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Phosphorus pentamer (cyclo-P5-) ions are unstable in nature but can besynthesized at the Ag(111) surface. Unlike monolayer black phosphorous, littleis known about their electronic properties when in contact with metalelectrodes, although this is crucial for future applications. Here wecharacterize the atomic structure of cyclo-P5 assembled on Ag(111) using atomicforce microscopy with functionalized tips and density functional theory.Combining force and tunneling spectroscopy, we find that a strong chargetransfer induces an inward dipole moment at the cyclo-P5/Ag interface as wellas the formation of an interface state. We probe the image potential states byfield-effect resonant tunneling and quantify the increase of the local changeof work function of 0.46 eV at the cyclo-P5 assembly. Our results suggest thatthe high-quality of the cyclo-P5/Ag interface might serve as a prototypicalsystem for electric contacts in phosphorus-based semiconductor devices.

Probing charge redistribution at the interface of self-assembled cyclo-P5 pentamers on Ag(111)