We have studied the interface properties of metal phthalocyanine (MPc, M = Zn, Cu) molecules at a methylammonium lead iodide (MAPbI3) surface using density functional theory (DFT) based simulations. From the adsorption energies, the face-on orientation is found to have an order of magnitude stronger binding energy than the edge-on orientation, where CuPc binds a little stronger than ZnPc with its closer interfacial distance. Our detailed analysis of interface electronic structure suggests that the edge-on configuration possesses a large energy barrier for the hole transfer from MAPbI3 to MPc molecules. In contrast, the face-on configuration has no such barrier, facilitating the hole transfer, while at the same time the desirable alignment of the conduction band suppresses the electron–hole recombination. Therefore, the face-on configuration is clearly found to be more suitable for the photovoltaic process, in line with the experimental reports. Our work emphasizes the impact of MPc orientation upon perovskite solar cell efficiency besides other factors such as Pc thin film's mobility and morphology, and provides insightful guidance to efficient and stable hole transport layers.
