STM driven modification of bismuth nanostructures

The tip of a scanning tunneling microscope (STM) gently interacting with the substrate is used to modify (110) bismuth islands deposited on highly oriented pyrolitic graphite (HOPG), and hence to investigate the atomic and electronic structure of the islands. The tip interaction leads to the evolution of metastable 3 ML thick regions into structures of higher thermodynamic stability, which in the case of bismuth on graphite are rods (typically ≥ 5 ML high) and stripes. The formation of trenches that extend along the stripes is observed which is related to the presence of kinks and weak bonds at the 3-5 ML interface. Migration of whole islands along particular substrate directions is evidence for superlubricity due to the misfit between Bi and HOPG unit cells. Perimeter diffusion through atoms and not vacancies is a driving force of all observed modifications. The Bi islands are found to be able to deform and their decay is not governed by Ostwald ripening (which is absent in this system). Instead quantum size effects play a major role in the evolution of the islands, as evidenced by the observation of preferred widths. Density functional theory calculations reveal an oval Fermi surface with de Broglie wavelength corresponding to observed width of islands. These results are all consistent with a thin film Bi allotrope which has both paired atomic layers on the surface and bulk-like chains of bonds vertically through the structure.