Effects of Bulky Substituents of Push–Pull Porphyrins on Photovoltaic Properties of Dye-Sensitized Solar Cells

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• 作者：Tomohiro Higashino ; Kyosuke Kawamoto ; Kenichi Sugiura ; Yamato Fujimori ; Yukihiro Tsuji ; Kei Kurotobi ; Seigo Ito ; Hiroshi Imahori
• 刊名：ACS Applied Materials & Interfaces
• 出版年：2016
• 出版时间：June 22, 2016
• 年：2016
• 卷：8
• 期：24
• 页码：15379-15390
• 全文大小：622K
• 年卷期：0
• ISSN：1944-8252

文摘

To evaluate the effects of substituent bulkiness around a porphyrin core on the photovoltaic properties of porphyrin-sensitized solar cells, long alkoxy groups were introduced at the meso-phenyl group (ZnPBAT-o-C8) and the anchoring group (ZnPBAT-o-C8Cn, n = 4, 8) of an asymmetrically substituted push–pull porphyrin with double electron-donating diarylamino groups and a single electron-withdrawing carboxyphenylethynyl anchoring group. The spectroscopic and electrochemical properties of ZnPBAT-o-C8 and ZnPBAT-o-C8Cn were found to be superior to those of a push–pull porphyrin reference (YD2-o-C8), demonstrating their excellent light-harvesting and redox properties for dye-sensitized solar cells. A power conversion efficiency (η) of the ZnPBAT-o-C8-sensitized solar cell (η = 9.1%) is higher than that of the YD2-o-C8-sensitized solar cell (η = 8.6%) using iodine-based electrolyte due to the enhanced light-harvesting ability of ZnPBAT-o-C8. In contrast, the solar cells based on ZnPBAT-o-C8Cn, possessing the additional alkoxy chains in the anchoring group, revealed the lower η values of 7.3% (n = 4) and 7.0% (n = 8). Although ZnPBAT-o-C8Cn exhibited higher resistance at the TiO₂–dye–electrolyte interface by virtue of the extra alkoxy chains, the reduced amount of the porphyrins on TiO₂ by excessive addition of coadsorbent chenodeoxycholic acid (CDCA) for mitigating the aggregation on TiO₂ resulted in the low η values. Meanwhile, the ZnPBAT-o-C8-sensitized solar cell showed the lower η value of 8.1% than the YD2-o-C8-sensitized solar cell (η = 9.8%) using cobalt-based electrolyte. The smaller η value of the ZnPBAT-o-C8-sensitized solar cell may be attributed to the insufficient blocking effect of the bulky substituents of ZnPBAT-o-C8 under the cobalt-based electrolyte conditions. Overall, the alkoxy chain length and substitution position around the porphyrin core are important factors to affect the cell performance.