Band alignment and charge transfer in rutile-TiO2/CH3NH3PbI3−xClx interfaces

Abstract

Rutile-TiO₂/hybrid halide perovskite CH₃NH₃PbI_3−xCl_x interfaces are investigated by ab initio density functional theory calculations. The role of chlorine in achieving enhanced solar cell power conversion efficiencies is in the focus of recent studies, which point to increased carrier mobilities, reduced recombination rates, a driven morphology evolution of the perovskite layer and improved carrier transport across the interface. As it was recently established that chlorine is preferentially localized in the vicinity of the interface and not in the bulk of the perovskite layer, we analyze the changes introduced in the electronic properties by varying the chlorine concentration near the interface. In particular, we discuss the effects introduced in the electronic band structure and show the role of chlorine in the enhanced electron injection into the rutile-TiO₂ layer. Taking into account these implications, we discuss the conditions for optimizing the solar cell efficiency in terms of interfacial chlorine concentration.