Bisphosphonate‐Anchored Self‐Assembled Molecules with Larger Dipole Moments for Efficient Inverted Perovskite Solar Cells with Excellent Stability

Abstract In the fabrication of inverted perovskite solar cells (PSCs), the wettability, adsorbability, and compactness of self‐assembled monolayers (SAMs) on conductive substrates have critical impacts on the quality of the perovskite films and the defects at the buried perovskite‐substrate interface, which control the efficiency and stability of the devices. Herein, three bisphosphonate‐anchored indolocarbazole (IDCz)‐derived SAMs, IDCz‐1, IDCz‐2, and IDCz‐3, are designed and synthesized by modulating the position of the two nitrogen atoms of the IDCz unit to improve the molecular dipole moments and strengthen the π–π interactions. Regulating the work functions (WF) of FTO electrodes through molecular dipole moments and energy levels, the perovskite band bends upwards with a small offset for ITO/IDCz‐3/perovskite, thereby promoting hole extraction and blocking electrons. As a result, the inverted PSC employing IDCz‐3 as hole‐collecting layer exhibits a champion PCE of 25.15%, which is a record efficiency for the multipodal SAMs‐based PSCs. Moreover, the unencapsulated device with IDCz‐3 can be stored for at least 1800 h with little degradation in performance.