Jing Yege, Wang Chen, Zhu Bo, Xiao Songwen, Guan Wei, Liu Shuainan, Zhang Ning, Wen Shanpeng, Zhu Guangshan
Faculty of Chemistry, Northeast Normal University, Changchun, 130024, P. R. China.
State Key Laboratory on Integrated Optoelectronics and College of Electronic Science & Engineering, Jilin University, Changchun, 130012, P. R. China.
Angew Chem Int Ed Engl. 2024 Oct 14;63(42):e202410069. doi: 10.1002/anie.202410069. Epub 2024 Sep 5.
Non-radiative recombination, caused by trap states, significantly hampers the efficiency and stability of perovskite solar cells (PSCs). The emerging porous organic polymers (POPs) show promise as a platform for designing novel defect passivation agents due to their rigid and porous structure. However, the POPs reported so far lack either sufficient stability or clear sites of interactions with the defects. Herein, two chlorine-functionalized, fully conjugated porous aromatic frameworks (PAFs) were constructed via a decarbonylation reaction. The chlorinated PAFs feature unique long-range conjugated networks bearing multiple chlorine atoms, significantly improving the photovoltaic performance and stability of doped solar cells. Combined experimental and theoretical analyses confirmed the strong passivation effects of conjugated structure to the defect through Cl sites. Specifically, PAF-159, bearing a triphenylamine moiety, demonstrated stronger Cl-Pb bonding and higher passivation efficiency due to the presence of π* anti-bonding orbitals, which elevate the HOMO energy level and facilitate Cl-Pb charge transfer. Consequently, we obtained high-performance PAF-159-doped devices with advanced PCE (24.3 %), good storage stability (retaining 86 % after 3000 hours), and good long-term operational stability (retaining 92 % after 350 hours).
由陷阱态引起的非辐射复合显著阻碍了钙钛矿太阳能电池（PSC）的效率和稳定性。新兴的多孔有机聚合物（POP）由于其刚性和多孔结构，有望成为设计新型缺陷钝化剂的平台。然而，迄今为止报道的POP要么缺乏足够的稳定性，要么与缺陷的相互作用位点不明确。在此，通过脱羰反应构建了两种氯官能化的全共轭多孔芳香骨架（PAF）。氯化PAF具有独特的带有多个氯原子的长程共轭网络，显著提高了掺杂太阳能电池的光伏性能和稳定性。结合实验和理论分析证实了共轭结构通过Cl位点对缺陷具有很强的钝化作用。具体而言，带有三苯胺部分的PAF-159由于存在π*反键轨道，表现出更强的Cl-Pb键合和更高的钝化效率，这提高了HOMO能级并促进了Cl-Pb电荷转移。因此，我们获得了具有先进光电转换效率（24.3%）、良好存储稳定性（3000小时后保留86%）和良好长期运行稳定性（350小时后保留92%）的高性能PAF-159掺杂器件。
