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    王芳, 张晓芳, 梁泽洲, 郭鹏智, 同军锋. 氟对含噻并[3, 2-b]噻吩π桥的苯并三氮唑基共聚物的光伏性能影响[J]. 功能高分子学报, 2018, 31(2): 128-139, 180. doi: 10.14133/j.cnki.1008-9357.20171129002
    引用本文: 王芳, 张晓芳, 梁泽洲, 郭鹏智, 同军锋. 氟对含噻并[3, 2-b]噻吩π桥的苯并三氮唑基共聚物的光伏性能影响[J]. 功能高分子学报, 2018, 31(2): 128-139, 180. doi: 10.14133/j.cnki.1008-9357.20171129002
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    WANG Fang, ZHANG Xiao-fang, LIANG Ze-zhou, GUO Peng-zhi, TONG Jun-feng. Effect of Fluorine on the Photovoltaic Property of Benzotriazole-Based Copolymers Containing Thieno[3, 2-b]thiophene π Bridge[J]. Journal of Functional Polymers, 2018, 31(2): 128-139, 180. doi: 10.14133/j.cnki.1008-9357.20171129002
    Citation: WANG Fang, ZHANG Xiao-fang, LIANG Ze-zhou, GUO Peng-zhi, TONG Jun-feng. Effect of Fluorine on the Photovoltaic Property of Benzotriazole-Based Copolymers Containing Thieno[3, 2-b]thiophene π Bridge[J]. Journal of Functional Polymers, 2018, 31(2): 128-139, 180. doi: 10.14133/j.cnki.1008-9357.20171129002
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    氟对含噻并3, 2-b噻吩π桥的苯并三氮唑基共聚物的光伏性能影响

    Effect of Fluorine on the Photovoltaic Property of Benzotriazole-Based Copolymers Containing Thieno3, 2-bthiophene π Bridge

      摘要
    • 摘要: 以噻并3，2-b噻吩（TT）修饰的二维苯并1，2-b：4，5-b'二噻吩（BDT）作给电子单元、TT作共轭π桥、苯并d1, 2, 3三氮唑（BTA）或5，6-二氟苯并d1, 2, 3三氮唑（FBTA）作缺电子单元，在三（二亚苄基丙酮）二钯（Pd2（dba）3）、三（邻甲苯基）膦（P（o-tol）3）催化剂体系下通过Stille缩合聚合方法制备了宽带隙共聚物PTTBDT-BTA和PTTBDT-FBTA。用核磁共振氢谱（1H-NMR）和碳谱（13C-NMR）、元素分析、凝胶渗透色谱（GPC）、热重分析、紫外-可见吸收光谱和循环伏安法等对其进行了表征。系统研究了氟取代对材料的热稳定性、成膜性、吸收光谱、溶液状态下的聚集行为、固态薄膜的光稳定性、能级和光伏性能的影响。研究表明：相比PTTBDT-BTA，氟代聚合物PTTBDT-FBTA失重5%的热分解温度提高了20℃、溶解性明显变差、薄膜态吸光范围稍微变窄、氯苯溶液状态下聚合物链间聚集作用显著增强、薄膜的光稳定性提高且最高分子占有轨道能级（EHOMO）下降了0.10 V。光伏性能测试显示氟取代使PTTBDT-FBTA基器件的能量转换效率（PCE）提高了49.3%，这获益于开路电压（UOC）提高了16.9%、短路电流密度（JSC）提高了13.2%和填充因子（FF）提高了11.8%。

       

      Abstract: Two wide bandgap copolymers, PTTBDT-BTA and PTTBDT-FBTA, have been prepared by the Stille coupling polymerization method in the presence of tris(dibenzylideneacetone) dipalladium (Pd2(dba)3) and tri(o-toyl) phosphine (P(o-tol)3), based on the two dimensional 4, 8-bis(5-(2-butyloctyl)thieno3, 2-bthiophen-2-yl)benzo1, 2-b:4, 5-b'dithiophene (BDT) as donor (D) moiety, thieno3, 2-bthiophene (TT) as conjugated π bridge and benzod 1, 2, 3triazole (BTA)/5, 6-difluorobenzod 1, 2, 3-triazole (FBTA) as acceptor (A) unit, respectively. Both copolymers were characterized by a set of methods including 1H-NMR, 13C-NMR, elemental analysis, gel permeation chromatography (GPC), thermogravimetric (TG) analysis, UV-Vis absorption and cyclic voltammetry (CV), etc. And the effects of fluorine on thermal stability, film-forming property, absorption spectra, aggregation ability in chlorobenzene (CB) solution, energy level and photovoltaic performance were investigated. Compared with PTTBDT-BTA, PTTBDT-FBTA showed an increase for decomposition temperature (Td, 5% mass-loss) of 20℃, decreased solubility, slightly narrowed absorption range, significantly enhanced aggregation in CB solution and a decrease for the highest occupied molecular orbital energy level (EHOMO) of 0.10 eV. The photovoltaic devices were fabricated with a structure of ITO/PEDOT:PSS/active layer/PFN/Al, using PTTBDT-BTA or PTTBDT-FBTA as donor and 6, 6phenyl-C61 butyric acid methyl ester (PC61BM) as acceptor, and their photovoltaic properties were investigated under the AM 1.5, 100 mW/cm2. It was found that the optimal device based on fluorinated PTTBDT-FBTA exhibited a 49.3% increase in power conversion efficiency (PCE), which was originated from a 16.9% enhancement of open circuit voltage (UOC), a 13.2% improvement of short circuit current density (JSC) and a 11.8% rise of fill factor (FF) compared with PTTBDT-BTA-based devices. These results demonstrated that fluorination was an effective strategy for tuning the material structure and improving the photovoltaic property.

       

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