An Effective Strategy of Combining Surface Passivation and Secondary Grain Growth for Highly Efficient and Stable Perovskite Solar Cells

Abstract Interfacial engineering methods have been developed to solve defect issues of perovskite solar cells (PSCs). However, traditional surface passivation has limited effects on eliminating defect‐forming residuals, while secondary grain growth (SGG) is restricted by limited choices of additives and intrinsic properties of perovskites. Here, a pincer strategy of taking advantages of surface passivation and SGG is proposed to modify both exterior and interior of CH 3 NH 3 PbI 3 (MAPbI 3 ) perovskite, by employing cyanoacetate‐containing donor‐acceptor compounds (CA‐D‐A) including 2‐cyano‐3‐(3,4,5‐trimethoxyphenyl)acrylic acid (CA), methanaminium 2‐cyano‐3‐(3,4,5‐trimethoxyphenyl)acrylate (CAMA), and aminomethaniminium (Z)‐2‐cyano‐3‐(3,4,5‐trimethoxyphenyl)acrylate (CAFA). In comparison to untreated perovskite, CA‐D‐A treated perovskites present better crystallinity because of SGG, lower trap densities due to the synergistic effect of surface passivation and SGG, and tuned energy levels induced by CA‐D‐A. Accordingly, the CA‐D‐A treated MAPbI 3 ‐based PSCs exhibit higher open‐circuit voltage and fill factor than the control PSC without any treatment, leading to improved power conversion efficiency (PCE) and enhanced device stability, especially the CAMA treated PSCs with an average PCE promoted from 17.77 (control PSCs) to 18.71%, and importantly an excellent PCE of 19.71% through further optimization. This work provides an effective strategy for developing highly efficient and stable PSCs with the assistance of both surface passivation and SGG.