CN110734539A - 基于五元或七元芳香稠环的聚合物及其在有机光电器件中的应用 - Google Patents

基于五元或七元芳香稠环的聚合物及其在有机光电器件中的应用 Download PDF

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CN110734539A
CN110734539A CN201910979949.3A CN201910979949A CN110734539A CN 110734539 A CN110734539 A CN 110734539A CN 201910979949 A CN201910979949 A CN 201910979949A CN 110734539 A CN110734539 A CN 110734539A
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黄飞
贾涛
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South China University of Technology SCUT
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Abstract

本发明涉及基于五元或七元芳香稠环的聚合物及其在有机光电器件中的应用。所述材料为主链包含一类五元或七元芳香稠环的共轭聚合物，具有较宽的光谱吸收与较高的摩尔吸收系数。该类聚合物可以作为电子受体用于有机光伏器件中，能够提高电池器件短路电流，获得高效率的有机太阳电池器件。

Description

基于五元或七元芳香稠环的聚合物及其在有机光电器件中的 应用
技术领域
本发明涉及高分子光电材料领域，具体涉及一类基于五元或七元芳香稠环的聚合物及其在有机光电器件中的应用。
背景技术
能源短缺、环境污染是我国经济可持续发展面临的重大问题。发展新型绿色能源技术是解决上述问题的重要途径之一，而太阳能发电(光伏发电)是众多绿色、可再生能源中的佼佼者，对于降低污染和减少二氧化碳排放，实现低碳经济的发展具有重要意义。有机/聚合物太阳电池因其具有成本低廉、可采用溶液加工制备大面积器件、以及可制成柔性器件等突出优点引起研究学者的广泛关注。
伴随近年来材料体系和器件工艺上的创新突破，基于富勒烯衍生物受体型的单节太阳电池的器件效率已经超过11％。但是富勒烯衍生物自身存在的可见光区吸光弱、能级调控范围窄、光化学不稳定、形貌稳定性差等缺点，使得科学家不得不寻找替代它们的受体材料(Acc.Chem.Res.2012,45,723-733)。作为聚合物太阳电池领域的一个重要分支，全聚合物太阳能电池使用n-型聚合物取代富勒烯衍生物或者非富勒烯共轭小分子作为受体的新型太阳电池技术。聚合物取代富勒烯衍生物与非富勒烯小分子作为受体材料具有更好的成膜与加工性能，光伏器件也具有更好的机械性能，有利于柔性有机太阳电池的大面积集成化制备(Acc.Chem.Res.2016,49,2424-2434；Chem.Rev.2019,119,8028–8086)。因此，近年来全聚合物太阳电池不断受到研究者的关注。
在诸多报道的n-型聚合物受体中，商业化的N2200是一种最成功，研究也最广泛的受体材料(Nature,2009,457,679-686.)。我们课题组基于自主发展的聚合物给体TzBI系列与N2200匹配，实现了超过11％的能量转换效率(Energy Environ.Sci.2017,10,1243；Adv.Mater.2017,29,1703906；Nat.Commun.2019,10,4100)。然而由于N2200在长波区具有较低的摩尔吸光系数，导致制备的全聚合物电池器件长波区光响应较弱，短路电流较低。中国科学院化学研究所与香港科技大学等报道了主链含有氰基茚酮单元的n-型聚合物受体(Angew.Chem.Int.Edit.2017,56,13503-13507；ACS Energy Lett.2019,4,417-422)。这类聚合物受体兼具非富勒烯小分子受体高摩尔吸光系数与传统聚合物受体优良的成膜加工性能，对应的器件也实现了超过10％的能量转换效率。然而，目前对这类聚合物受体的研究还十分有限，见诸报道的几篇文献所载的聚合物受体光谱吸收范围多在800nm以前，难以实现近红外区光谱的吸收与有效利用。通过聚合物主链引入多元稠环，提高聚合物的摩尔吸光系数，并将光谱吸收范围扩宽至近红外区，有望解决上述问题，并提升基于聚合物电子受体的有机光伏器件性能。
发明内容
本发明的目的在于设计并合成基于五元或七元芳香稠环的聚合物用于有机光电器件中。
本发明所提供的一类基于五元或七元芳香稠环的聚合物，其结构式如式I与式II所示：
所述式I与式II中，n代表所述聚合物的重复单元数，其为2～1000之间的自然数；R1、R2为烷基链；A为拉电子基团；共聚单元为共轭芳环单元。
进一步地，所述的R1、R2为氢原子、卤素原子；或者R1、R2为选自C1～C60的直链、支链或者环状烷基链，其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、甲基、乙基、甲氧基、硝基取代；或者所述直链、支链或者环状烷基链中的氢原子被氟原子或上述官能团取代。
进一步地，所述的A单元选自如下结构中的任一种：
Figure BDA0002234856950000022
其中，虚线①表示五元或七元稠环单元与A单元的连接位点，虚线②表示共聚单元与A单元的连接位点；X为氢原子、卤素原子。
进一步地，所述的共聚单元选自如下结构中的任一种及其组合：
Figure BDA0002234856950000031
其中，R3为氢原子、卤素原子；或者R3为选自C1～C60的直链、支链或者环状烷基链，其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、甲基、乙基、甲氧基、硝基取代；或者所述直链、支链或者环状烷基链中的氢原子被氟原子或上述官能团取代。
所述基于五元或七元芳香稠环的聚合物用于有机光电器件中。
与现有技术相比，本发明具有以下优点：
(1)本发明设计基于五元或七元芳香稠环的聚合物，能够扩宽聚合物的光谱吸收范围，提高聚合物的摩尔吸光系数，实现太阳光的有效吸收和利用。
(2)本发明提供的基于五元与七元芳香稠环的聚合物主链含有多个缺电性单元，可作为电子受体应用于有机光伏器件中，获得高短路电流、高能量转换效率的光伏器件。制备的光伏器件短路电流超过22mA cm-2，电池能量转换效率超过14％。
附图说明
图1为实施例所述的代表聚合物PJ1与PJ2的紫外-可见-近红外吸收光谱图；
图2为实施例所述的代表聚合物PJ1与PJ2的循环伏安(CV)曲线图；
图3为实施例所述的聚合物PJ1、PJ2作为电子受体，与PBDB-T匹配制备的有机太阳电池器件电流-电压(J-V)曲线图。
具体实施方式
下面通过具体实施例对本发明作进一步的说明，其目的在于帮助更好的理解本发明的内容，具体包括合成、器件制备与表征结果，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。
实施例1：化合物TTPBT按照[Joule 2019,3(4),1140-1151]公开的方法合成。
实施例2：稠环双醛化合物TTPBT-CHO的合成：
干燥的100mL两口烧瓶在抽换气三次且氮气填充后，加入无水N,N-二甲基甲酰胺(20ml)，室温下使用注射器往反应液中逐滴滴加三氯氧磷(1mL)。搅拌反应1小时后，将化合物TTPBT(710mg,0.5mmol)溶于10mL超干二氯甲烷中，逐滴滴加至反应液，将温度升至110℃搅拌12小时。反应液冷却至室温，加入冰水淬灭反应，并用饱和K2CO3水溶液调节PH为中性。二氯甲烷萃取，旋干溶剂，粗产物经硅胶柱层析分离提纯，得到亮黄色固体化合物TTPBT-CHO(635mg,产率86％)。1H NMR(500MHz,CDCl3):δ10.15(s,2H),4.63(d,J＝7.7Hz,4H),3.20(t,J＝7.8Hz,4H),2.11–1.99(m,2H),1.98–1.89(m,4H),1.54–1.44(m,4H),1.43–1.35(m,4H),1.34–1.11(m,60H),1.04(m,16H),0.99–0.84(m,46H).13C NMR(126MHz,CDCl3)δ181.67,147.48,146.76,143.18,137.02,136.80,132.95,129.64,127.41,112.42,55.25,38.87,31.96,31.92,30.40,30.31,29.73,29.68,29.66,29.65,29.62,29.59,29.55,29.54,29.50,29.39,29.37,29.35,29.30,28.19,25.42,22.72,14.14,14.12.MS(MALDI-TOF):m/z 1475.6799(M+).
Figure BDA0002234856950000041
实施例3：稠环结构聚合单体M1的合成
在两口圆底烧瓶中加入双醛化合物TTPBT-CHO(738mg,0.5mmol),化合物IC-Br(683mg,2.5mmol)，抽换气三次并使体系填充氮气。用注射器在反应瓶中加入氯仿(80mL)与吡啶(2mL)，反应液在80℃温度下搅拌反应18小时。待反应液冷却至室温，粗产物经硅胶柱层析提纯，洗脱剂是石油醚/二氯甲烷(2:1)，得黑色固体化合物M1(874mg，88％)。1H NMR(500MHz,CDCl3):δ9.13(s,2H),8.84(s,1H),8.52(d,J＝8.4Hz,1H),8.03(d,J＝1.6Hz,1H),7.89–7.78(m,3H),4.77(m,4H),3.20(t,J＝7.5Hz,4H),2.16(m,2H),1.91–1.83(m,4H),1.55-1.49(m,4H),1.38-1.36(m,4H),1.33-1.23(m,28H),1.24-1.12(m,36H),1.04-0.99(m,36H),0.88-0.81(m,22H).13C NMR(126MHz,CDCl3):δ187.32,186.91,159.83,159.21,153.59,147.46,145.13,141.35,138.49,138.29,137.78,137.60,137.17 136.01,135.42,134.15,134.12,134.09,133.49,130.80 130.77,130.74,130.71,130.14,129.46,128.15,126.70,126.34,124.50,120.13,115.26,115.11,114.90,114.55,113.60,113.56,68.80,68.28,55.70,39,13,31.97,31.95,31.93,31.23,30.54,29.90,29.82,29.79,29.74,29.71,29.69,29.65,29.57,29.49,29.46,29.42,29.37,25.59,22.72,22.70,14.14.MS(MALDI-TOF):m/z 1986.5157(M+).
实施例4：代表性聚合物PJ1的合成：
在25mL干燥的双口瓶中加入聚合单体M1(596mg，0.3mmol)与M2(123mg，0.3mmol)，催化剂三(二亚苄基茚丙酮)二钯(5.4mg)，配体三邻甲基苯基膦(8.1mg)，通过真空双排管进行抽换气三次，用注射器加入溶剂氯苯(6mL)。反应液在150℃温度下搅拌反应72小时。恢复至室温后，将聚合物溶液滴加到300mL的甲醇中，过滤得到聚合物沉淀。聚合物通过索氏抽提装置先后以甲醇、正己烷、二氯甲烷、氯仿抽提，收集抽提的氯仿相经浓缩后在甲醇中沉淀，过滤收集固体并烘干得黑色目标聚合物PJ1(435mg，76％)。GPC:Mn＝16.22kDa,Mw＝32.57kDa.1H NMR(600MHz,C2D2Cl4,120℃):δ9.22-8.78(m,4H),8.08-8.02(m,4H),7.73-7.56(m,2H),4.86(m,4H),3.30(m,4H),2.26(m,2H),1.99(m,4H),1.62(m,4H),1.48(m,4H),1.34-1.13(m,100H),0.90(m,22H)。
实施例5：代表性聚合物PJ2的合成：
在25mL干燥的双口瓶中加入聚合单体M1(596mg，0.3mmol)、聚合单体M3(148mg，0.3mmol)、催化剂三(二亚苄基茚丙酮)二钯(5.4mg)与配体三邻甲基苯基膦(8.1mg)，通过真空双排管进行抽换气三次，用注射器加入溶剂氯苯(6mL)。反应液在150℃温度下搅拌反应72小时。恢复至室温后，将聚合物溶液滴加到300mL的甲醇中，过滤得到聚合物沉淀。聚合物通过索氏抽提装置先后以甲醇、正己烷、二氯甲烷、氯仿抽提，收集抽提的氯仿相经浓缩后在甲醇中沉淀，过滤收集固体并烘干得黑色目标聚合物PJ2(478mg，80％)。GPC:Mn＝26.33kDa,Mw＝63.90kDa.1H NMR(600MHz,C2D2Cl4,120℃):δ9.20-8.75(m,4H),8.12-7.98(m,4H),7.76-7.60(m,4H),4.86(m,4H),3.35-3.20(m,4H),2.22(m,2H),2.01(m,4H),1.58(m,4H),1.42(m,4H),1.36-1.12(m,100H),0.88(m,22H)。
实施例6:
以实施例1～5合成的代表性聚合物PJ1与PJ2作为电子受体用于有机太阳电池器件中(ITO阳极/阳极界面层/活性层/阴机界面层/阴极)。
将购买到的氧化铟锡(ITO)玻璃分别依次用丙酮超声清洗10分钟；低浓度micro级洗涤剂超声清洗15分钟；超纯去离子水超声清洗2～3次，每次10分钟；色谱纯异丙醇超声清洗10～15分钟，经过清洗的ITO玻璃基片用氧气等离子处理5分钟待用。在ITO基片上旋涂一层聚乙撑二氧噻吩：聚苯乙烯磺酸盐(PEDOT:PSS),150℃干燥15min，将实施例1～5得到的聚合物PJ1与PJ2与给体PBDB-T共混配成氯仿溶液，旋涂在PEDOT:PSS阳极界面层作为活性层，在活性层上旋涂一层PFN-Br作为阴极界面层，在界面层上蒸镀厚度约80nm的Ag作为阴极。电池有效面积通过掩模版控制，为0.04cm2。所有制备过程均在氮气氛围的手套箱内进行。器件性能测试在Oriel91192型AM 1.5G太阳光模拟灯的照射下进行，辐射度为1kW/m2，使用Keithley 2400型数字源表测试J-V曲线。所制备的正装电池器件的电流-电压曲线分别如图3所示，相关的数据在表一中列出。可以看出，本发明所述的聚合物作为电子受体材料能够极大地扩宽器件的光谱响应范围，提升电池器件的短路电流，并且填充因子也较高，基于PJ1与PBDB-T匹配的电池器件效率最高可达14.38％。
表1为所述的代表性聚合物PJ1与PJ2作为电子受体制备的有机太阳电池的器件性能参数器件结构：ITO/PEDOT:PSS/PBDB-T:Acceptor/PFN-Br/Ag
Figure BDA0002234856950000062
Figure BDA0002234856950000071
图1为实施例所述的代表聚合物PJ1与PJ2的紫外-可见-近红外吸收光谱图，聚合物PJ1与PJ2对应的薄膜吸收边分别为892nm与872nm，对应的光学带隙为1.39eV与1.42eV。
图2为实施例所述的代表聚合物PJ1与PJ2的循环伏安(CV)曲线图，Ag/AgCl电极通过Fc/Fc+校正为0.38V，通过电化学计算的PJ1与PJ2的HOMO能级分别为-5.70eV与-5.50eV，LUMO能级分别-3.89eV与-3.86eV。

Claims (5)

1.基于五元或七元芳香稠环的聚合物，其特征在于，具有式I或式II的结构：
Figure FDA0002234856940000011
所述式I与式II中，n代表所述聚合物的重复单元数，其为2～1000之间的自然数；R1、R2为烷基链；A为拉电子基团；共聚单元为共轭芳环单元。
2.根据权利要求1所述基于五元或七元芳香稠环的聚合物，其特征在于，所述的R1、R2为氢原子、卤素原子；或者R1、R2选自C1～C60的直链、支链或者环状烷基链，其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、甲基、乙基、甲氧基、硝基取代；或者所述直链、支链或者环状烷基链中的氢原子被氟原子或上述官能团取代。
3.根据权利要求1所述的基于五元或七元芳香稠环的聚合物，其特征在于，所述的A单元选自如下结构中的任一种：
Figure FDA0002234856940000012
其中，虚线①表示五元或七元芳香稠环单元与A单元的连接位点，虚线②表示共聚单元与A单元的连接位点；X选自氢原子、卤素原子、C1～C60的直链、支链或环状烷基、C1～C60的烷氧基或C1～C60的烷硫基。
4.根据权利要求1所述基于五元或七元芳香稠环的聚合物，其特征在于，所述的共聚单元选自下述结构式中的任一种及其组合：
Figure FDA0002234856940000021
其中，R3为氢原子、卤素原子；或者R3为选自C1～C60的直链、支链或者环状烷基链，其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、甲基、乙基、甲氧基、硝基取代；或者所述直链、支链或者环状烷基链中的氢原子被氟原子或上述官能团取代。
5.权利要求1～4所述基于五元或七元芳香稠环的聚合物用于有机光电器件中。
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