Unusual Electronic States and Superconducting Proximity Effect of Bi Films Modulated by a NbSe2 Substrate.

Heterostructures of two-dimensional layered materials can be functionalized with exotic phenomena that are unpresented with each constituting component. The interface effect plays a key role in determining the electronic properties of the heterostructure, whose characterization requires a correlation with the morphology with atomic-scale precision. Here, we report an investigation on the electronic properties of few-layer Bi(110) films mediated by a NbSe2 substrate. By utilizing scanning tunneling microscopy and spectroscopy, we show a significant variation of the density of states at different Bi film thicknesses, resulting in an unusual superconducting proximity effect that deviates from the conventional monotonous decay behavior. Moreover, the electronic states of the Bi films are also prominently modulated by the Moiré pattern spatially. With first-principles calculations, we illuminate these findings as the results of covalent-like quasi-bonds formed at the Bi/NbSe2 interface, which profoundly alter the charge distributions in the Bi films. Our study indicates a viable way of modulating the electronic properties of ultrathin films by quasi-covalent interfacial couplings beyond conventional van der Waals interactions.