Chlorophyll (Chl) derivatives have recently been proposed as photoactive materials in next-generation bio-inspired solar cells, because of their natural abundance, environmental friendliness, excellent photoelectric performance, and biodegradability. However, the intrinsic excitation dynamics of Chl derivatives remain unclear. Here, we show sub-nanosecond pump–probe time-resolved absorption spectroscopy of Chl derivatives both in solution and solid film states. We observe the formation of triplet-excited states of Chl derivatives both in deoxygenated solutions and in film samples by adding all-trans-β-carotene as a triplet scavenger. In addition, radical species of the Chl derivatives in solution were identified by adding hydroquinone as a cation radical scavenger and/or anion radical donor. These radical species (either cations or anions) can become carriers in Chl-derivative-based solar cells. Remarkably, the introduction of hydroquinone to the film samples enhanced the carrier lifetimes and the power conversion efficiency of Chl-based solar cells by 20% (from pristine 1.29% to 1.55%). This enhancement is due to a charge recombination process of Chl-A⁺/Chl-D^–, which is based on the natural Z-scheme process of photosynthesis.

叶绿素（Chl）衍生物由于其天然丰富、环境友好、优异的光电性能和生物可降解性，最近被提议作为下一代仿生太阳能电池的光敏材料。然而，叶绿素衍生物的内在激发动力学仍不清楚。在这里，我们展示了溶液和固膜状态下叶绿素衍生物的亚纳秒泵浦探针时间分辨吸收光谱。通过添加全反式-β-胡萝卜素作为三线态清除剂，我们观察到在脱氧溶液和薄膜样品中叶绿素衍生物三线态激发态的形成。此外，通过添加氢醌作为阳离子自由基清除剂和/或阴离子自由基供体来鉴定溶液中叶绿素衍生物的自由基种类。这些自由基物质（阳离子或阴离子）可以成为基于叶绿素衍生物的太阳能电池中的载流子。值得注意的是，在薄膜样品中引入对苯二酚使基于 Chl 的太阳能电池的载流子寿命和功率转换效率提高了 20%（从原始的 1.29% 提高到 1.55%）。这种增强是由于 Chl-A ⁺ /Chl-D ^–的电荷重组过程所致，该过程基于光合作用的自然 Z 型过程。