Enhanced Thermal Stability of Inverted Perovskite Solar Cells by Bulky Passivation With Pyridine‐Functionalized Triphenylamine

Despite competitive efficiency compared to Si solar cells and relevant stability at near room temperatures, the rapid degradation at elevated temperatures remains the critical obstacle for the exploitation of perovskite photovoltaics. In this work, a 4‐(pyridin‐4‐yl)triphenylamine (TPA‐Py) with pyridine anchor group was employed for intergrain bulk modification of double‐cation CsCH(NH 2 ) 2 PbI 3 perovskite absorbers to enhance thermal stability. Through coordination and dipole–dipole interactions, nitrogen‐containing fragments (diphenylamine and pyridine) of TPA‐Py passivate uncoordinated cations and improve the phase resilience of perovskite films against segregation. This resulted in a power conversion efficiency of 21.3% with a high open‐circuit voltage of 1.14 V. Notable impact of self‐assembled monolayer incorporated into the bulk of the perovskite film manifested in a huge improvement of thermal stability at 85°C (ISOS‐D‐2). TPA‐Py modification extended the T80 lifetime to ≈700 h compared to only 200 h for the reference under harsh heating stress in ambient conditions. In‐depth analysis using photoinduced voltage transients and admittance spectroscopy after different stress periods revealed the screening of ion migration (0.45 eV) for devices with TPA‐Py. This work offers an important understanding of the bulk modification of microcrystalline perovskite absorbers and a guide for robust design of bulk and buried interfaces in highly efficient perovskite solar cells.