CN108084406B - 基于侧链含吸光型受体的n型共轭聚合物及其制备和应用 - Google Patents

基于侧链含吸光型受体的n型共轭聚合物及其制备和应用 Download PDF

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CN108084406B
CN108084406B CN201711304282.4A CN201711304282A CN108084406B CN 108084406 B CN108084406 B CN 108084406B CN 201711304282 A CN201711304282 A CN 201711304282A CN 108084406 B CN108084406 B CN 108084406B
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黄飞
胡志诚
应磊
曹镛
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Dongguan volt ampere Photoelectric Technology Co., Ltd
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Abstract

本发明属于高分子光电材料领域，公开了一种基于侧链含吸光型受体的n型共轭聚合物及其制备方法和在有机光电器件中的应用。本发明聚合物结构式如下所示：其中，n为小于100万的正整数，a为3～40的正整数，X为甲基或氟原子，R1、R2、R3、R4相同或不同的分别为烷基链；D为给电子共轭单元结构，为噻吩、呋喃、联噻吩、联呋喃、噻吩联呋喃、并噻吩、并呋喃及以上结构衍生物中的至少一种。本发明n型共轭聚合物的主链为高电子迁移率的n型主链，侧链引入高效窄带隙的吸光型n型小分子，使得共轭聚合物在具有较高吸收系数、较宽吸收光谱和较高迁移率的同时，还能保持有序的相分离，可作为高效的电子受体用于高效有机光伏器件中。

Description

基于侧链含吸光型受体的n型共轭聚合物及其制备和应用
技术领域
本发明属于高分子光电材料领域，特别涉及一种基于侧链含吸光型受体的n型共轭聚合物及其制备方法和在有机光电器件中的应用。
背景技术
随着全球对于能源需求的逐年增加，石油、煤炭等传统能源的日益枯竭，以及对保护地球生态环境的需要，全世界越来越多的科学家将研究集中在氢气、太阳能等取之不尽用之不竭的可再生清洁能源。已经成熟的无机硅、砷化镓、磷化铟等基于无机材料的光伏器件已经在市场上占有主导地位，然而由于其对于材料纯度的要求高，加工过程中会产生高能耗及污染等问题，且其价格非常昂贵，因此在追求低成本和绿色环保的今天，其大规模应用受到了限制。
有机光伏器件作为一种新型薄膜光伏电池技术，具有全固态、光伏材料性质可调范围宽、可实现半透明、柔性电池、具有大面积低成本制备潜力等突出优点。有机材料的光伏性能可调范围宽，可利用化学手段对材料的能级、载流子迁移率以及吸收等性能进行有效的调控。有机/聚合物光伏器件可采用打印、印刷等方法进行加工，可借鉴传统塑料的加工工艺，通过卷对卷滚动加工流程制造大面积、柔性的薄膜光伏器件，该生产工艺能够有效降低光伏电池的制造成本。有机光伏器件几乎不受环境和场地限制，在许多场合可将光能转换为电能，同时与无机半导体光伏器件有非常强的互补性，无疑具有巨大的商业开发价值和市场竞争力。因此有机光伏器件的研究引起了广泛关注，以有机光伏器件为核心的科学研究已经成为一个世界范围内竞争激烈的材料科学前沿研究领域。
有机光伏器件的受体研究进展缓慢，早期的研究以富勒烯为主。最近两年来，非富勒烯进展较快，然后以共轭聚合物为受体的报道相对较少，效率也不高。其主要原因是现有的受体的吸收系数不高，活性层薄膜相分离不可控，以及较低的电子迁移率。通过对于共轭聚合物分子结构的调节，保留高迁移率主链结构的同时侧链引入高效窄带隙的吸光型n型小分子，使得共轭聚合物在具有较高吸收系数，较宽吸收光谱和较高迁移率的同时，还能保持有序的相分离，可作为高效的电子受体用于高效有机光伏器件中
发明内容
为了克服上述现有技术的缺点与不足，本发明的首要目的在于提供一种基于侧链含吸光型受体的n型共轭聚合物。
本发明n型共轭聚合物的主链为萘二酰亚胺和电子杂环共轭单元，侧链为吸光型受体。其主链为高电子迁移率的n型主链，侧链引入高效窄带隙的吸光型n型小分子，使得共轭聚合物在具有较高吸收系数、较宽吸收光谱和较高迁移率的同时，还能保持有序的相分离，可作为高效的电子受体用于高效有机光伏器件中。
本发明另一目的在于提供一种上述基于侧链含吸光型受体的n型共轭聚合物的制备方法。
本发明再一目的在于提供上述基于侧链含吸光型受体的n型共轭聚合物在有机光电器件中的应用。
本发明的目的通过下述方案实现：
一种基于侧链含吸光型受体的n型共轭聚合物，结构式如下所示：
Figure BDA0001501659810000021
其中，n为小于100万的正整数，a为3～40的正整数，X为甲基或氟原子，R1、R2、R3、R4相同或不同的分别为烷基链；D为给电子共轭单元结构，可为噻吩、呋喃、联噻吩、联呋喃、噻吩联呋喃、并噻吩、并呋喃及以上结构衍生物中的至少一种。
进一步地，所述的R1、R2、R3、R4相同或不同的分别为具有1～40个碳原子的直链、支链或者环状烷基链；所述直链、支链或者环状烷基链中的一个或一个以上碳原子可被氧原子、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；所述直链、支链或者环状烷基链中的一个或一个以上氢原子可被氟原子、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。
进一步地，所述的D为给电子共轭单元结构，具有如下结构的至少一种：
Figure BDA0001501659810000031
本发明的基于侧链含吸光型受体的n型共轭聚合物可通过Stille聚合反应得到。
本发明的基于侧链含吸光型受体的n型共轭聚合物可由以下M1分别与M2、M3、M4、M5、M6通过Stille聚合反应得到。
Figure BDA0001501659810000032
M1
Figure BDA0001501659810000041
M2、
Figure BDA0001501659810000042
M3、M4、M5、M6。
其中，单体M1参考按照文献[Journal of medicinal chemistry,2013,56(7):2959-2974.]公开的方法合成。
单体M2，M3，M4，M5，M6分别按照文献[Journal of the American ChemicalSociety,2011,133(5):1405-1418.]公开的方法合成。
本发明还提供上述基于侧链含吸光型受体的n型共轭聚合物作为电子受体在有机光电器件中的应用。
本发明n型共轭聚合物的主链为萘二酰亚胺和电子杂环共轭单元，侧链为吸光型受体。其主链为高电子迁移率的n型主链，侧链引入高效窄带隙的吸光型n型小分子，使得共轭聚合物在具有较高吸收系数、较宽吸收光谱和较高迁移率的同时，还能保持有序的相分离，可作为高效的电子受体用于高效有机光伏器件中。
本发明的基于侧链含吸光型受体的n型共轭聚合物可应用于有机光电器件中，制备得到有机光伏器件，其结构如图1所示，由衬底、阴极、阴极界面层、光吸收层、阳极界面层、阳极或由衬底、阳极、阳极界面层、光吸收层、阴极界面层、阴极依次层叠构成。所述光吸收层含有本发明的基于侧链含吸光型受体的n型共轭聚合物。
上述有机光伏器件中，所述阳极的材料优选为铝、银、金、钙/铝合金或钙/银合金。
上述有机光伏器件中，所述阳极界面层的材料优选为有机共轭聚合物(如聚3,4-乙撑二氧噻吩/聚苯乙烯磺酸盐)或无机半导体。
上述有机光伏器件中，所述阴极的材料优选为金属、金属氧化物(如氧化铟锡导电膜(ITO)、掺杂二氧化锡(FTO)、氧化锌(ZnO)、铟镓锌氧化物(IGZO))和石墨烯及其衍生物中的至少一种。
上述有机光伏器件中，所述衬底的材料优选为玻璃、柔性材料(如聚酰亚胺、聚对苯二甲酸乙二醇酯、乙烯对苯二甲酸酯、聚萘二甲酸乙二醇酯或其他聚酯材料)、金属、合金和不锈钢薄膜中的至少一种。
本发明相对于现有技术，具有如下的优点及有益效果：
(1)本发明设计了侧链含吸光型受体的n型共轭聚合物，所述共轭聚合物侧链引入高效窄带隙的吸光型n型小分子，可以提高共轭聚合物的吸收系数，拓宽吸收光谱。
(2)所述的侧链含吸光型受体的n型共轭聚合物侧链含平面性很好的引达省氰基茚酮可诱导有效相分离，提高共轭聚合物的电子迁移率。
附图说明
图1为有机光伏器件结构示意图。
图2为本发明的基于侧链含吸光型受体的n型共轭聚合物(P1、P2、P3)的紫外-可见光-近红外吸收谱图。
图3为本发明的基于侧链含吸光型受体的n型共轭聚合物(P4、P5)的紫外-可见光-近红外吸收谱图。
图4为电池结构：ITO阴极/阴极界面层/活性层/阳机界面层/阳极(倒装结构)时，含本发明的基于侧链含吸光型受体的n型共轭聚合物(P1，P2，P3)作为电子受体材料时电池器件的电流-电压曲线图。
图5为电池结构：ITO阴极/阳极界面层/活性层/阴机界面层/阳极(正装结构)时，含为本发明的基于侧链含吸光型受体的n型共轭聚合物(P1，P2，P3)作为电子受体材料时电池器件的电流-电压曲线图。
图6为电池结构：ITO阴极/阴极界面层/活性层/阳机界面层/阳极(倒装结构)时，含为本发明的基于侧链含吸光型受体的n型共轭聚合物(P4，P5)作为电子受体材料时电池器件的电流-电压曲线图。
图7～图9为本发明的基于侧链含吸光型受体的n型共轭聚合物(P1，P2，P3，P4，P5)的合成路线图。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
下列实施例中涉及的物料均可从商业渠道获得。
实施例1
本发明的基于侧链含吸光型受体的n型共轭聚合物可通过Stille聚合反应得到，如可由图7～图9所示合成路线合成得到基于侧链含吸光型受体的n型共轭聚合物P1，P2，P3，P4，P5。
(1)单体M1参考按照文献[Journal of medicinal chemistry,2013,56(7):2959-2974.]公开的方法合成。
(2)单体M2，M3，M4，M5，M6按照文献[Journal of the American ChemicalSociety,2011,133(5):1405-1418.]公开的方法合成。
(3)聚合物的合成：
P1：将单体M1(0.5mmol)和单体M2(0.5mmol)混合，通入氮气保护，加入8mL甲苯。抽换气两次后加入5mg Pd(PPh3)4，95℃反应12h后用甲醇将聚合物沉淀出来，洗涤三次。得深色聚合物P1，产率80.7％。
1H NMR(CDCl3 500MHz):δ:8.53-8.84(m,6H),7.20-7.48(m,16H),4.13-3.50(m,8H),2.00-1.85(m,20H),1.05-1.30(br,76H),0.87(t,24H).
GPC:Mn＝47.8KDa,Mw＝264.4KDa,PDI＝5.53.
Elem.Anal.:C,74.44；H6.01；F,1.49；N,5.49；O,5.02；S,7.55.
P2：将单体M1(0.5mmol)和单体M3(0.5mmol)混合，通入氮气保护，加入12mL甲苯。抽换气两次后加入7mg Pd(PPh3)4，95℃反应12h后用甲醇将聚合物沉淀出来，洗涤三次。得深色聚合物P2，产率82.9％。
1H NMR(CDCl3 500MHz):δ:8.63-8.82(m,6H),7.22-7.41(m,16H),4.12-3.50(m,8H),2.00-1.85(m,20H),1.05-1.30(br,76H),0.87(t,24H).
GPC:Mn＝45.8KDa,Mw＝253.7KDa,PDI＝5.54.
Elem.Anal.:C,75.39；H,6.09；F,1.51；N,5.56；O,6.36；S,5.09.
P3：将单体M1(0.5mmol)和单体M4(0.5mmol)混合，通入氮气保护，加入11mL甲苯。抽换气两次后加入4mg Pd(PPh3)4，95℃反应12h后用甲醇将聚合物沉淀出来，洗涤三次。得深色聚合物P3，产率81.2％。
1H NMR(CDCl3 500MHz):δ:8.66-8.86(m,6H),7.24-7.45(m,16H),4.17-3.55(m,8H),2.04-1.87(m,20H),1.15-1.40(br,76H),0.90(t,24H).
GPC:Mn＝48.8KDa,Mw＝273.77KDa,PDI＝5.61.
Elem.Anal.:C,74.91；H,6.05；F,1.50；N,5.53；O,5.68；S,6.33.
P4：将单体M1(0.5mmol)和单体M5(0.5mmol)混合，通入氮气保护，加入11mL甲苯。抽换气两次后加入3mg Pd(PPh3)4，95℃反应12h后用甲醇将聚合物沉淀出来，洗涤三次。得深色聚合物P4，产率81.1％。
1H NMR(CDCl3 500MHz):δ:8.64-8.82(m,6H),7.34-7.55(m,16H),4.27-3.65(m,8H),2.08-1.88(m,20H),1.16-1.48(br,76H),0.85(t,24H).
GPC:Mn＝44.8KDa,Mw＝241.9KDa,PDI＝5.40.
Elem.Anal.:C,75.46；H,6.17；F,1.55；N,5.71；O,5.87；S,5.23.
P5：将单体M1(0.5mmol)和单体M6(0.5mmol)加入到25mL两口烧瓶中，通入氮气保护，加入11mL甲苯。抽换气两次后加入4mg Pd(PPh3)4，95℃反应12h后用甲醇将聚合物沉淀出来，洗涤三次。得深色聚合物P5，产率81.5％。
1H NMR(CDCl3 500MHz):δ:8.54-8.72(m,6H),7.35-7.56(m,16H),4.25-3.66(m,8H),2.18-1.98(m,20H),1.26-1.58(br,76H),0.91(t,24H).
GPC:Mn＝45.8KDa,Mw＝253.274KDa,PDI＝5.53.
Elem.Anal.:C,74.97；H,6.13；F,1.54；N,5.68；O,5.19；S,6.50.
将所得的聚合物进行溶液的吸收光谱的测定，结果如图2和图3所示。从溶液的浓度(0.02mg/ml)和所测得的吸收值可以计算出聚合物P1，P2，P3，P4，P5的吸收系数。P1，P2，P3，P4，P5在最高峰的吸收系数分别为1.37×106cm-1，1.21×106cm-1，1.23×106cm-1，1.45×106cm-1和1.19×106cm-1。
实施例2
以实施例1所合成的共轭聚合物P1，P2，P3作为电子受体在有机光伏器件(ITO阴极/阴极界面层/活性层/阳机界面层/阳极)中应用。
将ITO导电玻璃，方块电阻～20欧/平方厘米，预切成15毫米×15毫米方片。依次用丙酮、微米级半导体专用洗涤剂、去离子水、异丙醇超声清洗，氮气吹哨后置于恒温烘箱备用。在ITO上旋凃一层5nm厚的PFN-Br，然后旋涂活性层材料PBDB-T/P1，PBDB-T/P2，PBDB-T/P3，厚度为110纳米，最后蒸镀MoO3和Al电极。所有制备过程均在提供氮气氛围的手套箱内进行。所制备的倒装电池器件的电流-电压曲线如图4所示，相关的数据在表1中列出。可以看出，本发明的基于侧链含吸光型受体的n型共轭聚合物具有较高的光电流。
实施例3
以实施例1所合成的共轭聚合物P1，P2，P3(结构中AB组分相同)作为电子受体在有机光伏器件(ITO阳极/阳极界面层/活性层/阴机界面层/阴极)中应用。
将ITO导电玻璃，方块电阻～20欧/平方厘米，预切成15毫米×15毫米方片。依次用丙酮、微米级半导体专用洗涤剂、去离子水、异丙醇超声清洗，氮气吹哨后置于恒温烘箱备用。在ITO上旋凃一层20nm厚的PEDOT:PSS，然后旋涂活性层材料PBDB-T/P1，PBDB-T/P2，PBDB-T/P3，厚度均为100纳米。然后旋涂一层5nm厚的PFN-Br，最后蒸镀Al电极。所有制备过程均在提供氮气氛围的手套箱内进行。所制备的正装电池器件的电流-电压曲线如图5所示，相关的数据在表1中列出。
实施例4
以实施例1所合成的共轭聚合物P4，P5作为电子受体在有机光伏器件(ITO阳极/阳极界面层/活性层/阴机界面层/阴极)中应用。
将ITO导电玻璃，方块电阻～20欧/平方厘米，预切成15毫米×15毫米方片。依次用丙酮、微米级半导体专用洗涤剂、去离子水、异丙醇超声清洗，氮气吹哨后置于恒温烘箱备用。在ITO上旋凃一层20nm厚的PEDOT:PSS，然后旋涂活性层材料PBDB-T/P4，PBDB-T/P5，PBDB-T/P3，厚度均为100纳米。然后旋涂一层5nm厚的PFN-Br，最后蒸镀Al电极。所有制备过程均在提供氮气氛围的手套箱内进行。所制备的正装电池器件的电流-电压曲线如图6所示，相关的数据在表1中列出。
表1有机光伏器件的性能参数
Figure BDA0001501659810000091
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (7)

1.一种基于侧链含吸光型受体的n型共轭聚合物，其特征在于结构式如下所示：
Figure FDA0002212193890000011
其中，n为小于100万的正整数，a为3～40的正整数，X为甲基或氟原子，R1、R2、R3、R4相同或不同的分别为烷基链；D为给电子共轭单元结构，为噻吩、呋喃、联噻吩、联呋喃、噻吩联呋喃、并噻吩、并呋喃及以上结构衍生物中的至少一种。
2.根据权利要求1所述的基于侧链含吸光型受体的n型共轭聚合物，其特征在于：所述的R1、R2、R3、R4相同或不同的分别为具有1～40个碳原子的直链、支链或者环状烷基链。
3.根据权利要求2所述的基于侧链含吸光型受体的n型共轭聚合物，其特征在于：所述直链、支链或者环状烷基链中的一个或一个以上氢原子被氟原子、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。
4.根据权利要求1所述的基于侧链含吸光型受体的n型共轭聚合物，其特征在于：所述的D为给电子共轭单元结构，具有如下结构的至少一种：
Figure FDA0002212193890000012
5.一种权利要求1～4任一项所述的基于侧链含吸光型受体的n型共轭聚合物的制备方法，其特征在于通过Stille聚合反应得到。
6.根据权利要求5所述的基于侧链含吸光型受体的n型共轭聚合物的制备方法，其特征在于由以下M1分别与M2、M3、M5、M6通过Stille聚合反应得到；
Figure FDA0002212193890000021
7.权利要求1～4任一项所述的基于侧链含吸光型受体的n型共轭聚合物在有机光电器件中的应用。
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