Germanene Reformation from Oxidized Germanene on Ag(111)/Ge(111) by Vacuum Annealing.

For group 14 mono-elemental 2D materials, such as silicene, germanene, and stanene, oxidation is a severe problem that alters or degrades their physical properties. This study shows that the oxidized germanene on Ag(111)/Ge(111) can be reformed to germanene by simple heating ≈500 °C in a vacuum. The key reaction in reforming germanene is the desorption of GeO and GeO2 during heating ≈350 °C. After removing surface oxygen, Ge further segregates to the surface, resulting in the reformation of germanene. The reformed germanene has the same crystal structure, a (7√7 × 7√7) R19.1° supercell with respect to Ag(111), and has equivalent high quality to that of as-grown germanene on Ag(111)/Ge(111). Even after air oxidation, germanene can be reformed by annealing in a vacuum. On the other hand, the desorption of GeO and GeO2 at high temperatures is not suppressed in the O2 backfilling atmosphere. This instability of oxidized germanene/Ag(111)/Ge(111) at high temperatures contributes to the ease of germanene reformation without residual oxygen. In other words, the present germanene reformation, as well as the segregation of germanene on Ag(111)/Ge(111), is a highly robust process to synthesize germanene.

Growth of a quasicrystal-related structure and superstructure for ultrathin Ce-Ti-O films on Pt(111).

Herein, oxide quasicrystal-related (OQC-R) structure and Ce-Ti-O-(3 × 3) superstructure ultrathin films were prepared on Pt(111) and characterized using scanning tunneling microscopy (STM) and low-energy electron diffraction. The OQC-R structure with dodecagonal clusters consisting of triangles, squares, and rhombuses was observed in STM images. The first discovery of the OQC-R structure with a magnetic rare earth metal expands the possibility of discovering new oxide quasicrystals with novel magnetism or superconductivity. By depositing Ti on an OQC-R ultrathin film and post-annealing, a honeycomb lattice of the Ce-Ti-O-(3 × 3) superstructure was prepared. From X-ray photoelectron spectroscopy (XPS) and resonant-photoelectron spectroscopy, the chemical states of the Ce and Ti atoms in the OQC-R structure corresponded to the Ce3+ and Ti2+ states, while those for the Ce-Ti-O-(3 × 3) superstructure corresponded to the Ce3+, Ti3+, and Ti2+ states. The phase transformation from the OQC-R structure to the Ce-Ti-O-(3 × 3) honeycomb superstructure likely occurred when the amount of Ti increased and was more oxidized. The elemental atomic density was also calibrated using XPS and Rutherford backscattering spectroscopy. These results propose tentative structural models of the OQC-R structure as Ce18Ti14O41 and the Ce-Ti-O-(3 × 3) superstructure as CeTi6O9.

Graphene's Latest Cousin: Plumbene Epitaxial Growth on a "Nano WaterCube".

While theoretical studies predicted the stability and exotic properties of plumbene, the last group-14 cousin of graphene, its realization has remained a challenging quest. Here, it is shown with compelling evidence that plumbene is epitaxially grown by segregation on a Pd1- x Pbx (111) alloy surface. In scanning tunneling microscopy (STM), it exhibits a unique surface morphology resembling the famous Weaire-Phelan bubble structure of the Olympic "WaterCube" in Beijing. The "soap bubbles" of this "Nano WaterCube" are adjustable with their average sizes (in-between 15 and 80 nm) related to the Pb concentration (x < 0.2) dependence of the lattice parameter of the Pd1- x Pbx (111) alloy surface. Angle-resolved core-level measurements demonstrate that a lead sheet overlays the Pd1- x Pbx (111) alloy. Atomic-scale STM images of this Pb sheet show a planar honeycomb structure with a unit cell ranging from 0.48 to 0.49 nm corresponding to that of the standalone 2D topological insulator plumbene.

Germanene Epitaxial Growth by Segregation through Ag(111) Thin Films on Ge(111).

Large-scale two-dimensional sheets of graphene-like germanium, namely, germanene, have been epitaxially prepared on Ag(111) thin films grown on Ge(111), using a segregation method, differing from molecular beam epitaxy used in previous reports. From the scanning tunneling microscopy (STM) images, the surface is completely covered with an atom-thin layer showing a highly ordered long-range superstructure in wide scale. Two types of protrusions, named hexagon and line, form a (7√7 × 7√7) R19.1° supercell with respect to Ag(111), with a very large periodicity of 5.35 nm. Auger electron spectroscopy and high-resolution synchrotron radiation photoemission spectroscopy demonstrate that Ge atoms are segregated on the Ag(111) surface as an overlayer. Low-energy electron diffraction clearly shows incommensurate "(1.35 × 1.35)" R30° spots, corresponding to a lattice constant of 0.39 nm, in perfect accord with close-up STM images, which clearly reveal an internal honeycomb arrangement with corresponding parameter and low buckling within 0.01 nm. As this 0.39 nm value is in good agreement with the theoretical lattice constant of free-standing germanene, conclusively, the segregated Ge atoms with trivalent bonding in honeycomb configuration form a characteristic two-dimensional germanene-like structure.

Growth and structure of ultrathin cerium oxide films on Rh(111).

The geometric structure of ultra-thin cerium oxide films on Rh(111), prepared by annealing the metallic cerium films at a very low coverage between 0.3 and 1.5 monolayers in an oxygen atmosphere, is investigated using scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations. The STM image and LEED pattern indicate that cerium oxide films epitaxially grown as ordered CeO2(111) layers aligned to the 110 azimuthal direction of Rh(111). The in-plane lattice parameter measured from the LEED pattern appears to be contracted with respect to the bulk ceria lattice. The measured ratio Ce:O for two-trilayer cerium oxide film is 1.96:1, which is close to the stoichiometric ratio. The simulated STM image on the basis of DFT+U calculations is in good agreement with the experimental STM images.