Ligand Driven Control and F‐Doping of Surface Characteristics in FASnI3 Lead‐Free Perovskites: Relation Between Molecular Dipoles, Surface Dipoles, Work Function Shifts, and Surface Strain

Abstract

AbstractThe performance and operational stability of perovskite‐based devices heavily rely on the interfacial properties between the photoactive perovskite layer and charge transport layers. Understanding the theoretical relationship between surface/interface dipoles and surface energetics is crucial for scientific understanding and practical applications. In this study, a method is applied that bridges classical electromagnetism and modern atomistic approaches. The impact of dipolar ligand molecules functionalizing the FASnI3 perovskite surface is investigated, with inspection of the interplay between surface dipole, charge transfer, and local strain effect, and corresponding shifts in the valence level. The results reveal that the contribution of individual molecular entities to surface dipoles and electric susceptibilities follows an essentially additive behavior. The influence of F doping usually used to mitigate Sn oxidation in Sn‐based layer for photovoltaic applications, is also discussed. Furthermore, the findings are compared with predictions from classical approaches employing a capacitor model that links the induced vacuum level shift and the molecular dipole moment. The insights gained from the study provide theoretical guidelines for fine‐tuning the work functions of materials, thus enabling effective interfacial engineering in this class of semiconductors.