Semiconductor Halogenation in Molecular Highly‐Oriented Layered p–n (n–p) Junctions

Abstract Organic p–n junctions attract widespread interest in the field of molecular electronics because their unique optoelectronic singularities. Importantly, donor/acceptor character is strongly correlated to degree substitution, e.g., introduction electron‐withdrawing groups. Herein, by gradually increasing peripheral fluorination on planar, D 4h− symmetric iron(II) phthalocyanato (FePc) complexes, energy level alignment and order defined a metal‐supported bilayered Pc‐based junction using photoemission orbital tomography. This non‐destructive method selectively allows identifying levels hetero‐architectures. It demonstrates that, while FePc does not disrupt long‐range metal‐to‐molecule charge transfer first layer, it impacts both interface topmost layer structures. The formed bilayer perhydrogenated perfluorinated FeF 16 Pc may serve as an ideal model for understanding basic charge‐transport phenomena at organic–organic interfaces, with possible application photovoltaic devices.