Renaissance of Fused Porphyrins: Substituted Methylene-Bridged Thiophene-Fused Strategy for High-Performance Dye-Sensitized Solar Cells
Renaissance of Fused Porphyrins: Substituted Methylene-Bridged Thiophene-Fused Strategy for High-Performance Dye-Sensitized Solar Cells
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DOI：
10.1021/jacs.9b03302
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发表时间：
2019-06-26
影响因子：
15
通讯作者：
Imahori, Hiroshi
中科院分区：
文献类型：
--
作者：
Kurumisawa, Yuma;Higashino, Tomohiro;Imahori, Hiroshi
在过去的几十年里，卟啉敏化剂在染料敏化太阳能电池（DSSCs）的性能改进方面做出了显著的贡献。特别是，多用途的推挽型卟啉敏化剂由于其提高的光收集能力，已经实现了超过10%的功率转换效率（eta）。同时，芳香环融合到卟啉核是高效DSSCs的一个有吸引力的选择，因为它扩大了π共轭和产生的红移吸收。然而，芳香融合卟啉增敏剂由于其HOMO-LUMO水平的不匹配、高聚集倾向和激发态寿命短，导致其细胞性能较低。考虑到这些，我们设想将取代亚甲基桥接的小芳香环与卟啉核心融合将克服这些缺点，提高电池性能。在此，我们报道了一系列取代亚甲基桥接噻吩-熔融卟啉，AfZnP， DfZnP和DfZnP- ipr。优化后，配以供侧噻吩- DfZnP-iPr的DSSC的eta值为10.1%，与配以具有代表性的高性能推拉型卟啉增敏剂GYSO的DSSC的eta值（10.0%）相当。更重要的是，DfZnP-iPr与互补敏化剂LEG4的共敏化进一步导致了10.7%的eta值，这是迄今为止报道的融合卟啉敏化剂的DSSCs的最高值。因此，我们的策略将重启对高性能DSSCs的芳香族熔融卟啉增敏剂的探索。
Over the last decades, porphyrin sensitizers have made a remarkable contribution to performance improvement in dye-sensitized solar cells (DSSCs). In particular, versatile push pull-type porphyrin sensitizers have achieved power conversion efficiencies (eta) over 10% as a result of their improved light-harvesting abilities. Meanwhile, aromatic ring fusion to a porphyrin core is an attractive option for highly efficient DSSCs because of its expanded pi-conjugation and resultant red-shifted absorption. Nevertheless, aromatic-fused porphyrin sensitizers have suffered rather low cell performances due to their mismatch of HOMO-LUMO levels, high aggregation tendency, and short lifetime of the excited states. Bearing these in mind, we envisioned that the fusion of substituted methylene-bridged small aromatic ring to a porphyrin core would overcome these drawbacks, boosting the cell performance. Herein, we report a series of substituted methylene-bridged thiophene-fused porphyrins, AfZnP, DfZnP, and DfZnP-iPr. After optimization, DSSC with the donor-side thiophene-fused DfZnP-iPr achieved an eta-value of 10.1%, which is comparable to that of DSSC with GYSO (10.0%), a representative high-performance push-pull-type porphyrin sensitizer. More importantly, cosensitization of DfZnP-iPr with a complementary sensitizer LEG4 further led to an eta-value of 10.7%, which is the highest value ever reported for DSSCs with fused porphyrin sensitizers. Therefore, our strategy will reboot the exploration of aromatic fused porphyrin sensitizers for high-performance DSSCs.