CN116041672A - 基于4-烷硫基噻吩/4-烷硒基噻吩的聚合物和制备方法及应用 - Google Patents
基于4-烷硫基噻吩/4-烷硒基噻吩的聚合物和制备方法及应用 Download PDFInfo
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- CN116041672A CN116041672A CN202211510730.7A CN202211510730A CN116041672A CN 116041672 A CN116041672 A CN 116041672A CN 202211510730 A CN202211510730 A CN 202211510730A CN 116041672 A CN116041672 A CN 116041672A
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- Prior art keywords
- thiophene
- donor
- polymer
- alkylseleno
- alkylthio
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
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Abstract
本发明公开了基于4‑烷硫基噻吩/4‑烷硒基噻吩的聚合物和制备方法及应用,所述聚合物包括作为共轭侧链连接至给体‑受体聚合物的主链上的4‑烷硫基噻吩环和/或4‑烷硒基噻吩环;所述4‑烷硫基噻吩环和/或4‑烷硒基噻吩环连接在聚合物主链的给体单元上。本发明将含有硫或者硒原子的4‑烷硫基噻吩(AST)或4‑烷硒基噻吩(ASeT)引入修饰BDT单元侧链,从而制备性能更强的非富勒烯多聚物太阳能电池。此外,本发明采用比卤素溶剂毒性更低的非卤素溶剂处理AST或ASeT多聚物材料,提供了制备高效、低成本、环境友好的非富勒烯多聚物太阳能电池的新途径。
Description
技术领域
本发明涉及有机半导体材料领域,特别是涉及一种基于4-烷硫基噻吩/4-烷硒基噻吩的聚合物和制备方法及应用。
背景技术
本体异质结聚合物太阳电池因为其新应用的潜力,比如它的柔性、轻便、环保及低成本发电,一直受到广泛关注。一般来说,聚合物作为电子给体,和一种富勒烯衍生物作为电子受体材料,来共同制备经典的本体异质结聚合物太阳电池,其能量转换效率已经达到11%。但是,由于其在可见光区的吸收较弱、能级调节困难、高成本,富勒烯衍生物已经不是聚合物太阳能电池中理想的受体材料。因此,非富勒烯(NF)受体,由于其再可见光或近红外的强吸收,易于调节能级及相容的形貌,使聚合物太阳电池可以进一步提高能量转换效率。随着高效的ITIC及其衍生物的发展,聚合物太阳能电池的效率已经提高至13-14%,为未来的商业化应用打开了一个光明的未来。
与受体材料类似的是,多聚物电子给体在聚合物太阳能电池中同样重要。高效的非富勒烯聚合物太阳能电池,首先需要多聚物给体和非富勒烯受体有相匹配的吸收光谱、能级及在纳米结构较为合适的相分离,从而确保捕获光子,以及电荷分离和传输尽可能有效。因此,研发一种新的多聚物给体,来满足现在较少的有效的非富勒烯受体材料,是可以进一步提高多聚物太阳能电池效率的有效方法。新的基础单元、不同的给体-受体聚合物结构以及侧链的修饰已经被选为可以有效提高多聚物给体材料性能的有效方法。在这些新的方法当中,侧链的修饰是较为容易的办法。
在现有技术中,4-烷氧基噻吩(AOT)作为拉电子侧链和苯并[1,2-b:4,5-b']二噻吩-4,8-二酮偶联,显示出较低HOMO能级,这样可以提高器件的开路电压(Voc)以及效率。然而,基于AOT的多聚物与现在经典的NF给体不能很好的匹配,导致多聚物太阳能电池的性能较低。此外,AOT多聚物因其复杂的合成路线,一直受到高合成成本和低产率的困扰。
综上所述,亟需研发一种新的技术方案,以解决现有技术中存在的问题,满足实际应用的需求。
发明内容
基于此,本发明提供了一种可行且有效的分子合成方法,以获得更高效的多聚物太阳能电池。在本发明中,将含有硫或者硒原子的4-烷硫基噻吩(AST)或4-烷硒基噻吩(ASeT)引入修饰BDT单元侧链,从而制备性能更强的非富勒烯多聚物太阳能电池。此外,本发明采用比卤素溶剂毒性更低的非卤素溶剂处理AST或ASeT多聚物材料,提供了制备高效、低成本、环境友好的非富勒烯多聚物太阳能电池的新途径。
本发明的一个目的在于,提供一种给体-受体聚合物,包括作为共轭侧链连接至所述给体-受体聚合物的主链上的4-烷硫基噻吩环和/或4-烷硒基噻吩环;
所述4-烷硫基噻吩环的结构式为
所述4-烷硒基噻吩环的结构式为
其中,R1选自氢原子、-(CH2)mH、-O(CH2)mH和-S(CH2)mH中的一种或多种,m选自1~20范围内的整数;R2为-(CH2)nH,n选自1~12范围内的整数。
进一步地,R1可以是氢原子、-CH3、-C2H5、-C4H9、-C6H13、-C8H17、-C12H25、2-乙基己基、2-丁基辛基、2-己基癸基或2-辛基十二烷基;优选地,R1是2-乙基己基。
进一步地,所述4-烷硫基噻吩环和/或4-烷硒基噻吩环连接在聚合物主链的给体单元上。
进一步地,所述4-烷硫基噻吩环和/或4-烷硒基噻吩环与聚合物主链的给体单元的摩尔比为(1~2):1。
优选地,所述4-烷硫基噻吩环和/或4-烷硒基噻吩环与聚合物主链的给体单元的摩尔比为2:1。
优选地,共轭聚合物的主链为给体-受体结构,给体单元与受体单元的摩尔比(D/A比)为1:1,如下所示
进一步地,所述给体单元选自苯并[3,4-b]二噻吩、噻吩、苯及其衍生物中的一种或多种。
进一步地,所述给体单元包括但不限于以下的结构之一:
其中,R1为4-烷硫基噻吩环或4-烷硒基噻吩环。特别地,给体单元是苯并[3,4-b]双噻吩或其衍生物。
进一步地,所述给体-受体聚合物中,主链上的受体单元选自由苯并[c][1,2,5]噻二唑、苯并[c][1,2,5]噁二唑、异吲哚啉-1,3-二酮、喹喔啉、苯并[d][1,2,3]三唑、噻吩并[3,4-c][1,2,5]噻二唑、噻吩并[3,4-b]吡嗪、噻吩并[3,4-b]噻吩、苯并[1,2-c:4,5-c']双([1,2,5]噻二唑)、[1,2,5]噻二唑并[3,4-g]喹喔啉、吡嗪并[2,3-g]喹喔啉、[3,3'-二吲哚亚基]-2,2'-二酮、二酮吡咯并吡咯、噻吩并吡咯二酮、噻吩并异吲哚以及具有未取代或烷基取代的噻吩或未取代或烷基取代的噻吩并[2,3-b]噻吩作为其桥连基团的衍生物组成的组。
进一步地,所述受体单元包括但不限于以下的结构之一:
特别地,共轭聚合物主链上的受体包括但不限于苯并[c][1,2,5]噻二唑、苯并[c][1,2,5]噁二唑、异吲哚-1,3-二酮、喹喔啉、苯并[d][1,2,3]噻三唑、噻并[3,4-c][1,2,5]噻二唑、噻并[3,4-b]吡嗪、噻并[3,4-b]噻吩、苯并[1,2-c:4,5-c’]双([1,2,5]噻二唑)、[1,2,5]噻二唑[3,4-g]喹喔啉、吡嗪并[2,3-g]喹喔啉、[3,3’-二吲哚啉亚基]-2,2’-二酮、苯并[1,2-c:4,5-c]并噻吩-4,8-二酮、噻吩[3,4-c]吡咯-4,6(5h)-二酮、2,5-双氢吡咯并[3,4-c]吡咯-1,4-二酮和在它们两侧具有作为桥连基团的未取代或烷基取代噻吩或未取代或烷基取代噻吩并[2,3-b]噻吩的衍生物组成的组,如以下结构所示,
其中R选自氢原子、-CH3、-C2H5、-C4H9、-C6H13、-C8H17、-C12H25、2-乙基己基、2-丁基辛基、2-己基癸基或2-辛基十二烷基;R2选自H、CH3、C2H5、C4H9、C6H13、C8H17、C12H25、2-乙基己基、2-丁基辛基、2-己基癸基或2-辛基十二烷基。
进一步地,所述给体-受体聚合物中的重复单元个数为10~100。
优选的,受体材料选自噻吩修饰的1,3-并(噻吩-2-yl)-5,7-并(2-乙基己基)苯并-[1,2-c:4,5-c]双噻吩-4,8-二酮(BDD-T)、噻吩修饰的2,3-二苯基-5,8-二(噻吩-2-yl)喹喔啉(DTQx-2F-T)、噻吩修饰的5,6二氟苯并[1,2,3]三唑(FTAZ-T)、噻吩并[3,4-b]噻吩(TT)修饰的噻吩并[3,4-c]吡咯-4,6(5H)-二酮(TPD-TT)以及2,5-二噻吩基-1,3,4-噻二唑(TDZ)。上述单体可以使聚合物具有良好的光伏性能,而被采用作本发明实施例的受体单元。
本发明的另一个目的在于,提供一种组合物,包括由上述给体-受体聚合物以及非富勒烯衍生物所组成的共混物。
进一步地,所述非富勒烯衍生物选自ITIC-2F或ITIC-4F中的一种;
所述ITIC-2F的结构式为
所述ITIC-4F的结构式为
本发明的另一个目的在于,提供上述4-烷硫基噻吩环或4-烷硒基噻吩环的制备方法,包括如下步骤:
4-烷硫基噻吩环的制备方法:
将3-溴代-2-(2-乙基己基)噻吩加入溶剂中,低温冷却后,在惰性气体氛围下,加入正丁基锂溶液,搅拌后,加入1,2-二甲基二硫烷,搅拌反应后,用水淬灭反应然后提纯,得到所述4-烷硫基噻吩环;
4-烷硒基噻吩环的制备方法:
将3-甲硒基噻吩加入溶剂中,低温冷却后,在惰性气体氛围下,加入正丁基锂溶液,搅拌后,加入烷基溴,搅拌反应后,用水淬灭反应然后提纯,得到所述4-烷硒基噻吩环。
本发明的另一个目的在于,提供一种光伏器件,包括上述组合物。
优先地,本发明技术方案采用甲苯来作为溶剂,溶解聚合物:受体的共混物,并且旋涂在器件上干燥。
本发明的另一个目的在于,提供一种将上述给体-受体聚合物应用于提高给体-受体聚合物的开路电压的方法。
本发明的光伏器件包含了半导性共轭聚合物与富勒烯或非富勒烯分子共混作为光活性层。半导性聚合物具有AST或ASeT功能团作为侧链,可以有效降低聚合物的最高占据轨道(HOMO)能级,从而提高开路电压。重要的是,器件的短路电流和填充因子没有明显改变。结果,实现了能量转化效率的提高。
与AOT功能团作为侧链的聚合物相比,由于S、Se原子具有比O原子更大的电子亲核能和与共轭侧基之间的较大的超共轭效应,基于AST或ASeT功能团作为侧链的聚合物具有更低的HOMO能级。与基于AOT侧链的聚合物器件相比,基于AST或ASeT的聚合物器件可以获得更高的开路电压,从而获得更高的能量转化效率。
本发明具有以下有益效果:
依据本发明实施例,与基于AOT官能团的聚合物相比,AST或其类似官能团的引入,可以更有效降低共轭聚合物HOMO能级,BDT上每个AST可以降低0.05-0.1eV,每2个AST可以降低到0.1~0.2eV。结果,具有AST器件的开路电压相比参比器件的相应地增加。与基于AOT侧链的聚合物器件相比,AST器件的短路电流和填充因子并没有降低,从而导致能量转换效率的提高。此外,基于AST聚合物光伏器件采用非卤素溶剂(如甲苯,邻-二甲苯)处理同样表现出很好的性能。这种方法可以适用许多给体-受体型半导性聚合物。
附图说明
图1示出了应用例1制备的光伏器件结构示意图。
图2示出了聚合物材料以及与ITIC衍生物共混后的吸收光谱图;
其中,
图2(a)为单一聚合物材料的吸收光谱图;
图2(b)为聚合物材料与ITIC衍生物共混后的吸收光谱图。
图3示出了聚合物材料的能级分布图。
图4示出了基于不同聚合物材料的光伏器件的电流-电压曲线(J-V)图;
其中,
图4(a)为PMTT56:ITIC-2F光伏器件的电流-电压曲线(J-V)图;
图4(b)为PMOT39:ITIC-2F光伏器件的电流-电压曲线(J-V)图;
图4(c)为PMSeT1:ITIC-2F和PMSeT2:ITIC-4F光伏器件的电流-电压曲线(J-V)图。
图5示出了基于不同聚合物材料的光伏器件的外量子效率曲线(EQE)图;
其中,
图5(a)为PMTT56:ITIC-2F光伏器件在不同溶剂下的外量子效率曲线图;
图5(b)为PMOT39:ITIC-2F光伏器件的的外量子效率曲线图;
图5(c)为PMSeT1:ITIC-2F和PMSeT2:ITIC-4F光伏器件的外量子效率曲线图。
图6示出了基于PMTT56:ITIC-2F制备混合薄膜的TEM照片;
其中,
图6(a)薄膜为甲苯和1%DPE处理;
图6(b)薄膜为邻二甲苯和1%DPE处理;
图6(c)薄膜为氯苯和1%DPE处理。
图7示出了基于PMTT56:ITIC-2F制备混合薄膜的AFM照片(尺寸:5μm×5μm);
其中,
图7(a)薄膜为甲苯和1%DPE处理;
图7(b)薄膜为邻二甲苯和1%DPE处理;
图7(c)薄膜为氯苯和1%DPE处理。
具体实施方式
为了更清楚地说明本发明的技术方案,列举如下实施例。实施例中所出现的原料、反应和后处理手段,除非特别声明,均为市面上常见原料,以及本领域技术人员所熟知的技术手段。
本发明中的词语“优选的”、“优选地”、“更优选的”等是指,在某些情况下可提供某些有益效果的本发明实施方案。然而,在相同的情况下或其他情况下,其他实施方案也可能是优选的。此外,对一个或多个优选实施方案的表述并不暗示其他实施方案不可用,也并非旨在将其他实施方案排除在本发明的范围之外。
应当理解,除了在任何操作实例中,或者以其他方式指出的情况下,表示例如说明书和权利要求中使用的成分的量的所有数字应被理解为在所有情况下被术语“约”修饰。因此,除非相反指出,否则在以下说明书和所附权利要求中阐述的数值参数是根据本发明所要获得的期望性能而变化的近似值。
本发明实施例中的ITIC-2F的结构式为
本发明实施例中的ITIC-4F的结构式为
制备例1
2-(2-乙基己基)-3-甲硒基噻吩(3ASeT)的制备,包括如下步骤:
向预先干燥的500mL烧瓶中加入3-甲硒基噻吩(19.57g,110.50mmol)和无水四氢呋喃(120mL),将该溶液冷却至-78℃,在氩气保护下,逐滴加入48.4mL的2.4mol/L浓度的正丁基锂溶液。将混合物在该温度下搅拌1.0h,然后缓慢的加入2-乙基己基溴(42.7g,221mmol),然后在室温下过夜搅拌,之后用水淬灭该反应。有机层通过乙酸乙酯萃取得到,用水清洗3次,用无水硫酸镁干燥,然后减压除去溶剂。目标产物最终通过蒸馏(0.1MPa,101-110℃)获得19.53g,产率:61.1%。
1H NMR(400MHz,CDCl3,δ):7.17(d,J=5.2Hz,1H),7.01(d,J=5.2Hz,1H),2.86(d,J=7.1Hz,2H),2.24(s,3H),1.64(dt,J=11.9,6.5Hz,1H),1.33(dq,J=9.8,5.8,4.6Hz,8H),0.92(q,J=4.0,3.5Hz,6H).
制备例2
2-(2-乙基己基)-3-甲硫基噻吩(3AST)的制备,包括如下步骤:
将3-溴代-2-(2-乙基己基)噻吩(5.74g,20.85mmol)和无水己烷(30mL)加入预先干燥的250mL烧瓶中,将溶液冷却至-78℃。在氩气保护下,逐滴加入正丁基锂溶液(1.6M inhexane,13.03mL)。在此温度下保持1h,然后缓慢滴入1,2-二甲基二硫烷(1.96g,20.85mmol)。在室温下搅拌过夜,之后用水淬灭该反应。有机层通过二氯甲烷萃取得到,用水冲洗3次,用无水硫酸镁干燥,然后减压除去溶剂。通过蒸馏(0.1MPa,82-88℃)得到目标产物4.03g,产率:79.8%。
1H NMR(400MHz,CDCl3,δ):7.13(d,J=5.3Hz,1H),6.97(d,J=5.3Hz,1H),2.81(d,J=7.1Hz,2H),2.36(s,3H),1.66-1.58(m,1H),1.31(dq,J=15.0,5.0,4.2Hz,8H),0.95-0.79(m,6H).
实施例1
PASeT2的合成,包括如下步骤:
1.Sn2-BDT-ASeT作为给体的一部分的制备,合成路线如下:
通过3ASeT和苯并[1,2-b:4,5-b']二噻吩-4,8-二酮反应得到3ASeT取代的苯并二噻吩(BDT-ASeT)。然后将得到的BDT-ASeT和正丁基锂(n-BuLi)进行锂化反应,随后和Me3SnCl进行锡化得到目标产物。
具体的,包括如下步骤:
(1)BDT-ASeT的合成:
向预干燥的250mL烧瓶中加入3ASeT(8.68g,30.0mmol)和无水四氢呋喃(110mL),将该溶液冷却至0℃,在氩气保护下,逐滴加入20.6mL的1.6mol/L浓度的正丁基锂溶液。将混合物在0℃保持1.5h,然后温热至室温。之后,一次性加入苯并[1,2-b:4,5-b']二噻吩-4,8-二酮(2.75g,12.5mmol)。反应在80℃下进行1.5h。冷却至0℃后,加入10%HCl(70mL)中的SnCl 2·2H2O(16.86g,74.75mmol)溶液,在80℃下再搅拌2h。冷却至室温后,用乙酸乙酯萃取,并用盐水洗涤几次。通过用二氯甲烷/己烷(v/v:1/9)作为洗脱液的柱色谱法进一步纯化,得到5.37g黄色油,产率:56.2%。
1H NMR(400MHz,CDCl3,δ):7.65(d,J=5.7Hz,2H),7.48(d,J=5.7Hz,2H),7.37(s,2H),2.94(d,J=7.1Hz,4H),2.32(s,6H),1.72(dt,J=12.2,5.9Hz,2H),1.49-1.29(m,16H),1.01-0.86(m,12H).
(2)Sn2-BDT-ASeT的合成:
在100mL氩气吹扫过的烧瓶中,将BDT-ASeT(1.04g,1.36mmol)溶于无水四氢呋喃(20mL)中,然后在-78℃下加入2.04mL的1.6mol/L浓度的正丁基锂溶液。然后将反应混合物在此温度下搅拌1.5h。随后,加入3.67mL的1.0mol/L浓度的三甲基甲锡烷基氯溶液,并将混合物在室温下搅拌过夜。有机层用乙醚萃取,用水洗涤几次,浓缩得到粗产物。通过从异丙醇中重结晶获得1.06g的目标产物,产率:71.7%。
1H NMR(400MHz,CDCl3,δ):7.67(s,2H),7.38(s,2H),3.02-2.85(m,4H),2.32(s,6H),1.73(dt,J=11.8,6.1Hz,2H),1.40(ddd,J=32.1,18.3,6.3Hz,16H),0.94(dt,J=20.0,7.2Hz,12H),0.41(s,18H).
2.Br2-FTAZ-T作为受体部分的制备
根据现有报道的方法(J.Am.Chem.Soc.2011,133,4625.)合成4,7-二(5-溴噻吩)-5,6-2-(2-异十六烷基)-2-氢-苯并[1,2,3]三唑(Br2-FTAZ-T)。
3.给体-受体聚合物PASeT2的制备
给体-受体聚合物的制备通过双锡化的BDT供体单元与二溴化的受体单元,在甲苯/DMF混合溶剂中,利用Pd(PPh3)4作为催化剂,通过Stille缩聚反应得到聚合物。
PASeT2的合成路线如下:
向25mL预干燥的烧瓶中分别加入Sn2-BDT-ASeT(230.1mg,0.211mmol)、Br2-FTAZ-T(148.0mg,0.211mmol)和Pd(PPh3)4(10.1mg,0.009mmol),然后加入10mL甲苯和1.0mL DMF。在氩气保护下,混合物在120℃保持24h。当冷却至室温,粗产物通过硅藻土过滤,并通过从丙酮中沉淀来收集。然后将固体依次用甲醇、丙酮、己烷在索氏提取器中冲洗,来除去寡聚物和杂质。之后,所剩的固体溶解在氯仿中并再次在甲醇中沉淀收集。得到259.7mg红色固体,产率:94.2%。Mn:38.2kDa;PDI:1.99.
实施例2
PASeT1的合成,合成路线如下:
在25mL的干净烧瓶里加入Sn2-BDT-ASeT(244.8mg,0.2245mmol)、TPD-TT-Br2(232.61mg,0.2245mmol)以及Pd(PPh3)4(11.41mg,0.00988mmol)。在氩气保护下,加入10mL甲苯,在120℃反应12h后,用甲醇冲洗收集所得产物。接着采用甲醇、丙酮、正己烷、与氯仿通过索氏提取法进一步冲洗产物。将在氯仿中的溶液浓缩,然后在甲醇中沉淀。经泵抽干后,获得320.8mg聚合物。产率:84.20%。Mn:36.2kDa;PDI:2.07。
实施例3
PMTT56的合成,合成路线如下:
在25mL的干净烧瓶里加入Sn2-BDT-AST(174.83mg,0.1754mmol)、TPD-TT-Br2(181.75mg,0.1754mmol)以及Pd(PPh3)4(8.8mg,0.00778mmol)。在氩气保护下,加入4.5mL甲苯,在120℃反应12h后,用甲醇冲洗收集所得产物。接着采用甲醇、丙酮、正己烷、与氯仿通过索氏提取法进一步冲洗产物。将在氯仿中的溶液浓缩,然后在甲醇中沉淀。经泵抽干后,获得256.2mg聚合物。产率:92.70%。Mn:60.0kDa;PDI:1.98。
应用例1
含PMTT56的光伏器件的制备。
制备结构为ITO/PEDOT:PSS/光活性层/PDINO/Ag的光伏器件。其中氧化铟锡(ITO)为底层。该器件包括透明金属氧化物电极,即ITO和聚(3,4-亚乙基二氧噻吩):聚(苯乙烯磺酸酯)(PEDOT:PSS)层作为阳极,以PDINO修饰的Ag电极作为阴极,AST或ASeT聚合物和ITIC衍生物制成的光活性层夹在两个电极之间。在本实施例中,AST的聚合物是PMTT56,ITIC衍生物选用的是ITIC-2F。
器件制备的过程包括如下步骤:首先,将ITO基底依次在清洁剂、去离子水、丙酮以及异丙醇中超声清洗,然后放在烘箱内烘干,之后用紫外-臭氧清洗处理15min。PEDOT:PSS的水溶液通过0.22μm的过滤头过滤,然后以2500rpm/30s的参数旋涂在ITO电极上,在空气中150℃退火处理10min。PEDOT:PSS层的厚度大约是40nm。随后,将其转移到氮气氛围的手套箱内。将PMTT56:ITIC-2F按照质量比为1:1混合溶解在邻二氯苯/1,8-二碘辛烷(99:1,v/v)或二甲苯/二苯醚(99:1,v/v)或甲苯/二苯醚(99:1,v/v)中,其中聚合物的浓度为8mg/mL。
在氮气手套箱内,将混合溶液在旋涂在PEDOT:PSS基底上形成PMTT56:ITIC-2F的薄膜,厚度大约为110nm,之后将PDINO旋涂在活性层上,并且蒸镀电极。最终获得的器件被转移到真空蒸镀舱内,在3×10-6mbar的真空下蒸镀100nm的金属银,光伏器件的面积是4.5mm2。
图1示出了应用例1制备的光伏器件结构示意图。
应用例2
含PASeT1的光伏器件的制备。本应用例与应用例1的区别在于:光活性层采用PASeT1:ITIC-2F,其他成分和制备方法相同。
应用例3
含PASeT2的光伏器件的制备。本应用例与应用例1的区别在于:光活性层采用PASeT2:ITIC-4F,其他成分和制备方法相同。
对比应用例1
含PMOT39的光伏器件的制备。
PMOT39的分子结构如下:
制备结构为ITO/PEDOT:PSS/光活性层/PDINO/Ag的光伏器件。其中氧化铟锡(ITO)为底层。该器件包括透明金属氧化物电极,即ITO和聚(3,4-亚乙基二氧噻吩):聚(苯乙烯磺酸酯)(PEDOT:PSS)层作为阳极,以PDINO修饰的Ag电极作为阴极,MOT聚合物和ITIC衍生物制成的光活性层夹在两个电极之间。在本实施例中,MOT的聚合物是PMOT39,ITIC衍生物选用的是ITIC-2F。
器件制备的过程包括如下步骤:首先,将ITO基底依次在清洁剂、去离子水、丙酮以及异丙醇中超声清洗,然后放在烘箱内烘干,之后用紫外-臭氧清洗处理15min。PEDOT:PSS的水溶液通过0.22μm的过滤头过滤,然后以2500rpm/30s的参数旋涂在ITO电极上,在空气中150℃退火处理10min。PEDOT:PSS层的厚度大约是40nm。随后,将其转移到氮气氛围的手套箱内。将PMOT39:ITIC-2F按照质量比为1:1混合溶解在邻二氯苯/1,8-二碘辛烷(99:1,v/v)或二甲苯/二苯醚(99:1,v/v)或甲苯/二苯醚(99:1,v/v)中,其中聚合物的浓度为8mg/mL。
在氮气手套箱内,将混合溶液在旋涂在PEDOT:PSS基底上形成PMOT39:ITIC-2F的薄膜,厚度大约为110nm,之后将PDINO旋涂在活性层上,并且蒸镀电极。最终获得的器件被转移到真空蒸镀舱内,在3×10-6mbar的真空下蒸镀100nm的金属银,光伏器件的面积是4.5mm2。
测试例1
对给体-受体聚合物进行性能测试。
测试方法:
首先测试PMTT56、PMOT39、PASeT1和PASeT2的吸收光谱,然后测试不同聚合物与ITIC衍生物共混后的吸收光谱。
然后通过在乙腈溶液中的循环伏安法测定聚合物的HOMO/LUMO能级,使用二茂铁作为外标,使用n-Bu4NPF6作为导电电解质。
测试结果如图2、图3和表1所示。
图2示出了聚合物材料以及与ITIC衍生物共混后的吸收光谱图;
其中,
图2(a)为单一聚合物材料的吸收光谱图;
图2(b)为聚合物材料与ITIC衍生物共混后的吸收光谱图。
图3示出了聚合物材料的能级分布图。
表1示出了PMTT56、PASeT2、PASeT1和PMOT39的光学物理性能。
表1聚合物光学物理性能
根据图2可以得出,在吸收光谱图中,三种聚合物材料PMTT56、POT39和PASeT1的吸收边带极其接近,表明三种聚合物具有非常接近的光学带隙,间接说明原子半径更大的硒原子和硫原子并没有破坏分子骨架的共轭和分子间的π-π堆积。然而PASeT1聚合物的π-π*吸收更宽,使得含有硒原子的聚合物材料具有更宽的吸收。此外,也可以看到PASeT1具有更强的π-π*吸收,表明该聚合物材料更容易实现光激发因而具有更好的光响应性。根据吸收边带,可以估算PMTT56、PMOT39、PASeT1和PASeT2的光学带隙分别为1.87、1.87、1.86和1.97ev。
在与ITIC-2F共混后,三个聚合物材料的共混膜吸收出现了显著的差异:PMTT56:ITIC-2F和PMOT39:ITIC-2F共混膜中ITIC-2F的特征吸收峰较弱,而在PASeT1:ITIC-2F共混膜中ITIC-2F的特征吸收峰则与聚合物的特征吸收峰较为平衡,说明PASeT1与ITIC-2F具有更好的共混相溶性。PASeT1:ITIC-2F共混体系更好的吸收性能有望使得该材料体系获得更好的光电流进而获得更高的光伏性能。
根据图3可以得出,PMTT56、PMOT39、PASeT1和PASeT2的HOMO/LUMO能级分别为5.39eV/3.40eV、5.34eV/3.38eV、5.41eV/3.40eV和5.36eV/3.38eV。相较于MOT的聚合物PMOT39,AST聚合物PMTT56和ASeT聚合物PASeT1表现出更深的HOMO能级。聚合物与ITIC-2F之间的LUMO能级差都大于0.3eV,这有利于给体受体界面处实现有效的激子拆分。聚合物较深的HOMO能级有利于聚合物材料在光伏器件中获得更高的开路电压。
测试例2
对应用例1-3和对比应用例1制备的光伏器件进行性能测试。
测试方法:
1.在AM1.5G太阳能模拟器照明(100mW cm-2)下,通过空气中Keithley 2400源测量装置测试得到器件的电流-电压曲线,利用量子效率系统(QE-R),在室温条件下测量外部量子效率(EQE)。光源为溴钨灯。
2.考虑到PMTT56:ITIC-2F在氯苯和二甲苯中的优异溶解性,故而在甲苯中的溶解性不会成为加工的限制因素,加之甲苯较低的沸点,有望提高器件的短路电流,因此进一步使用甲苯作为加工溶剂来制备光伏器件,然后对相关性能进行测试,并进一步通过透射电子显微镜(TEM)和原子力显微镜(AFM)研究PMTT56:ITIC-2F的共混薄膜形貌。
测试结果如图4-图7和表2所示。
图4示出了基于不同聚合物材料的光伏器件的电流-电压曲线(J-V)图;
其中,
图4(a)为PMTT56:ITIC-2F光伏器件的电流-电压曲线(J-V)图;
图4(b)为PMOT39:ITIC-2F光伏器件的电流-电压曲线(J-V)图;
图4(c)为PMSeT1:ITIC-2F和PMSeT2:ITIC-4F光伏器件的电流-电压曲线(J-V)图。
图5示出了基于不同聚合物材料的光伏器件的外量子效率曲线(EQE)图;
其中,
图5(a)为PMTT56:ITIC-2F光伏器件在不同溶剂下的外量子效率曲线图;
图5(b)为PMOT39:ITIC-2F光伏器件的的外量子效率曲线图;
图5(c)为PMSeT1:ITIC-2F和PMSeT2:ITIC-4F光伏器件的外量子效率曲线图。
图6示出了基于PMTT56:ITIC-2F制备混合薄膜的TEM照片;
其中,
图6(a)薄膜为甲苯和1%DPE处理;
图6(b)薄膜为邻二甲苯和1%DPE处理;
图6(c)薄膜为氯苯和1%DPE处理。
图7示出了基于PMTT56:ITIC-2F制备混合薄膜的AFM照片(尺寸:5μm×5μm);
其中,
图7(a)薄膜为甲苯和1%DPE处理;
图7(b)薄膜为邻二甲苯和1%DPE处理;
图7(c)薄膜为氯苯和1%DPE处理。
表2示出了不同结构光伏器件的性能。
表2基于不同聚合物的光伏器件性能
本测试例中,首先使用氯苯来制备光伏器件,配置聚合物:受体的氯苯的溶液(浓度为8mg/mL)通过旋涂的方法制备活性层。在氯苯制备的器件中,PMTT56达到了11.17%的光电转换效率,其中Jsc=17.76mAcm-2,Voc=0.935V,FF=67.3%。值得一提的是,由于PMTT56更深的HOMO能级,相比于PMOT39,PMTT56得到了更大的开路电压,达到0.94V,一般认为开路电压与给体的HOMO能级和受体的LUMO能级之差线性相关。然后采用作为常用于制备有机光电器件的非氯溶剂二甲苯作为加工溶剂制备光伏器件。低极性的共轭聚合物材料在二甲苯中的良好溶解性。从二甲苯溶液中旋涂得到的PMTT56/ITIC-2F共混薄膜具有非常好的均匀性,表明共混体系在二甲苯溶液中具有很好的成膜性能。然而由于短路电流的轻微下降(这可能是二甲苯较高的沸点使得旋涂膜厚度较低所致),使得采用二甲苯加工的器件的光电转换效率略有下降。
从图4中可以看出,采用甲苯溶液中制备的光伏器件保持了PMTT56:ITIC-2F非常高的开路电压,同时大幅度的提高了短路电流。
根据图6可以看出PMTT56:ITIC-2F共混薄膜表现出非常平整的形貌,根据图7可以看出,其表面粗糙度低于1.5nm。基于良好的形貌,甲苯制备的PMTT56:ITIC-2F器件得到了12.41%的光电转换效率。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
Claims (9)
2.根据权利要求1所述给体-受体聚合物,其特征在于,所述给体-受体聚合物中,所述给体选自苯并[3,4-b]二噻吩、噻吩、苯及其衍生物中的一种或多种。
3.根据权利要求1所述给体-受体聚合物,其特征在于,所述给体-受体聚合物中,主链上的所述受体选自由苯并[c][1,2,5]噻二唑、苯并[c][1,2,5]噁二唑、异吲哚啉-1,3-二酮、喹喔啉、苯并[d][1,2,3]三唑、噻吩并[3,4-c][1,2,5]噻二唑、噻吩并[3,4-b]吡嗪、噻吩并[3,4-b]噻吩、苯并[1,2-c:4,5-c']双([1,2,5]噻二唑)、[1,2,5]噻二唑并[3,4-g]喹喔啉、吡嗪并[2,3-g]喹喔啉、[3,3'-二吲哚亚基]-2,2'-二酮、二酮吡咯并吡咯、噻吩并吡咯二酮、噻吩并异吲哚以及具有未取代或烷基取代的噻吩或未取代或烷基取代的噻吩并[2,3-b]噻吩作为其桥连基团的衍生物组成的组。
4.根据权利要求1所述给体-受体聚合物,其特征在于,所述给体-受体聚合物中的重复单元个数为10~100。
5.一种组合物,其特征在于,包括由权利要求1-4任一项所述给体-受体聚合物以及非富勒烯衍生物所组成的共混物。
6.根据权利要求5所述组合物,其特征在于,所述非富勒烯衍生物选自ITIC-2F或ITIC-4F中的一种。
7.权利要求1-4任一项所述4-烷硫基噻吩环或4-烷硒基噻吩环的制备方法,其特征在于,包括如下步骤:
4-烷硫基噻吩环的制备方法:
将3-溴代-2-(2-乙基己基)噻吩加入溶剂中,低温冷却后,在惰性气体氛围下,加入正丁基锂溶液,搅拌后,加入1,2-二甲基二硫烷,搅拌反应后,用水淬灭反应然后提纯,得到所述4-烷硫基噻吩环;
4-烷硒基噻吩环的制备方法:
将3-甲硒基噻吩加入溶剂中,低温冷却后,在惰性气体氛围下,加入正丁基锂溶液,搅拌后,加入烷基溴,搅拌反应后,用水淬灭反应然后提纯,得到所述4-烷硒基噻吩环。
8.一种光伏器件,其特征在于,包括权利要求5-6任一项所述的组合物。
9.一种将权利要求1-4所述给体-受体聚合物应用于提高给体-受体聚合物的开路电压的方法。
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