CN113956447B - 基于稠环酰亚胺结构的电子型聚合物及其制备方法和器件应用 - Google Patents
基于稠环酰亚胺结构的电子型聚合物及其制备方法和器件应用 Download PDFInfo
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Abstract
本发明公开了一种基于稠环酰亚胺结构的电子型聚合物及其制备方法和器件应用，通过选用光照环化的合成方法，将醛基噻唑和胺基取代的苝二酰亚胺结构单元反应，成功实现了对苝二酰亚胺结构单元的湾位修饰，结构单元之间的空间位阻可以得到明显改善；进一步通过stille偶联反应得到基于湾位修饰的苝二酰亚胺和噻唑结构单元的聚合物。本发明形成的A‑A(受体‑受体)型聚合物拥有良好的共轭特性和优异的电子传输特性以及空气稳定性，材料的合成简单、产率高。而基于本发明的聚合物作为电子传输层材料应用到钙钛矿太阳能电池中，能够取得超过20％的光电转化效率，具有取代目前无机和有机小分子电子传输材料的潜力，具备良好的产业化前景。
Description
技术领域
本发明涉及钙钛矿太阳能电池领域，具体涉及一种基于稠环酰亚胺结构的电子型聚合物及其制备方法和器件应用。
背景技术
具有电荷输运特性的聚合物半导体材料，又被称为第四代聚合物材料，是最近四十年高分子领域和分子材料领域最重大的发现之一。根据电荷传输特性不同，聚合物可以分为空穴型(p)、电子型(n)和双极性型。近十年，空穴传输型的聚合物半导体材料在电荷传输性能和稳定性方面都取得了很大的进步。相较于空穴传输型的聚合物半导体材料，电子传输型的聚合物半导体材料的发展较为缓慢。然而电子传输型聚合物材料在有机光电器件方面和空穴传输型聚合物互为补充，作用同样重要，因此开发高性能的电子传输型聚合物成为聚合物半导体材料领域的重点和难点。
苝二酰亚胺类聚合物是目前研究较为广泛的一类电子传输型聚合物，然而苝二酰亚胺湾位的空间位阻会导致聚合物主链的空间构型扭曲，减弱聚合物链内和链间的相互作用，进而导致材料的分子堆积和结晶性较差，影响材料作为电子传输材料的性能。
发明内容
鉴于上述技术问题，本发明目的在于提供了一种基于稠环酰亚胺结构的电子型聚合物，该类材料具有合成简单、电荷迁移率高、稳定性和溶解性好等优点，可以作为电子传输材料应用到钙钛矿太阳能电池中。
本发明的技术方案如下：
一种基于稠环酰亚胺结构的电子型聚合物，该聚合物具有如下所示的结构式：
R选自C5-C40取代或未取代的烷基，C5-C40取代或未取代的烯基，C5-C40取代或未取代的炔基，C3-C30取代或未取代的环烷基，C6-C60取代或未取代的芳基，C5-C40 取代或未取代的杂环芳基，C5-C40取代或未取代的烷氧基，C5-C40取代或未取代的硅烷基；
X1为C原子、X2为N原子或X1为N原子、X2为C原子。
L为单键或乙烯基键。
R选自C5-C40的支链或直链烷基。
上述聚合物结构式具有任一如下所示结构：
其中，R选自C5-C40的支链或直链烷基。
稠环酰亚胺聚合物通式包含且不限于如下结构：
基于上述通式的聚合物，上述聚合物具有良好的光电特性，并可以作为电子传输材料应用到钙钛矿太阳能电池器件中。
本发明提供了一种聚合物的钙钛矿太阳能电池器件，聚合物作为电子传输材料应用于钙钛矿太阳能电池器件中。
本发明相对于现有技术具有以下显著优点：1、稠环酰亚胺结构单元相比于传统苝二酰亚胺结构具有更良好的共轭特性，以及平面性，可以保证材料在薄膜中形成有效的Π-Π堆积，进而拥有良好的电荷迁移率；2、通过将噻唑结构单元和稠环酰亚胺结构单元结合，制备聚合物，可以有效减小结构单元之间的空间位阻，进而保证聚合物拥有平面的骨架结构；3、同时，稠环酰亚胺结构和噻唑结构可以形成有效的分子内氢键，进一步提升聚合物的空间规整性；刚性、平整的分子骨架赋予该类聚合物良好的链内和链间相互作用，有效提升了聚合物的结晶性，保证了电子在链内和链间的有效输运；4、 A-A的分子设计让聚合物拥有低LUMO能级，进而表现出良好的电子传输特性；5、由于合适的能级和优异电子传输性能，基于本发明的聚合物可作为电子传输材料应用到钙钛矿太阳能电池中时，酰亚胺结构和N原子可以和钙钛矿中的铅形成相互作用，有效钝化钙钛矿层的缺陷，进一步提升器件的效率和稳定性。最终，基于本发明的聚合物作为电子传输层可以在钙钛矿太阳能电池中实现超过20％的效率。对比目前常用的电子传输材料PCBM，本发明的聚合物在器件效率、稳定性方面具有明显优势，同时聚合物的原料易得、合成简单产率高，溶解性和成膜性好，具备良好的应用前景。
附图说明
图1为本发明的钙钛矿太阳能电池器件的结构示意图。
具体实施方式
下面结合实施例对本发明做进一步说明
该方法的制备通式如下：
实施例1
合成聚合物P-1
化合物1-3合成：
称取化合物1-1(1equiv)和化合物1-2(10equiv)加入反应瓶中，依次加入甲苯(0.1mmol每30mL)，催化量的碘，光照情况下搅拌反应(光源：400nm，LED，70W)，连续光照反应，TLC监控反应进程，反应完全后，将反应液倒入大量的甲醇中，过滤得到粗产物，依次用正己烷、丙酮清洗，选用氯仿、甲醇重结晶，得到目标化合物1-3，产率为78％。
元素分析：(C72H88Br2N6O4S2)理论值：C,65.24；H,6.69；N,6.34；；实测值：C,65.21；H,6.72；N,6.37，HRMS(ESI)m/z：理论值：1324.46；实测值：1325.45 (M+1)+。
化合物P-1合成：
称取200mg化合物1-3，化合物1-4(1equiv)，Pd2(PPh3)4(0.05equiv)，甲苯15mL，DMF 2mL加入到30mL反应管中，用隔膜泵置换氮气三次，加热回流反应24小时候后，冷却至室温，倒入甲醇中，过滤，一次用甲醇、丙酮、二氯甲烷、氯仿在索式提取器内进行抽提，收集氯仿抽提得到的组分，浓缩倒入甲醇中，过滤、烘干得到聚合物 P-1，产率为91％。
元素分析理论值：C,74.19；H,7.61；N,7.21；实测值：C,74.11；H,7.53；N,7.20。
实施例2
合成化合物P-2
聚合物P-2合成：
称取200mg化合物1-3，化合物2-1(1equiv),Pd2(PPh3)4(0.05equiv)，甲苯15mL，DMF 2mL加入到30mL反应管中，用隔膜泵置换氮气三次，加热回流反应24小时候后，冷却至室温，倒入甲醇中，过滤，一次用甲醇、丙酮、二氯甲烷、氯仿在索式提取器内进行抽提，收集氯仿抽提得到的组分，浓缩倒入甲醇中，过滤、烘干得到聚合物 P-2，产率为87％。
元素分析理论值：C,74.58；H,7.61；N,7.05；；实测值：C,74.51；H,7.63；N,7.01。
实施例3
合成聚合物P-3
聚合物P-3的合成方法和处理过程与P-1相同，仅将起始反应物1-1换成如下所示3-1：
实施例4
合成聚合物P-4
聚合物P-4的合成方法和处理过程与P-2相同，仅将起始反应物1-1换成化合物 3-1。
元素分析理论值：C,75.31；H,8.06；N,6.59；实测值：C,75.23；H,8.02；N,6.60。
实施例5
合成化合物P-5
化合物5-2合成：
称取化合物1-1(1equiv)和化合物5-1(10equiv)加入反应瓶中，依次加入甲苯(0.1mmol每30mL)，催化量的碘，光照情况下搅拌反应(光源：400nm，LED，70W)，连续光照反应，TLC监控反应进程，反应完全后，将反应液倒入大量的甲醇中，过滤得到粗产物，依次用正己烷、丙酮清洗，选用氯仿、甲醇重结晶，得到目标化合物5-2，产率为83％。
元素分析：(C72H88Br2N6O4S2)理论值：C,65.24；H,6.69；N,6.34；；实测值：C,65.19；H,6.70；N,6.31，HRMS(ESI)m/z：理论值：1324.46；实测值：1324.43(M)+。
化合物P-5合成：
称取200mg化合物5-2，化合物1-4(1equiv),Pd2(PPh3)4(0.05equiv)，甲苯15mL，DMF 2mL加入到30mL反应管中，用隔膜泵置换氮气三次，加热回流反应24小时候后，冷却至室温，倒入甲醇中，过滤，一次用甲醇、丙酮、二氯甲烷、氯仿在索式提取器内进行抽提，收集氯仿抽提得到的组分，浓缩倒入甲醇中，过滤、烘干得到聚合物 P-5，产率为93％。
元素分析理论值：C,74.19；H,7.61；N,7.21；实测值：C,74.12；H,7.57；N,7.20。
实施例6
合成化合物P-6
聚合物P-6合成：
称取200mg化合物5-2，化合物2-1(1equiv),Pd2(PPh3)4(0.05equiv)，甲苯15mL，DMF 2mL加入到30mL反应管中，用隔膜泵置换氮气三次，加热回流反应24小时候后，冷却至室温，倒入甲醇中，过滤，一次用甲醇、丙酮、二氯甲烷、氯仿在索式提取器内进行抽提，收集氯仿抽提得到的组分，浓缩倒入甲醇中，过滤、烘干得到聚合物 P-6，产率为93％。
元素分析理论值：C,74.58；H,7.61；N,7.05；；实测值：C,74.53；H,7.53；N,7.04。
实施例7
合成聚合物P-7
聚合物P-7的合成方法和处理过程与P-5相同，仅将起始反应物1-1换成化合物 3-1：
元素分析理论值：C,74.96；H,8.07；N,6.72；实测值：C,74.91；H,8.03；N,6.70。
实施例8
合成聚合物P-8
聚合物P-8的合成方法和处理过程与P-6相同，仅将起始反应物1-1换成化合物3-1。
元素分析理论值：C,75.31；H,8.06；N,6.59；实测值：C,75.30；H,8.01；N,6.54。
凝胶渗透色谱测试(GPC)：聚合物的分子量和分子量分布通过GPC，以氯仿为流动相，聚苯乙烯为参照标准进行测试。
器件测试：
钙钛矿太阳能电池选用p-i-n结构，具体结构为：
ITO/空穴传输层(聚[双(4-苯基)(2,4,6-三甲基苯基)胺]：PTAA)/钙钛矿层(MA0.7FA0.3PbI2.85Br0.15)/电子传输材料(PCBM或本发明中化合物)/电子传输层(2,9- 二甲基-4,7-二苯基-1,10-菲咯啉:BCP)/阴极(Ag)
器件实施例1(对比例1)：
基板清理：
将涂布了ITO透明电机基板在商用清洗剂中超声处理，在去离子水中冲洗，在丙酮：乙醇混合溶剂(体积比1：1)中超声除油，在洁净环境下烘烤至完全除去水份，然后用紫外光和臭氧清洗。
器件制备：
在手套箱中，ITO上旋涂10nm PTAA(100℃退火10分钟)作为空穴传输层；依次旋涂600nm钙钛矿层(将MAI(0.7mmol),FAI(0.3mmol),PbI2(0.925mmol),PbBr2(0.075mmol),DMSO(71μL)，Pb(SCN)2(9.22mg)溶于DMF(1mL)中制成旋涂液)， 100℃退火5分钟；旋涂PCBM(10nm)，蒸镀BCP(8nm)作为电子传输层；蒸镀 100nm银作为阴极。
器件实施例2
本实施例与器件实施例1的不同之处在于：钙钛矿太阳能电池器件的电子传输材料 PCBM替换为本发明聚合物P-1。
器件实施例3
本实施例与器件实施例1的不同之处在于：钙钛矿太阳能电池器件的电子传输材料 PCBM替换为本发明聚合物P-2。
器件实施例4
本实施例与器件实施例1的不同之处在于：钙钛矿太阳能电池器件的电子传输材料 PCBM替换为本发明聚合物P-3。
器件实施例5
本实施例与器件实施例1的不同之处在于：钙钛矿太阳能电池器件的电子传输材料 PCBM替换为本发明聚合物P-4。
器件实施例6
本实施例与器件实施例1的不同之处在于：钙钛矿太阳能电池器件的电子传输材料 PCBM替换为本发明聚合物P-5。
器件实施例7
本实施例与器件实施例1的不同之处在于：钙钛矿太阳能电池器件的电子传输材料 PCBM替换为本发明聚合物P-6。
器件实施例8
本实施例与器件实施例1的不同之处在于：钙钛矿太阳能电池器件的电子传输材料 PCBM替换为本发明聚合物P-7。
器件实施例9
本实施例与器件实施例1的不同之处在于：钙钛矿太阳能电池器件的电子传输材料 PCBM替换为本发明聚合物P-8。
测试例1
器件光伏性能测试：器件的有效面积为0.4cm2。测试条件：光谱分布AM1.5G，光照强度100mW/cm2，AAA太阳光模拟器(北京卓立汉光公司)，J-V曲线用 Keithly2400型数字源表进行测量，所有器件利用紫外胶简单封装，测试在大气环境中正常测量。
结果见表1。
表1器件实施例对应性能
从上述器件实施例的性能可以看出，实施例与对比例相比，采用本申请的电子传输材料同PCBM相比更加优异的光电转化效率，稳定性方面优势更加明显，表明本发明公布的材料相比于目前的电子传输材料具有明显的性能优势。
Claims (7)
1.一种基于稠环酰亚胺结构的电子型聚合物，其特征在于，该聚合物具有如下所示的结构式：
R选自C5-C40的支链或直链烷基，C5-C40取代或未取代的烯基，C5-C40取代或未取代的炔基，C3-C30取代或未取代的环烷基，C6-C60取代或未取代的芳基，C5-C40取代或未取代的杂环芳基，C5-C40取代或未取代的烷氧基，C5-C40取代或未取代的硅烷基；
X1为C原子、X2为N原子或X1为N原子、X2为C原子；
L为单键或乙烯基键。
2.根据权利要求1所述的基于稠环酰亚胺结构的电子型聚合物，其特征在于，聚合物结构式具有如下所示结构：
R选自C5-C40的支链或直链烷基。
3.根据权利要求1所述的基于稠环酰亚胺结构的电子型聚合物，其特征在于，稠环酰亚胺聚合物通式包括：
4.一种基于权利要求1任一项所述的基于稠环酰亚胺结构的电子型聚合物的制备方法，其特征在于，该方法的制备通式如下：
5.一种根据权利要求1-3任一项所述的基于稠环酰亚胺结构的电子型聚合物的应用，其特征在于，所述的聚合物应用到钙钛矿太阳能电池器件中。
6.一种聚合物的钙钛矿太阳能电池器件，其特征在于，所述的钙钛矿太阳能电池器件至少有一个功能层包括权利要求1-3任一项的聚合物。
7.根据权利要求6所述的钙钛矿太阳能电池器件，其特征在于，所述功能层为电子传输层。
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