Electronic Structure of Ultrathin Bismuth Films with A7 and Black-Phosphorus-like Structures

Using scanning tunneling spectroscopy and first-principles calculations, we have studied the electronic structure of two different ultrathin bismuth films on a Si(111)-7×7 substrate; a hexagonal film (HEX film) having a bulklike (A7-like) structure and a film having a black-phosphorus-like structure (BP film). The HEX film is metallic because of spin–orbit (SO)-split surface-state bands lying inside the projected bulk band gap near the Fermi level. Another SO-split surface state is also observed inside the SO gap. The BP film exhibits a significant reduction in metallicity in contrast to the HEX film. This is related to the formation of a very stable paired-layer structure, the mechanism of which is similar to that of the stabilization of semiconducting bulk black P. However, unlike bulk black P, a certain extent of metallicity still remains. This slight metallicity can be associated with buckling and strain in the BP film, which is analogous to the fact that shear angle distortion in bulk Bi is responsible for its semimetallicity.