Chemical Interaction at the MoO₃/CH₃NH₃PbI₃–ₓClₓ Interface

The limited long-term stability of metal halide perovskite-based solar cells is a bottleneck in their drive toward widespread commercial adaptation. The organic hole-transport materials (HTMs) have been implicated in the degradation, and metal oxide layers are proposed as alternatives. One of the most prominent metal oxide HTM in organic photovoltaics is MoO₃. However, the use of MoO₃ as HTM in metal halide perovskite-based devices causes a severe solar cell deterioration. Thus, the formation of the MoO₃/CH₃NH₃PbI₃–ₓClₓ (MAPbI₃–ₓClₓ) heterojunction is systematically studied by synchrotron-based hard X-ray photoelectron spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and Raman spectroscopy. Upon MoO₃ deposition, significant chemical interaction is induced at the MoO₃/MAPbI₃–ₓClₓ interface: substoichiometric molybdenum oxide is present, and the perovskite decomposes in the proximity of the interface, leading to accumulation of PbI₂ on the MoO₃ cover layer. Furthermore, we find evidence for the formation of new compounds such as PbMoO₄, PbN₂O₂, and PbO as a result of the MAPbI₃–ₓClₓ decomposition and suggest chemical reaction pathways to describe the underlying mechanism. These findings suggest that the (direct) MoO₃/MAPbI₃–ₓClₓ interface may be inherently unstable. It provides an explanation for the low power conversion efficiencies of metal halide perovskite solar cells that use MoO₃ as a hole-transport material and in which there is a direct contact between MoO₃ and perovskite.