Polyfluorene Copolymers as High‐Performance Hole‐Transport Materials for Inverted Perovskite Solar Cells

Inverted perovskite solar cells (PSCs) that can be entirely processed at low temperatures have attracted growing attention due to their cost‐effective production. Hole‐transport materials (HTMs) play an essential role in achieving efficient inverted PSCs, as they determine the effectiveness of charge extraction and recombination at interfaces. Herein, three polyfluorene copolymers (TFB, PFB, and PFO) are investigated as HTMs for construction of inverted PSCs. It is found that the photovoltaic performance of the solar cells is closely correlated with the electronic properties of the HTMs. Due to its high mobility along with the favored energy‐level alignment with perovskite, TFB shows superior charge extraction and suppressed interfacial recombination than PFB‐ and PFO‐based devices, which delivers a high efficiency of 18.48% with an open‐circuit voltage ( V OC ) of up to 1.1 V. In contrast, the presence of a large energy barrier in the PFO‐based devices results in substantial losses in both V OC and photocurrent. These results demonstrate that TFB can serve as a superior HTM for inverted PSCs. Moreover, it is anticipated that the performance of the three HTMs identified here might guide the molecular design of novel HTMs for the manufacture of highly efficient inverted PSCs.