CN112390937A - 一类含b–n共价键的共轭聚合物及其光伏应用 - Google Patents

一类含b–n共价键的共轭聚合物及其光伏应用 Download PDF

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CN112390937A
CN112390937A CN202011177300.9A CN202011177300A CN112390937A CN 112390937 A CN112390937 A CN 112390937A CN 202011177300 A CN202011177300 A CN 202011177300A CN 112390937 A CN112390937 A CN 112390937A
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段春晖
庞淑婷
黄飞
曹镛
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South China University of Technology SCUT
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Abstract

本发明涉及有机光伏材料领域，具体涉及一类含B–N共价键的共轭聚合物及其光伏应用。所述的含B–N共价键的共轭聚合物结构通式M如下，其中Ar1、Ar2、Ar3为芳香基团，R1为H或C1～C40的烷基链、烷氧链、烷硫链、烷基硅烷、卤素原子或氰基取代基，共聚单体为芳香共聚单元，n为1～10000的自然数。通过共聚单元可调控聚合物的吸收、能级等性质。该聚合物具有合适的电荷传输性能，适于用作有机光伏器件的活性层材料。同时，该类含B–N共价键的共轭聚合物具有高三线态能级，对光伏器件的三线态复合有抑制作用。

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一类含B–N共价键的共轭聚合物及其光伏应用
技术领域
本发明涉及有机光伏领域，具体涉及一类含B–N共价键的共轭聚合物及其光伏应用。
背景技术
有机太阳电池具有质轻、柔性、半透明、可进行卷对卷大面积加工等优点，在新能源领域具有重大潜力，近年来得到广泛关注和研究。有机光伏领域的快速发展与新型、高性能材料的开发有着密不可分的关系。因此，开发新型共聚单元以及共轭聚合物将为器件效率提升带来新的潜力和动力。
在诸多共聚单元中，硼氮单元由于其特殊的结构和电子特性而在光伏领域得到关注。J.Liu等开发了B←N配位键桥连的双联吡啶(BNBP)新型缺电子单元用于构筑聚合物受体材料。B←N配位键作为联吡啶的桥连键，固定了分子的平面结构，同时起到了降低能级的作用，相应的聚合物受体在全聚合物有机太阳电池中获得了超过10％光电转换效率，说明硼氮单元在有机光伏领域具有巨大潜力。
在本发明中，我们以含B–N共价键的硼氮单元作为给电子单元，开发了一类含B–N共价键的共轭聚合物，通过共聚单元、侧链取代基等对聚合物光伏性能和聚集形态进行调控，优选光吸收互补、能级匹配的给受体材料，并结合活性层形貌优化，能够制备高效率有机太阳电池。同时，这类含B–N共价键的共轭聚合物具有高三线态能级(E(T1))，能够抑制有机太阳电池中的三线态复合，提高激子利用率进而提高器件光电转换效率。
含B–N共价键的共轭聚合物是以含B–N共价键的单体与其他共聚单体通过金属钯催化剂催化聚合，后经纯化得到相应的聚合物材料，作为具有高三线态能级的新型材料，在有机太阳电池的研究历史上是一个空白，因此本发明具有原创性。
发明内容
本发明的目的通过下述方案实现：一类含B-N共价键的共轭聚合物，其特征在于，具有如下结构：
Figure BDA0002749059990000021
Ar1包括如下结构中的一种
Figure BDA0002749059990000022
Ar2包括如下结构中的一种
Figure BDA0002749059990000023
Ar3包括如下结构中的一种
Figure BDA0002749059990000024
共聚单体包括如下结构中的一种
Figure BDA0002749059990000031
Figure BDA0002749059990000041
其中，n为1～10000的自然数，R1-86为H或C1～C40的烷基链、烷氧链、烷硫链、烷基硅烷、卤素原子或氰基取代基，X1-4为O、S、Se、Te中的任一种，X5-7为C、Si、Ge中的任一种，X8-12为O、S、Se、Te中的任一种，X13-16为C、Si、Ge中的任一种，X17-31为O、S、Se、Te中的任一种，X32-33为H或卤素原子或氰基取代基，Y1-8为H或C1～C40的烷基链、烷氧链、烷硫链、烷基硅烷、卤素原子、氰基或硝基取代基。
所述聚合物材料的制备方法，其特征在于，具体为如下步骤：将一定物质的量的含B–N共价键的单体同其他等物质的量的共聚单体混合，在钯催化剂催化下进行聚合，后经纯化得到相应的聚合物材料。
本发明与现有技术相比具有以下优点：
(1)本发明设计了一类含B–N共价键的共轭聚合物。
(2)本发明实现了具有优异性能的有机光伏器件。
(3)基于本发明的B–N共轭聚合物具有高三线态能级，能够抑制有机太阳电池中的三线态复合。
(4)本发明展示了含B–N共价键的共轭聚合物在实现高效有机光伏器件中的优异潜力。
附图说明
图1为具体实施的含B–N共价键的共轭聚合物(PBNBDD、PBNBDD-TT、PBNTzTz)的合成路线图。
图2为PBNBDD:[70]PCBM/IT-4F/Y6/Y6-BO有机太阳电池器件的材料化学结构以及器件结构示意图。
图3为PBNBDD:[70]PCBM/IT-4F/Y6/Y6-BO有机太阳电池器件的电流密度–电压曲线。
图4a为含B–N共价键的共轭聚合物(PBNBDD)的低温磷光光谱。
图4b为PBNBDD:[70]PCBM有机太阳电池器件的电致发光光谱。
具体实施方式
为了使本发明的目的、技术方案以及优点更加清楚明了，以下结合附图和实施案例，对本发明进行进一步详细说明。
实施例1
含B–N共价键的单体(结构5、6)的制备，化学反应流程如下所示，具体反应步骤和反应条件如下：
Figure BDA0002749059990000061
(1)原料或中间反应物，正丁基锂(浓度1.6M)、5-溴甲基-十一烷、四(三苯基膦)钯、三苯基膦、二氯苯硼烷、溴代丁二酰亚胺、三乙胺、四氢呋喃、甲苯、氯苯、氯仿，为安耐吉、百灵威、苏州纳凯等公司购买所得。
(2)化合物2的制备
以2，5-二溴对苯二胺为原料合成烷基取代的二溴苯胺，具体步骤为：将2，5-二溴对苯二胺(5g)加入到无水四氢呋喃(100mL)中，搅拌至完全溶解。并在无水无氧的环境下冷却到–78℃，缓慢滴加正丁基锂的正己烷溶液(1.6M)，搅拌半小时，缓慢升温到室温反应半小时；再次冷却到–78℃滴加5-溴甲基-十一烷(25g)，缓慢升温到室温，并加热回流，过夜反应。反应结束后加入大量水淬灭，经二氯甲烷萃取，干燥柱层析提纯分离得到烷基取代的二溴苯胺(10g，产率约78％)。
(3)化合物3的制备
将化合物2和噻吩硼酸酯进行Suzuki偶联反应，具体为：在N2保护下，以甲苯为反应溶剂，加入10g碳酸铯和0.3g催化剂四(三苯基膦)钯，将噻吩硼酸酯(6g)和上述产物(5g)在无水无氧下进行回流反应，反应过夜，监控反应待原料消失可以停止反应。经萃取、水洗、干燥后将反应物直接进行柱层析分离产物为黄色黏稠液体(5.2g，产率82％)。
(4)化合物4的制备
将化合物3(2g)溶解在氯苯(25mL)中，在0℃下将二氯苯硼烷缓慢加入上述反应液中，滴加完成后将反应升到室温，并加热回流，避光反应过夜。反应结束后，用水淬灭反应，并用二氯甲烷萃取，进行柱层析分离。产物为黄色固体(2.5g，产率60％)。
(5)单体5的制备
将化合物4溶解在氯仿中，加入0.6g的溴代丁二酰亚胺，避光搅拌反应过夜。经萃取、水洗、干燥后进行柱层析分离，再进行2次重结晶。产物为黄色固体(2.5g，产率85％)。
(6)化合物6的制备
将化合物2和并噻吩硼酸酯进行Suzuki偶联反应，具体为：在N2保护下，以甲苯为反应溶剂，加入10g碳酸铯和0.3g催化剂四(三苯基膦)钯，将并噻吩硼酸酯(6.5g)和化合物2(5g)在无水无氧下进行回流反应，反应过夜，监控反应待原料消失可以停止反应。经萃取、水洗、干燥后将反应物直接进行柱层析分离产物为黄色黏稠液体(5.8g，产率80％)。
(7)单体7的制备
将化合物6(2.4g)溶解在氯苯(25mL)中，在0℃下将二氯苯硼烷缓慢加入上述反应液中，滴加完成后将反应升到室温，并加热回流，避光反应过夜。反应结束后，用水淬灭反应，并用二氯甲烷萃取，进行柱层析分离。产物为黄色固体(2.1g，产率70％)。
(8)单体8的制备
将化合物7溶解在氯仿中，加入0.6g的溴代丁二酰亚胺，避光搅拌反应过夜。经萃取、水洗、干燥后进行柱层析分离，再进行2次重结晶。产物为黄色固体(2.1g，产率85％)。
实施例2
含B–N共价键的共轭聚合物(PBNBDD、PBNTzTz、PBNBDD-TT)的制备
化学反应流程如下所示，具体反应步骤和反应条件如下：
Figure BDA0002749059990000081
(1)单体9、单体10、三(二亚苄基丙酮)二钯、三(邻甲基苯基)磷、邻二甲苯、二甲基甲酰胺，为百灵威、苏州纳凯等公司购买所得。
(2)在氮气保护下，将单体5(0.1mmol)、单体9(0.1mmol)、1.5mg三(二亚苄基丙酮)二钯和4.9mg三(邻甲基苯基)磷溶解于2mL邻二甲苯和0.2mL二甲基甲酰胺的混合溶剂中，120℃搅拌12小时。反应结束后将聚合物在甲醇中沉淀，经甲醇、丙酮、正己烷、氯仿依次抽提，氯仿组份在甲醇中沉淀，烘干后得到聚合物PBNBDD(110mg)，产率87％。
(3)在氮气保护下，将单体5(0.1mmol)、单体10(0.1mmol)、1.5mg三(二亚苄基丙酮)二钯和4.9mg三(邻甲基苯基)磷溶解于2mL邻二甲苯和0.2mL二甲基甲酰胺的混合溶剂中，120℃搅拌12小时。反应结束后将聚合物在甲醇中沉淀，经甲醇、丙酮、正己烷、氯仿依次抽提，氯仿组份在甲醇中沉淀，烘干后得到聚合物PBNBDD-TT(139mg)，产率96％。
(4)在氮气保护下，将单体8(0.1mmol)、单体9(0.1mmol)、1.5mg三(二亚苄基丙酮)二钯和4.9mg三(邻甲基苯基)磷溶解于2mL邻二甲苯和0.2mL二甲基甲酰胺的混合溶剂中，120℃搅拌12小时。反应结束后将聚合物在甲醇中沉淀，经甲醇、丙酮、正己烷、氯仿依次抽提，氯仿组份在甲醇中沉淀，烘干后得到聚合物PBNTzTz(142mg)，产率93％。
实施例3
以实施例2所得材料(PBNBDD)为例说明本发明所述含B–N共价键的共轭聚合物在有机光伏器件中的应用，但本发明不限于所举之例。
器件的具体制备过程如下：
在ITO上旋涂一层40nm的PEDOT:PSS空穴传输层，接着旋涂100nm左右的PBNBDD和受体材料([70]PCBM，IT-4F，Y6，Y6-BO)共混的光活性层，接着旋涂5nm左右的胺基聚芴的溴化季铵盐(PFN-Br)作为阴极界面层，再蒸镀100nm Ag层，即完成器件制备。随后在标准模拟太阳光下进行J–V曲线测试，得到器件的相关参数如表1和图3所示。
表1.器件ITO/PEDOT:PSS/PBNBDD:受体材料/PFN-Br/Ag的性能参数
Figure BDA0002749059990000101
实施例4
本发明所述含B–N共价键的共轭聚合物在有机太阳电池中对三线态复合的抑制作用
以实施例2所得材料(PBNBDD)和以实施例3所得PBNBDD:[70]PCBM有机太阳电池器件为例，探究本发明所述含B–N共价键的共轭聚合物对有机太阳电池中三线态复合的抑制作用。根据荧光和磷光的寿命不同的原理，通过低温延迟磷光实验测试PBNBDD的三线态能级E(T1)约为1.63eV，如图4(a)所示。对器件进行电致发光表征得到器件的CT态能级E(CT)约为1.39eV，如图4(b)所示。通过对比可知E(T1)>E(CT)，PBNBDD的高三线态能级能够抑制有机太阳电池中三线态复合。
本发明的上述实施例仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (4)

1.一类含B-N共价键的共轭聚合物，其特征在于，结构通式M如下：
Figure FDA0002749059980000011
Ar1包括如下结构中的一种
Figure FDA0002749059980000012
Ar2包括如下结构中的一种
Figure FDA0002749059980000013
Ar3包括如下结构中的一种
Figure FDA0002749059980000014
共聚单体包括如下结构中的一种
Figure FDA0002749059980000015
Figure FDA0002749059980000021
Figure FDA0002749059980000031
其中，n为1～10000的自然数，R1-86为H或C1～C40的烷基链、烷氧链、烷硫链、烷基硅烷、卤素原子或氰基取代基，X1-4为O、S、Se、Te中的任一种，X5-7为C、Si、Ge中的任一种，X8-12为O、S、Se、Te中的任一种，X13-16为C、Si、Ge中的任一种，X17-31为O、S、Se、Te中的任一种，X32-33为H、卤素原子、氰基或硝基取代基，Y1-8为H或C1～C40的烷基链、烷氧链、烷硫链、烷基硅烷、卤素原子、氰基或硝基取代基。
2.权利要求1所述聚合物材料的制备方法，其特征在于，包括如下步骤：将含B-N共价键的硼氮单体同其他等物质的量的共聚单体混合，在钯催化剂催化下进行聚合，后经纯化得到相应的聚合物材料。
3.根据权利要求2所述制备方法，其特征在于，具体步骤为：在低温条件下，通过2，5-二溴对苯二胺制备烷基链修饰的中间体，然后经过Suzuki偶联、硼氮关环反应以及溴化制备含B-N共价键的硼氮单体；含B-N共价键的硼氮单体同其他等物质的量的共聚单体混合，在钯催化剂催化下进行聚合，后经纯化得到相应的聚合物材料。
4.权利要求1所述的含B-N共价键的共轭聚合物应用在有机太阳电池中。
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