Preventing sintering of nanoclusters on graphene by radical adsorption.

Metal nanoclusters, supported on inert substrates, exhibiting well-defined shapes and sizes in a broad range of temperatures are a major object of desire in nanotechnology. Here, a technique is presented that improves the thermal stability of monodisperse and crystalline transition metal nanoclusters grown in a regular array on metal-supported graphene. To stabilize the clusters after growth under ultrahigh vacuum the system composed of the aggregates and the graphene/metal interface is exposed to radicals resulting from the dissociation of diatomic gases. As a model system we have used Pt as the metal element for cluster growth and the template consisting of the moiré pattern resulting from the lattice mismatch between graphene and the Ir(111) surface. The study has been performed for deuterium and oxygen radicals, which interact very differently with graphene. Our results reveal that after radical exposure the thermally activated motion of Pt nanoclusters to adjacent moiré cells and the subsequent sintering of neighbor aggregates are avoided, most pronounced for the case of atomic O. For the case of D the limits of the improvement are given by radical desorption, whereas for the case of O they are defined by an interplay between coalescence and graphene etching followed by Pt intercalation, which can be controlled by the amount of exposure. Finally, we determined the mechanism of how radical adsorption improves the thermal stability of the aggregates.

Oxygen orders differently under graphene: new superstructures on Ir(111).

Using scanning tunneling microscopy, the oxygen adsorbate superstructures on bare Ir(111) are identified and compared to the ones formed by intercalation in between graphene and the Ir(111) substrate. For bare Ir(111) we observe O-(2 × 2) and O-(2 × 1) structures, thereby clarifying a persistent uncertainty about the existence of these structures and the role of defects for their stability. For the case of graphene-covered Ir(111), oxygen intercalation superstructures can be imaged through the graphene monolayer by choosing proper tunneling conditions. Depending on the pressure, temperature and duration of O2 exposure as well as on the graphene morphology, O-(2 × 2), O-(√3×√3)-R30°, O-(2 × 1) and O-(2√3 × 2√3)-R30° superstructures with respect to Ir(111) are observed under the graphene cover. Two of these structures, the O-(√3 × âˆš3)-R30° and the (2√3 × 2√3)-R30° structure are only observed when the graphene layer is on top. Phase coexistence and formation conditions of the intercalation structures between graphene and Ir(111) are analyzed. The experimental results are compared to density functional theory calculations including dispersive forces. The existence of these phases under graphene and their absence on bare Ir(111) are discussed in terms of possible changes in the adsorbate-substrate interaction due to the presence of the graphene cover.

The mechanism of caesium intercalation of graphene.

Properties of many layered materials, including copper- and iron-based superconductors, topological insulators, graphite and epitaxial graphene, can be manipulated by the inclusion of different atomic and molecular species between the layers via a process known as intercalation. For example, intercalation in graphite can lead to superconductivity and is crucial in the working cycle of modern batteries and supercapacitors. Intercalation involves complex diffusion processes along and across the layers; however, the microscopic mechanisms and dynamics of these processes are not well understood. Here we report on a novel mechanism for intercalation and entrapment of alkali atoms under epitaxial graphene. We find that the intercalation is adjusted by the van der Waals interaction, with the dynamics governed by defects anchored to graphene wrinkles. Our findings are relevant for the future design and application of graphene-based nano-structures. Similar mechanisms can also have a role for intercalation of layered materials.

Atomic structure and crystalline order of graphene-supported ir nanoparticle lattices.

We present the atomic structure of Ir nanoparticles with 1.5 nm diameter at half height and three layers average height grown on graphene/Ir(111). Using surface x-ray diffraction, we demonstrate that Ir nanoparticles on graphene/Ir(111) form a crystallographic superlattice with high perfection. The superlattice arrangement allows us to obtain detailed information on the atomic structure of the nanoparticles themselves, such as size, shape, internal layer stacking and strain. Our experiments disclose that the nanoparticles reside epitaxially on top of the graphene moiré structure on Ir(111), resulting in significant lateral compressive intraparticle strain. Normal incidence x-ray standing wave experiments deliver additional information on the particle formation induced restructuring of the graphene layer.

Wave-function mapping of graphene quantum dots with soft confinement.

Using low-temperature scanning tunneling spectroscopy, we map the local density of states of graphene quantum dots supported on Ir(111). Because of a band gap in the projected Ir band structure around the graphene K point, the electronic properties of the QDs are dominantly graphenelike. Indeed, we compare the results favorably with tight binding calculations on the honeycomb lattice based on parameters derived from density functional theory. We find that the interaction with the substrate near the edge of the island gradually opens a gap in the Dirac cone, which implies soft-wall confinement. Interestingly, this confinement results in highly symmetric wave functions. Further influences of the substrate are given by the known moiré potential and a 10% penetration of an Ir surface resonance into the graphene layer.

Dirac cones and minigaps for graphene on Ir(111).

Epitaxial graphene on Ir(111) prepared in excellent structural quality is investigated by angle-resolved photoelectron spectroscopy. It clearly displays a Dirac cone with the Dirac point shifted only slightly above the Fermi level. The moiré resulting from the overlaid graphene and Ir(111) surface lattices imposes a superperiodic potential giving rise to Dirac cone replicas and the opening of minigaps in the band structure.

Step edge diffusion and step atom detachment in surface evolution: ion erosion of Pt(111).

The temperature dependent morphological evolution of Pt(111) under 1 keV Xe+ normal incidence ion bombardment has been investigated up to 600 monolayers removed. Coarsening of the surface structures during erosion and a qualitative change in roughness evolution between 650 and 700 K are found to be caused by different atomic processes: the former by diffusion of atoms along steps, the latter by the onset of step atom detachment.

Atomic layer growth on Al(111) by ion bombardment

Instead of the expected erosion morphology composed of craters, rare gas ion bombardment of the Al(111) surface is found to cause initial surface growth of several atomic layers. This phenomenon is observed for Ne+, Ar+, and Xe+ at all temperatures at which bombardment induces morphological surface changes and for ion energies down to a few hundred eV. The effect is interpreted on the basis of a thermal spike induced separation of damage into subsurface vacancy clusters and surface adatom clusters.