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

Organic p-n junctions attract widespread interest in the field of molecular electronics because of their unique optoelectronic singularities. Importantly, the molecular donor/acceptor character is strongly correlated to the degree of substitution, e.g., the introduction of electron-withdrawing groups. Herein, by gradually increasing the degree of peripheral fluorination on planar, D(4h-)symmetric iron(II) phthalocyanato (FePc) complexes, the energy level alignment and molecular order is defined in a metal-supported bilayered Pc-based junction using photoemission orbital tomography. This non-destructive method selectively allows identifying molecular levels of the hetero-architectures. It demonstrates that, while the symmetric fluorination of FePc does not disrupt the long-range order and degree of metal-to-molecule charge transfer in the first molecular layer, it strongly impacts the energy alignment in both the interface and topmost layer in the bilayered structures. The p-n junction formed in the bilayer of perhydrogenated FePc and perfluorinated FeF16Pc may serve as an ideal model for understanding the basic charge-transport phenomena at the metal-supported organic-organic interfaces, with possible application in photovoltaic devices.