化学学报 ›› 2015, Vol. 73 ›› Issue (11): 1153-1160.DOI: 10.6023/A15080546 上一篇    下一篇

研究论文

水醇溶性小分子卟啉衍生物的合成及其在聚合物太阳电池中的应用

卢俊明, 蔡万清, 张桂传, 刘升建, 应磊, 黄飞   

  1. 华南理工大学 高分子光电材料与器件研究所 发光材料与器件国家重点实验室 广州 510640
  • 收稿日期:2015-08-16 出版日期:2015-11-15 发布日期:2015-11-19
  • 通讯作者: 应磊, 黄飞 E-mail:msleiying@scut.edu.cn;msfhuang@scut.edu.cn
  • 基金资助:

    项目受科技部973计划(No. 2014CB643501)、国家自然科学基金(Nos. 51303056, 21125419, 21490573, 51361165301)及广东省自然科学基金(No. S2012030006232)资助.

Synthesis and Photovoltaic Performance of Water/Alcohol Soluble Small Phorphyrin Derivatives for Polymer Solar Cells

Lu Junming, Cai Wanqing, Zhang Guichuan, Liu Shengjian, Ying Lei, Huang Fei   

  1. State Key Laboratory of Luminescent Materials and Devices, Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology, Guangzhou 510640
  • Received:2015-08-16 Online:2015-11-15 Published:2015-11-19
  • Supported by:

    Project supported by the Ministry of Science and Technology (No. 2014CB643501), the National Natural Science Foundation of China (Nos. 51303056, 21125419, 21490573 and 51361165301) and the Natural Science Foundation of Guangdong Province (No. S2012030006232).

设计合成了Por-N, Por-NBr, Por-Cu-NPor-Cu-NBr四种水醇溶性小分子卟啉衍生物. 对这类卟啉小分子衍生物的紫外可见吸收光谱研究表明, 基于金属铜配位的卟啉小分子衍生物较未配位化合物有微弱的蓝移. 循环伏安法对这类小分子卟啉衍生物的研究表明, 基于金属铜配合物的卟啉衍生物的最高占有分子轨道能级均没有明显变化. 采用空间电荷限制电流方法对小分子卟啉衍生物的研究表明, 基于金属铜配位的卟啉小分子衍生物的电子迁移率得到明显提高. 以聚合物PCE10为给体材料, 富勒烯衍生物PC71BM为受体材料, 以及合成的小分子卟啉衍生物为阴极界面层制备了结构为ITO/PEDOT:PSS/PCE10:PC71BM/卟啉小分子衍生物/Al的聚合物太阳电池器件. 器件研究结果表明, 化合物Por-NBr, Por-Cu-NPor-Cu-NBr作为电子传输层的器件的光电转换效率达到9%以上, 其中以Por-Cu-N作为阴极界面层的器件达到的最高效率为9.12%, 相应器件的短路电流密度, 开路电压以及填充因子分别为16.91 mA· cm-2, 0.79 V和68.1%. 表明这类水醇溶性小分子卟啉衍生物作为聚合物太阳电池的阴极界面层有着广阔的应用前景.

关键词: 水醇溶, 卟啉衍生物, 阴极界面层, 溶液加工, 聚合物太阳电池

A series of novel water/alcohol soluble small molecular phorphyrin derivatives, Por-N, Por-NBr, Por-Cu-N and Por-Cu-NBr, were designed and synthesized. Differential scanning calorimetry measurements indicated that the neutral molecules Por-N and Por-Cu-N exhibited distinct melting point and crystallinity, while no observable characteristics were realized for the quaternized molecules. All these small molecules exhibited good thermal stability as evaluated by thermal gravimetric analysis. The photophysical properties of these small molecules were systematically investigated by UV-vis spectroscopy in both solutions and as thin films. It was found that the absorption spectra of Por-Cu-N and Por-Cu-NBr were slightly blue-shifted due to the formation of complex between porphyrin and copper. The highest occupied molecular orbitals energy levels showed negligible changes as determined by cyclic voltammetry measurements. The bulk-heterojunction solar cells utilizing these phorphyrin derivatives as the cathode interlayer and PCE10:PC71BM as the photoactive layer were fabricated. The single carrier devices revealed that the electron mobility of these phorphyrin derivatives are much higher than the hole-mobility except Por-N. Polymer solar cell devices with the structure of ITO/PEDOT:PSS/PCE10: PC71BM/Porphyrin derivatives/Al were fabricated to evaluate the function of cathode interlayer of these molecules. It was also worth noting that the polymer solar cell devices by using these molecules as the cathode interlayer exhibited obviously improved performances than the methanol treated device. Devices based on the molecules of Por-NBr, Por-Cu-N and Por-Cu-NBr as the cathode interlayer and narrow bandgap PCE10:PC71BM blend film as the photoactive layer exhibited comparatively high power conversion efficiency exceeding 9%. The best power conversion efficiency of 9.12% was achieved by the device based on Por-Cu-N as the cathode inter layer, with corresponding parameters of short circuit current of 16.91 mA·cm-2, open circuit voltage of 0.79 V and fill factor of 68.1%. These observations demonstrated that the synthesized water/alcohol soluble small molecules based on porphyrin derivatives can be prominent cathode interfacial layers for polymer solar cells.

Key words: water/alcohol soluble, phorphyrin derivatives, cathode interlayer, solution-processed, polymer solar cell