Intrinsic Dipole Arrangement to Coordinate Energy Levels for Efficient and Stable Perovskite Solar Cells

Abstract Despite great progress in perovskite photovoltaics, it should be noted that the intrinsic disorder dipolar cations in organic–inorganic hybrid perovskites exert negative effects on the energy band structure as well as the carrier separation and transfer dynamics. However, oriented polarization achieved by applying an external electric field may cause irreversible damage to perovskites. Herein, a unique and efficient strategy is developed to modulate the intrinsic dipole arrangement in perovskite films for high‐performance and stable perovskite solar cells (PSCs). The spontaneous reorientation of dipolar cation methylamine is triggered by a polar molecule, constructing a vertical polarization during crystallization regulation. The oriented dipole determines a gradient energy‐level arrangement in PSCs and more favorable energetics at interfaces, effectively enhancing the built‐in electric field and suppressing the nonradiative recombination. Besides, the dipole reorientation induces a local dielectric environment to remarkably reduce exciton binding energy, leading to an ultralong carrier diffusion length of up to 1708 nm. Accordingly, the n–i–p PSCs achieve a significant increase in power conversion efficiency, reaching 24.63% with negligible hysteresis and exhibiting outstanding stabilities. This strategy also provides a facile route to eliminate the mismatched energetics and enhance carrier dynamics for other novel photovoltaic devices.