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投稿时间：2017-11-29
投稿时间：2017-11-29
中文摘要: 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[d][1，2，3]三氮唑（BTA）或5，6-二氟苯并[d][1，2，3]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%。
中文关键词: 氟效应 噻并[3,2-b]噻吩 苯并三氮唑 光伏性能
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)thieno[3,2-b]thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene (BDT) as donor (D) moiety, thieno[3,2-b]thiophene (TT) as conjugated π bridge and benzo[d] [1,2,3]triazole (BTA)/5,6-difluorobenzo[d] [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[6,6]phenyl-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.
文章编号： 中图分类号：TM914.4 文献标志码：
基金项目:国家自然科学基金（51463011，61264002，61404067和61166002）；兰州交通大学青年骨干教师百人计划（152022）；优秀科研团队资助（201705和201703）
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.
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.
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.
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.
