B-Site Co-Doping Coupled with Additive Passivation Pushes the Efficiency of Pb-Sn Mixed Inorganic Perovskite Solar Cells to Over 17.

Abstract

Pb-Sn mixed inorganic perovskite solar cells (PSCs) have garnered increasing interest as a viable solution to mitigate the thermal instability and lead toxicity of hybrid lead-based PSCs. However, the relatively poor structural stability and low device efficiency hinder its further development. Herein, high-performance manganese (Mn)-doped Pb-Sn-Mn-based inorganic perovskite solar cells (PSCs) are successfully developed by introducing Benzhydroxamic Acid (BHA) as multifunctional additive. The incorporation of smaller divalent Mn cations contributes to a contraction of the perovskite crystal, leading to an improvement in structural stability. The BHA additive containing a reductive hydroxamic acid group (O═C-NHOH) not only mitigates the notorious oxidation of Sn²⁺ but also interacts with metal ions at the B-site and passivates related defects. This results in films with high crystallinity and low defect density. Moreover, the BHA molecules tend to introduce a near-vertical dipole moment that parallels the built-in electric field, thus facilitating charge carrier extraction. Consequently, the resulting device delivers a champion PCE as high as 17.12%, which represents the highest reported efficiency for Pb-Sn-based inorganic PSCs thus far. Furthermore, the BHA molecule provides an in situ encapsulation of the perovskite grain boundary, resulting in significant enhancement of device air stability.