The exploration of wide‐bandgap metal compound films with excellent passivation and contact properties on crystalline silicon (c‐Si) surface, as alternatives to traditional‐doped Si thin films, holds significant promise for the future enhancement of c‐Si solar cell efficiency. Herein, conductive boron‐doped zinc oxide (ZnO:B) films are deposited by atomic layer deposition (ALD) process and investigated as electron‐selective contacts, in combination with a thin SiOx passivating interlayer. This combination demonstrates a relative low contact resistivity of ≈2 mΩ cm2 and improved passivation quality. Further application of this SiOx/ZnO:B stack as a full‐area electron‐selective passivating contact in proof‐of‐concept n‐type c‐Si solar cells results in a satisfactory power conversion efficiency of over 22.0%. This electron‐selective passivating contact structure, prepared via low‐temperature, simplified, and the compositionally controlled ALD process, offers a promising pathway for the development of high‐efficiency and low‐cost c‐Si solar cells.
