷墨打印方法,其中所用溶剂为有机溶剂。
附图说明
图1为本发明DFT(TDPP-TZ)2的热失重曲线图。
图2为本发明DFT(TDPP-TZ)2在二氯甲烷溶液中的紫外-可见吸收光谱图。
图3为本发明DFT(TDPP-TZ)2在固体膜中的紫外-可见吸收光谱图。
图4为本发明DFT(TDPP-TZ)2在固体膜上的循环伏安曲线图。
图5为本发明DFT(TDPP-TZ)2与PC71BM的混合比例为1:1(w/w,12mg/mL) 下的J-V曲线图。
图6为本发明DFT(TDPP-TZ)2与PC71BM的混合比例为1:1(w/w,12mg/mL) 下EQE曲线图。
图7为DFT(TDPP-TZ)2与PC71BM的混合比例为1:1(w/w,12mg/mL)时单电子器件的J1 /2-V曲线。
图8为本发明DFT(TDPP-TZS)2的热失重曲线图。
图9为本发明DFT(TDPP-TZS)2在二氯甲烷溶液中的紫外-可见吸收光谱图。
图10为本发明DFT(TDPP-TZS)2在固体膜中的紫外-可见吸收光谱图。
图11为本发明DFT(TDPP-TZS)2在固体膜上的循环伏安曲线图。
图12为本发明DFT(TDPP-TZS)2与PC71BM的混合比例为1:1(w/w, 12mg/mL)下的J-V曲线图。
图13为本发明DFT(TDPP-TZS)2与PC71BM的混合比例为1:1(w/w,12 mg/mL)下EQE曲线图。
图14为DFT(TDPP-TZS)2与PC71BM的混合比例为1:1(w/w,12mg/mL)时单电子器件的J1/2-V曲线。
具体实施方式
下面通过具体实施例对本发明作进一步说明,但这些具体实施方案不以任何方式限制本发明的保护范围。
基于烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭分子的制备路线如下所示,
实施例1,化合物2-辛基噻唑(TZR1)的合成路线如下:
氮气保护下,在100mL三口瓶中,用干燥的***溶解2-溴噻唑(6.0g,36.58 mmol)、于-78℃下滴加2.5M正丁基锂(16.0ml,40.24mmol)、-78℃下反应两小时后,一次性加入溴代正辛烷(7.0g,36.58mmol),保温反应半小时后,转到室温反应过夜。直接减压旋干溶剂,得浅黄色液体,以石油醚为洗脱剂进行柱层析分离,得产物(TZR1)6.0g,产率84%。1H NMR(500MHz,CDCl3)δ7.66(d, J=3.3Hz,1H),7.18(d,J=3.3Hz,1H),3.05–2.97(m,2H),1.79(dt,J=15.4,7.6 Hz,2H),1.33–1.26(m,11H),0.87(s,3H).
实施例2,2-辛基噻唑-5-三丁基锡(SnTZR1)的合成路线如下:
氮气保护下,在100mL三口瓶中,用干燥的四氢呋喃溶解2-辛基噻唑(2.46 g,10.8mmol)、于-78℃下滴加2.5M正丁基锂(4.75ml,11.88mmol)、-78℃下反应两小时后,一次性加入三丁基氯化锡(3.22ml,11.88mmol),保温反应半小时后,转到室温反应过夜。直接减压旋干溶剂,得浅黄色稠液体(SnTZR1),直接用于下一步反应。1H NMR(400MHz,CDCl3)δ7.58(s,1H),3.06–3.03(m,2H), 1.80(dt,J=15.0,7.4Hz,2H),1.58–1.51(m,6H),1.46(dt,J=16.1,8.7Hz,6H), 1.39-1.17(m,22H),0.89(t,J=7.2Hz,12H).
实施例3,3-(5-溴-2-噻吩基)-2,5-二(2-乙基己基)-6-(5-(2-辛基-5-噻唑基)-2-噻吩基)吡咯并吡咯二酮(BrTDPP-TZR1)的合成路线如下:
氮气保护下,在100mL三口瓶中加入20mL甲苯、2-辛基噻唑-5-三丁基锡(286mg,0.59mmol)、3,6-二(5-溴-2-噻吩基)-2,5-二(2-乙基己基)-吡咯并吡咯二酮(400mg,0.59mmol)、四三苯基膦钯(34mg,0.03mmol)。在氮气氛围下搅拌加热至80℃,4h后停止反应,冷却至室温。旋蒸除去溶剂,以石油醚/ 二氯加烷体积比为5:1的混合溶液为洗脱剂进行柱层析分离,得产物(BrTDPP- TZR1)172mg,产率30.0%。1H NMR(400MHz,CDCl3)δ8.90(d,J=4.1Hz,1H), 8.64(d,J=4.2Hz,1H),7.84(s,1H),7.27(s,1H),7.23(d,J=4.2Hz,1H),3.98(dt, J=13.7,7.2Hz,4H),3.02(t,J=7.7Hz,2H),1.82(dt,J=15.3,7.6Hz,4H),1.32(ddd,J=25.4,15.9,8.4Hz,34H),0.94–0.86(m,15H).
实施例4,2-硫辛基噻唑(TZSR1)的合成路线如下:
在氮气保护和冰浴下,于100mL单口瓶中加入80mL无水乙醇、叔丁醇钾(14.36g,0.128mol)和2-噻唑硫醇(5g,42.7mmol),搅拌反应30min后,缓慢加入溴代正辛烷(8.66g,44.8mmol)。加完后,回流反应12h,反应完,加水淬灭。水洗用***(3×20mL)萃取,合并有机层并用无水硫酸镁干燥,过滤得滤液,除去溶剂,以石油醚为洗脱剂进行柱层析分离,得产物(TZSR1)9.06g,产率92.4%。1H NMR(400MHz,CDCl3)δ7.66(d,J=3.4Hz,1H),7.20(d,J=3.4 Hz,1H),3.30–3.15(m,2H),1.75(dt,J=15.0,7.4Hz,2H),1.51–1.36(m,2H), 1.33–1.15(m,9H),0.88(t,J=6.9Hz,3H).
实施例5,2-硫辛基噻唑-5-三丁基锡(SnTZSR1)的合成路线如下:
氮气保护下,在100mL三口瓶中,用干燥的四氢呋喃溶解2-硫辛噻唑(2.0 g,8.90mmol)、于-78℃下滴加2.5M正丁基锂(3.92ml,9.8mmol)、-78℃下反应两小时后,一次性加入三丁基氯化锡(2.66ml,9.8mmol),保温反应半小时后,转到室温反应过夜。直接减压旋干溶剂,得浅黄色稠液体(SnTZSR1),直接用于下一步反应。1H NMR(400MHz,CDCl3)δ7.57(s,1H),7.26(s,1H),3.30–3.05(m, 3H),1.76(dt,J=15.0,7.4Hz,3H),1.58–1.48(m,6H),1.45(dt,J=16.1,8.7Hz, 5H),1.39-1.18(m,22H),0.89(t,J=7.2Hz,18H).
实施例6,3-(5-溴-2-噻吩基)-2,5-二(2-乙基己基)-6-(5-(2-硫辛基-5-噻唑基)-2-噻吩基)吡咯并吡咯二酮(BrTDPP-TZSR1)的合成路线如下:
氮气保护下,在100mL三口瓶中加入20mL甲苯、2-硫辛基噻唑-5-三丁基锡(213mg,0.41mmol)、3,6-二(5-溴-2-噻吩基)-2,5-二(2-乙基己基)-吡咯并吡咯二酮(280mg,0.41mmol)、四三苯基膦钯(7.12mg,0.0062mmol)。在氮气氛围下搅拌加热至80℃,4h后停止反应,冷却至室温。旋蒸除去溶剂,以石油醚/二氯加烷体积比为5:1的混合溶液为洗脱剂进行柱层析分离,得产物 (BrTDPP-TZSR1)172mg,产率30.0%。1H NMR(300MHz,CDCl3)δ8.89(d,J= 4.2Hz,1H),8.64(d,J=4.1Hz,1H),7.80(s,1H),7.22(dd,J=4.2,1.7Hz,2H),3.97(dd,J=12.7,7.6Hz,4H),3.29–3.18(m,2H),1.84(dd,J=11.8,7.2Hz,2H), 1.81–1.68(m,2H),1.30(d,J=14.3Hz,30H),0.89–0.79(m,15H).
实施例7,目标化合物FBT(TDPP-TZR1)2的合成路线如下:
氮气保护下,在100mL单口瓶中加入10mL甲苯、3-(5-溴-2-噻吩基)-2,5- 二(2-乙基己基)-6-(5-(2-辛基-5-噻唑基)-2-噻吩基)吡咯并吡咯二酮(126mg, 0.157mmol)、(3,3'-二氟-[2,2'-双噻吩]-5,5'-二-三丁基锡(42mg,0.078mmol)、四三苯基膦钯(5.46mg,0.0048mmol)。在氮气氛围下搅拌加热至110℃,12h 后停止反应,冷却至室温。旋蒸除去溶剂,以石油醚/二氯加烷体积比为2:1的混合溶液为洗脱剂进行柱层析分离,得产物FBT(TDPP-TZR1)2160mg,产率 72.0%。1H NMR(400MHz,CDCl3)δ8.93(d,J=4.3Hz,2H),7.75(s,1H),7.22(s, 1H),7.15(s,1H),6.99(s,1H),3.98(s,4H),2.91(t,J=7.1Hz,2H),1.88(s,2H), 1.75(s,2H),1.31(d,J=47.2Hz,60H),0.93–0.86(m,30H).
实施例8,目标化合物FBT(TDPP-TZSR1)2的合成路线如下:
氮气保护下,在100mL单口瓶中加入10mL甲苯、3-(5-溴-2-噻吩基)-2,5- 二(2-乙基己基)-6-(5-(2-硫辛基-5-噻唑基)-2-噻吩基)吡咯并吡咯二酮(150mg, 0.18mmol)、(3,3'-二氟-[2,2'-双噻吩]-5,5'-二-三丁基锡(48mg,0.09mmol)、四三苯基膦钯(6.3mg,0.0054mmol)。在氮气氛围下搅拌加热至110℃,12h后停止反应,冷却至室温。旋蒸除去溶剂,以石油醚/二氯加烷体积比为2:1的混合溶液为洗脱剂进行柱层析分离,得产物FBT(TDPP-TZSR1)2160mg,产率 72.0%。1H NMR(400MHz,CDCl3)δ8.96–8.90(m,2H),7.67(s,1H),7.12(s,1H), 7.03(d,J=4.0Hz,1H),6.89(s,1H),3.93(d,J=13.3Hz,4H),3.11(t,J=7.3Hz, 2H),1.87(s,2H),1.73–1.65(m,2H),1.32(dd,J=38.3,7.0Hz,60H),0.93(ddd,J=19.8,18.9,6.3Hz,30H).
实施例9
D(A-Ar)2型小分子光伏材料的性能表征及其光伏光器件的制作和发光性能的测试。
D(A-Ar)2型小分子光伏材料的1H NMR光谱通过Bruker Dex-400NMR仪器测定,紫外-可见吸收光谱通过HP-8453紫外-可见光谱仪测定,荧光光谱通过 HITACHI-850荧光光谱仪测定。
基于D(A-Ar)2型小分子材料的光伏器件包括:氧化锡铟(ITO)导电玻璃阳极层、聚二氧乙基噻吩(PEDOT)阳极修饰层。活化层层由所述小分子材料和 PC71BM共混构成,其共混比列为1:1。阴极由Ca(10nm)/Al(100nm)层构成。
实施例10
DFT(TDPP-TZ)2光物理性能及其小分子光伏器件性能
DFT(TDPP-TZ)2的热失重曲线图如图1所示。其分解温度为378℃。
DFT(TDPP-TZ)2在CHCl3溶液中的紫外吸收光谱如图2所示;其中363nm的吸收峰为该小分子材料的π-π*跃迁吸收峰,650nm的吸收峰为给体单元(DFT) 到受体单元(DPP)的电荷转移(ICT)跃迁吸收峰。
DFT(TDPP-TZ)2在固体膜中的紫外吸收光谱如图3所示。其中吸收光谱的图形大致相同,但吸收峰均有不同程度的红移,这是由于固体膜中π-π堆积所致。由起峰位置计算出该材料的带隙为1.56eV。
DFT(TDPP-TZ)2在固体膜中的循环伏安曲线如图4所示。其表现出两组可逆的氧化峰,可分别归属为给体单元DFT和受体单元DPP的氧化峰。由此得出该材料的HOMO能级为-5.41eV。
DFT(TDPP-TZ)2与PC71BM的混合比例为1:1(w/w,12mg/mL)下的J-V曲线图如图5所示;在该条件下,器件的短路电流为16.12mA/cm2,开路电压为0.75V,填充因子为63.09%,光伏效率为7.63%。
DFT(TDPP-TZ)2与PC71BM的混合比例为1:1(w/w,12mg/mL)下EQE曲线图如图6所示;该图显示的EQE测试范围为300-800nm,在610nm处有最大 EQE值,为78.64%。
DFT(TDPP-TZ)2与PC71BM的混合比例为1:1(w/w,12mg/mL)时单电子器件的J1/2-V曲线如图7所示,其空穴迁移率最大为4.95×10-4cm2V-1s-1。
实施例11
DFT(TDPP-TZS)2光物理性能及其小分子光伏器件性能
DFT(TDPP-TZS)2的热失重曲线图如图8所示,其分解温度为367℃。
DFT(TDPP-TZS)2在CHCl3溶液中的紫外吸收光谱如图9所示。其中377nm 左右的吸收峰为该小分子材料的π-π*跃迁吸收峰,632nm左右的吸收峰为给体单元(DFT)到受体单元(DPP)的电荷转移(ICT)跃迁吸收峰。
DFT(TDPP-TZS)2在固体膜中的紫外吸收光谱如图10所示。其中吸收光谱的峰形大致相同,但吸收峰均有不同程度的红移,这是由于固体膜中π-π堆积所致。由起峰位置计算出该材料的带隙为1.57eV。
DFT(TDPP-TZS)2在固体膜中的循环伏安曲线如图11所示。其表现出两组可逆的氧化峰,可分别归属为给体单元DFT和受体单元DPP的氧化峰。由此得出该材料的HOMO能级为-5.25eV。
DFT(TDPP-TZS)2与PC71BM的混合比例为1:1(w/w,12mg/mL)下的J-V曲线图如图12所示。在该条件下,器件的短路电流为16.75mA/cm2,开路电压为 0.795V,填充因子为66.93%,光伏效率为8.91%。
DFT(TDPP-TZS)2与PC71BM的混合比例为1:1(w/w,12mg/mL)下EQE曲线图如图13所示。该图显示的EQE测试范围为300-800nm,在661nm左右处有最大EQE值,为78.89%。
DFT(TDPP-TZS)2与PC71BM的混合比例为1:1(w/w,12mg/mL)时单电子器件的J1/2-V曲线如图14所示,其空穴迁移率最大为7.78×10-4cm2V-1s-1。
尽管结合了优选实施例对本发明进行了说明,但本发明并不局限于上述实施例,应当理解所附权利要求概括了本发明的范围。在本发明构思的指导下,本领域的技术人员应当意识到,对本发明的各实施例方案所进行的一定的改变,都将被本发明的权利要求书的精神和范围所覆盖。
Claims (8)
2.根据权利要求1所述的烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭化合物的制备方法,其特征在于,制备方法如下:
合成侧链DPP-TZ-Br:2,5-二溴噻吩基吡咯并吡咯二酮在四三苯基膦钯的作用下,与2-辛基-5-噻唑三丁基锡发生stille偶联反应,合成得到单侧含溴的DPP-TZ-Br粗产品,经柱层析分离得到纯品;
或,合成侧链DPP-TZS-Br:2,5-二溴噻吩基吡咯并吡咯二酮在四三苯基膦钯的作用下,与2-硫辛基-5-噻唑三丁基锡发生stille偶联反应,合成得到单侧含溴的DPP-TZS-Br粗产品,经柱层析分离得到纯品;
合成目标分子DFT(TDPP-TZ)2或DFT(TDPP-TZS)2:侧链DPP-TZ-Br或DPP-TZS-Br与双氟联噻吩在四三苯基膦钯催化下发生stille偶联反应,合成得到D(A-Ar)2型小分子光伏材料DFT(TDPP-TZ)2或DFT(TDPP-TZS)2,粗产品经柱层析分离得到纯品。
3.根据权利要求1所述的烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭化合物的应用,其特征在于,将所述的D(A-Ar)2型共轭化合物与PC71BM共混,制作小分子光伏器件。
4.根据权利要求3所述的烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭化合物的应用,其特征在于,D(A-Ar)2型共轭化合物作为活性层应用于有机太阳能电池、有机场效应晶体管、有机电致发光二极管或有机近红外光电探测器中。
5.根据权利要求3所述的烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭化合物的应用,其特征在于,所述的D(A-Ar)2型共轭化合物与PC71BM共混质量比为1:1。
6.根据权利要求3所述的烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭化合物的应用,其特征在于,所述的小分子光伏器件的阳极修饰层为聚二氧乙基噻吩(PEDOT)涂层。
7.根据权利要求4所述的烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭化合物的应用,其特征在于,活性层的厚度介于20纳米~1000纳米之间。
8.根据权利要求4所述的烷基/硫烷基氮杂芳环封端的D(A-Ar)2型共轭化合物的应用,其特征在于,所述的活性层通过溶液加工法实现。
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