Nanoclusters and nanolines: the effect of molybdenum oxide substrate stoichiometry on iron self-assembly.

The growth of Fe nanostructures on the stoichiometric MoO2/Mo(110) and oxygen-rich MoO2+x /Mo(110) surfaces has been studied using low-temperature scanning tunnelling microscopy (STM) and density functional theory calculations. STM results indicate that at low coverage Fe nucleates on the MoO2/Mo(110) surface, forming small, well-ordered nanoclusters of uniform size, each consisting of five Fe atoms. These five-atom clusters can agglomerate into larger nanostructures reflecting the substrate geometry, but they retain their individual character within the structure. Linear Fe nanocluster arrays are formed on the MoO2/Mo(110) surface at room temperature when the surface coverage is greater than 0.6 monolayers. These nanocluster arrays follow the direction of the oxide rows of the strained MoO2/Mo(110) surface. Slightly altering the preparation procedure of MoO2/Mo(110) leads to the presence of oxygen adatoms on this surface. Fe deposition onto the oxygen-rich MoO2+x /Mo(110) surface results in elongated nanostructures that reach up to 24 nm in length. These nanolines have a zigzag shape and are likely composed of partially oxidised Fe formed upon reaction with the oxygen-rich surface.

Atomically resolved STM imaging with a diamond tip: simulation and experiment.

The spatial resolution of a scanning tunneling microscope (STM) can be enhanced using light element-terminated probes with spatially localized electron orbitals at the apex atom. Conductive diamond probes can provide carbon atomic orbitals suitable for STM imaging with sub-Ångström lateral resolution and high apex stability crucial for the small tunneling gaps necessary for high-resolution experiments. Here we demonstrate that high spatial resolution can be achieved in STM experiments with single-crystal diamond tips, which are generally only considered for use as probes for atomic force microscopy. The results of STM experiments with a heavily boron-doped, diamond probe on a graphite surface; density functional theory calculations of the tip and surface electronic structure; and first-principles tunneling current calculations demonstrate that the highest spatial resolution can be achieved with diamond tips at tip-sample distances of 3-5 Å when frontier p-orbitals of the tip provide their maximum contribution to the tunneling current. At the same time, atomic resolution is feasible even at extremely small gaps with very high noise in the tunneling current.

Growth and ordering of Ni(II) diphenylporphyrin monolayers on Ag(111) and Ag/Si(111) studied by STM and LEED.

The room temperature self-assembly and ordering of (5,15-diphenylporphyrinato)nickel(II) (NiDPP) on the Ag(111) and Ag/Si(111)-(√3 × âˆš3)R30° surfaces have been investigated using scanning tunnelling microscopy and low-energy electron diffraction. The self-assembled structures and lattice parameters of the NiDPP monolayer are shown to be extremely dependent on the reactivity of the substrate, and probable molecular binding sites are proposed. The NiDPP overlayer on Ag(111) grows from the substrate step edges, which results in a single-domain structure. This close-packed structure has an oblique unit cell and consists of molecular rows. The molecules in adjacent rows are rotated by approximately 17° with respect to each other. In turn, the NiDPP molecules form three equivalent domains on the Ag/Si(111)-(√3 × âˆš3)R30° surface, which follow the three-fold symmetry of the substrate. The molecules adopt one of three equivalent orientations on the surface, acting as nucleation sites for these domains, due to the stronger molecule-substrate interaction compared to the case of the Ag(111). The results are explained in terms of the substrate reactivity and the lattice mismatch between the substrate and the molecular overlayer.