Unveiling and Modulating the Interfacial Reaction at the Metal–Hole Conductor Heterojunction toward Reliable Perovskite Solar Cells

Interfaces between functional layers in perovskite solar cells (PSCs) are of paramount importance in determining their efficiency and stability, but the interaction and stability of metal-hole conductor (HC) interfaces have received less attention. Here, we discover an intriguing transient behavior in devices which induces a profound efficiency fluctuation from 9 to 20% during the initial performance testing. Air exposure (e.g., oxygen and moisture) can significantly accelerate this nonequilibrium process and simultaneously enhance the device maximal efficiency. Structural analysis reveals that the chemical reaction between Ag and HC occurred during the metal deposition by thermal evaporation, leading to the formation of an insulating barrier layer at their interfaces, which results in a high charge-transport barrier and poor device performance. Accordingly, we propose a metal diffusion-associated barrier evolution mechanism to understand the metal/HC interfaces. To mitigate these detrimental effects, we strategically develop an interlayer strategy by introducing an ultrathin layer of molybdenum oxide (MoO₃) between Ag and HC, which is found to effectively suppress the interfacial reaction, yielding highly reliable PSCs with instant high efficiency. This work provides new insights into understanding the metal-organic interfaces, and the developed interlayer strategy can be generally applicable to engineer other interfaces in realizing efficient and stable contacts.