Dual‐Site Molecular Dipole Enables Tunable Interfacial Field Toward Efficient and Stable Perovskite Solar Cells

Abstract The interfacial management in perovskite solar cells (PSCs), including mitigating the carrier transport barrier and suppressing non‐radiative recombination, still remains a significant challenge for efficiency and stability enhancement. Herein, by screening a family of fluorine (F) terminated dual‐site organic dipole molecules, the study aims to gain insight into the molecular dipole array toward tunable interfacial field. Both experimental and theoretical results reveal that these functional interfacial dipole molecules can effectively anchor on perovskite surface through Lewis acid‐base interaction. In addition, the tailored side‐chain with terminated F atoms allows for altering and constructing a well matched perovskite/Spiro‐OMeTAD interfacial contact. As a result, the inserting dual‐site organic dipole array effectively modulates the interface to deliver a gradient energy level alignment, facilitating carrier extraction and transport. The optimal dual‐site dipole trifluoro‐methanesulfonamide mediated N‐i‐P PSCs achieve the highest efficiency of 25.47%, together with enhanced operational stability under 1000 h of the simulated 1‐sun illumination exposure. These findings are believed to provide insight into the design of dual‐site molecular dipole with sufficient interfacial tunability for perovskite‐based optoelectronic devices.