Electron Transport Layer Engineering Induced Carrier Dynamics Optimization for Efficient Cd‐Free Sb2Se3 Thin‐Film Solar Cells

Abstract Antimony selenide (Sb 2 Se 3 ) is a highly promising photovoltaic material thanks to its outstanding optoelectronic properties, as well as its cost‐effective and eco‐friendly merits. However, toxic CdS is widely used as an electron transport layer (ETL) in efficient Sb 2 Se 3 solar cells, which largely limit their development toward market commercialization. Herein, an effective green Cd‐free ETL of SnO x is introduced and deposited by atomic layer deposition method. Additionally, an important post‐annealing treatment is designed to further optimize the functional layers and the heterojunction interface properties. Such engineering strategy can optimize SnO x ETL with higher nano‐crystallinity, higher carrier density, and less defect groups, modify Sb 2 Se 3 /SnO x heterojunction with better interface performance and much desirable “spike‐like” band alignment, and also improve the Sb 2 Se 3 light absorber layer quality with passivated bulk defects and prolonged carrier lifetime, and therefore to enhance carrier separation and transport while suppressing non‐radiative recombination. Finally, the as‐fabricated Cd‐free Mo/Sb 2 Se 3 /SnO x /ITO/Ag thin‐film solar cell exhibits a stimulating efficiency of 7.39%, contributing a record value for Cd‐free substrate structured Sb 2 Se 3 solar cells reported to date. This work provides a viable strategy for developing and broadening practical applications of environmental‐friendly Sb 2 Se 3 photovoltaic devices.