Resolving the Intrinsic Bandgap and Edge Effect of BiI3 Film Epitaxially Grown on Graphene.

Two-dimensional materials with layered structures, appropriate bandgap, and high carrier mobilities have gathered tremendous interests due to their potential applications in optoelectronic and photovoltaic devices. Here, we report the growth of BiI3 thin film with controllable atomic thickness on graphene-terminated 6H-SiC(0001) substrate by molecular beam epitaxy (MBE) method. The growth kinetic processes and crystalline properties of the BiI3 film are studied by scanning tunneling microscopy (STM). The scanning tunneling spectroscopy (STS) reveals a bandgap of 2.8 eV for monolayer BiI3 with a weak dependence on film thickness for few-layer BiI3, which greatly exceeds the previous reported values identified by macroscopic optical measurements. This discrepancy originates from the edge effect of BiI3 that renders the bandgap downshift to 1.5 - 1.6 eV, as identified by the STS curves and the further confirmed by density functional theory (DFT) calculations. Our work provides a method to fabricate high-quality monolayer BiI3 film and resolves its intrinsic bandgap as well as the edge effect on reduction of bandgap, benefitting not only to fundamental researches but also to nanoelectronic and optoelectronic applications.