Atomistic Mechanism of Surface-Defect Passivation: Toward Stable and Efficient Perovskite Solar Cells

Molecular engineering has been demonstrated to be a predominant strategy for augmenting the long-term stability and passivating adverse defects for perovskite solar cells (PSCs). Here, using density functional theory calculations combined with ab initio molecular dynamics (AIMD) simulations, the passivation effects of bidentate passivation molecules, 2-MP and 2-MDEP, on the iodine vacancy MAPbI3 were comprehensively investigated. We demonstrate that 2-MDEP engenders stronger adsorption and localized charges on Pb atoms because the separated binding sites match with the MAPbI3 lattice. Moreover, the activation barriers for ion migrations are improved by the passivation of 2-MP and 2-MDEP. Furthermore, AIMD simulations verify the improved structural stability and restrained nonradiative recombination after passivation. More importantly, the durable Pb-heteroatom interactions at the interface and stronger hydrophobicity endow 2-MDEP with more remarkable shielding effects against moisture compared to those of 2-MP. This work deepens our understanding of the passivation effects and paves the way for the design of passivation molecules toward the attainment of efficient and stable PSCs.