Supramolecular Aza Crown Ether Modulator for Efficient and Stable Perovskite Solar Cells

Abstract Molecular modulators have been demonstrated to be an effectual strategy for reducing the defect at the interface and in bulk of perovskite and ameliorating the performance and stability of perovskite solar cells (PSCs). Herein, 1‐aza‐15‐crown 5‐ether (A15C5), with a unique nitrogen heterocyclic structure as a molecular modulator is introduced at the interface between perovskite layer and hole transport layer of PSCs. Multiple supramolecular synergistic interaction between A15C5 and perovskite dramatically suppress and passivate defects, resulting in a 38% decrease in electron trap‐state density in perovskite. The formation of two‐dimensional/th3D perovskite heterojunctions induced by planar A15C5 releases residual strain of perovskite film, optimizes the match of energy level array and boosts the stability of devices. Consequently, A15C5‐modulated PSC achieves an impressing efficiency of 24.13% along with excellent humidity, light and thermal stability. This work provides a typical strategy to utilize supramolecular crown ether in PSCs.