A moderate intensity ligand works best: a theoretical study on passivation effects of pyridine-based molecules for perovskite solar cells.

Improving battery stability while maintaining high photoelectric conversion efficiency remains the bottleneck in the current development of perovskite solar cells (PSCs). Three π-conjugated pyridine-based molecules, pyridine (Py), bipyridine (Bpy), and terpyridine (Tpy), were adopted to passivate the PSCs in recent experiments (J. Chen, S.-G. Kim, X. Ren, H. S. Jung and N.-G. Park, J. Mater. Chem. A, 2019, 7, 4977-4987; J. Zhang, J. Duan, Q. Zhang, Q. Guo, F. Yan, X. Yang, Y. Duan and Q. Tang, , 2022, , 134230), in which Bpy works best in terms of photovoltaic properties and moisture tolerance. In this work, based on density functional theory (DFT) calculations and molecular dynamics (AIMD) simulations, we demonstrate that Bpy displays the least structural fluctuation when adsorbed on the perovskite surface, enlarges the bandgap suppressing electron-hole recombination, and exhibits remarkable shielding effects against moisture. The appropriate anchoring ability of Bpy retains robust binding strength and preferable charge transfer ability compared to Py at the interfaces between the passivation molecules (PMs) and MAPbI. In contrast, although Tpy possesses the strongest charge-transfer capability, it introduces midgap states owing to intense electronegativity, providing additional pathways for nonradiative charge relaxation. Besides, Tpy triggers rapid diffusions of water and larger atomic fluctuations, destroying the structures of the perovskite through the removal of lead atoms. Our computational results not only rationalize the experimental observations but also provide valuable guidance at the atomic level to design novel PMs that endow PSCs with outstanding photovoltaic performance as well as stability against moisture.