A p‐p+ Homojunction‐Enhanced Hole Transfer in Inverted Planar Perovskite Solar Cells

Perovskite solar cells (PSCs) have triggered a research trend in solar energy devices in view of their high power conversion efficiency and ease of fabrication. However, more delicate strategies are still required to suppress carrier recombination at charge transfer interfaces, which is the necessary path to high‐efficiency solar cells. Here, a p–p+ homojunction was constructed on basis of NiO film to enhance hole transfer in an inverted planar perovskite solar cell. The homojunction was generated by fabricating a NiO/Cu:NiO bilayer film. The density functional theory calculation demonstrated the charge density difference in the two layers, which could generate a space charge region and a band bending at the junction, and the result was further proved by energy level structure analysis of NiO and Cu:NiO films. The designed homojunction could accelerate the hole transfer and inhibit carrier recombination at the interface between hole transfer layer and perovskite layer. Finally, the inverted planar perovskite solar cell with p–p+ homojunction showed an efficiency of 18.30 % and a high fill factor of 0.81, which were much higher than the counterpart of the PSCs individually using NiO or Cu:NiO as hole transfer layer. This work developed a new structure of hole transport layer to enhance the performance of PSCs, and also provided new ideas for design of charge transfer films. p‐p+ Homojunction: A new structure of hole transport layer based on a p‐p+ homojunction (NiO/Cu:NiO bilayer) is constructed for an inverted planar perovskite solar cell. The band alignment in the bilayer can impel effective hole transport, further accelerate carrier transfer, and suppress carrier recombination at interface between hole transfer layer and perovskite layer, yielding a device with enhanced photovoltaic performance.