Atomic Scale Investigation of the CuPc–MAPbX3 Interface and the Effect of Non-Stoichiometric Perovskite Films on Interfacial Structures

Metal halide perovskites (MHPs) have become a major topic of research in thin film photovoltaics due to their advantageous optoelectronic properties. These devices typically have the MHP absorber layer sandwiched between two charge selective layers (CSLs). The interfaces between the perovskite layer and these CSLs are potential areas of higher charge recombination. Understanding the nature of these interfaces is key for device improvement. Additionally, non-stoichiometric perovskite films are expected to strongly impact the interfacial properties. In this study, the interface between CH3NH3PbI3 (MAPbI3) and copper phthalocyanine (CuPc), a hole transport layer (HTL), is studied at the atomic scale. We use scanning tunneling microscopy (STM) combined with density functional theory (DFT) predictions to show that CuPc deposited on MAPbX3 (X = I,Br) forms a self-assembled layer consistent with the α-polymorph of CuPc. Additionally, STM images show a distinctly different adsorption orientation for CuPc on non-perovskite domains of the thin film samples. These findings highlight the effect of non-stoichiometric films on the relative orientation at the MHP/HTL interface, which may affect interfacial charge transport in a device. Our work provides an atomic scale view of the MHP/CuPc interface and underscores the importance of understanding interfacial structures and the effect that the film stoichiometry can have on interfacial properties.