Adsorption of Water and Ammonia on Graphene: Evidence for Chemisorption from X-ray Absorption Spectra.

While the bonding of molecular adsorbates to graphene has so far been characterized as physisorption, our study of adsorbed ammonia and water using near-edge X-ray absorption spectroscopy provides unambiguous evidence for a chemical contribution to the adsorption bond. We use the situation, unique to graphene, to characterize the unoccupied valence band states of the partners in the bond on the basis of the complementary adsorbate and substrate X-ray absorption K edges. New adsorbate-induced features on the substrate (carbon) K edge are interpreted as hybrid states in terms of a simple model of chemical interaction.

In situ fabrication of quasi-free-standing epitaxial graphene nanoflakes on gold.

Addressing the multitude of electronic phenomena theoretically predicted for confined graphene structures requires appropriate in situ fabrication procedures yielding graphene nanoflakes (GNFs) with well-defined geometries and accessible electronic properties. Here, we present a simple strategy to fabricate quasi-free-standing GNFs of variable sizes, performing temperature programmed growth of graphene flakes on the Ir(111) surface and subsequent intercalation of gold. Using scanning tunneling microscopy (STM), we show that epitaxial GNFs on a perfectly ordered Au(111) surface are formed while maintaining an unreconstructed, singly hydrogen-terminated edge structure, as confirmed by the accompanying density functional theory (DFT) calculations. Using tip-induced lateral displacement of GNFs, we demonstrate that GNFs on Au(111) are to a large extent decoupled from the Au(111) substrate. The direct accessibility of the electronic states of a single GNF is demonstrated upon analysis of the quasiparticle interference patterns obtained by low-temperature STM. These findings open up an interesting playground for diverse investigations of graphene nanostructures with possible implications for device fabrication.

Size-selected epitaxial nanoislands underneath graphene moiré on Rh(111).

We use in situ scanning tunneling microscopy (STM) to investigate intercalation of the ferromagnetic 3d metals Ni and Fe underneath a graphene monolayer on Rh(111). Upon thermal annealing of graphene/Rh(111) with the deposited metal on top, we observe the formation of epitaxial monatomic nanoislands grown pseudomorphically on Rh(111) and covered by graphene. The size and shape of intercalated nanoislands is strongly influenced by the local spatial variation of the graphene-Rh bonding strength. In particular, the side length of the intercalated nanoislands shows maxima around discrete values imposed by the periodicity of the graphene moiré. Intercalation can be performed efficiently and without any visible damage of the graphene overlayer in the studied temperature range between 670 and 870 K. We identify the main intercalation path to be via diffusion through pre-existing lattice defects in graphene, accompanied by the second mechanism which is based on the material diffusion via metal-generated defects followed by the defect healing of the graphene lattice. We deem these graphene-capped and sharply confined ferromagnetic nanoislands interesting in the fields of spintronics and nanomagnetism.

Ge(001) as a template for long-range assembly of π-stacked coronene rows.

The adsorption of coronene molecules (C(24)H(12)) on the Ge(001) surface has been studied by means of scanning tunnelling microscopy (STM). Upon room temperature deposition, the coronene molecules adsorb in an upright geometry forming compact layers patterned in rows for coverages of one monolayer and less, being the only example investigated so far in which a pure aromatic hydrocarbon forms a well-ordered monolayer on a non-passivated semiconductor surface. At half monolayer, the molecular rows consist of long chains of π-stacked molecules and the distance between molecular planes is 8 Å. This configuration is maintained upon cooling the system below the transition temperature of Ge(001) (~220 K), but the molecular layer experiences also a transition from rows perpendicular to rows parallel to the Ge dimer rows. We interpret our observations in terms of a weak bonging between molecules and substrate, which facilitates the formation of large ordered domains of molecules, revealing Ge(001) as an ideal template for the growth of this and other aromatic hydrocarbons.

Graphene on ferromagnetic surfaces and its functionalization with water and ammonia.

In this article, an angle-resolved photoelectron spectroscopy (ARPES), X-ray absorption spectroscopy (XAS), and density-functional theory (DFT) investigations of water and ammonia adsorption on graphene/Ni(111) are presented. The results of adsorption on graphene/Ni(111) obtained in this study reveal the existence of interface states, originating from the strong hybridization of the graphene π and spin-polarized Ni 3d valence band states. ARPES and XAS data of the H2O (NH3)/graphene/Ni(111) system give an information regarding the kind of interaction between the adsorbed molecules and the graphene on Ni(111). The presented experimental data are compared with the results obtained in the framework of the DFT approach.

Photoemission and near-edge X-ray absorption fine structure studies of the bacterial surface protein layer of Bacillus sphaericus NCTC 9602.

The electronic structure of the regular, two-dimensional bacterial surface protein layer of Bacillus sphaericus NCTC 9602 has been examined by photoemission (PE) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Both the O 1s and the N 1s core-level PE spectra show a single structure, whereas the C 1s core-level spectrum appears manifold, suggesting similar chemical states for each oxygen atom and also for each nitrogen atom, while carbon atoms exhibit a range of chemical environments in the different functional groups of the amino acids. This result is supported by the element-specific NEXAFS spectra of the unoccupied valence electronic states, which exhibit a series of characteristic NEXAFS peaks that can be assigned to particular molecular orbitals of the amino acids by applying a phenomenological building-block model. The relative contributions of the C-O, C-N, and C-C bond originating signals into the C 1s PE spectrum are in good agreement with the number ratios of the corresponding bonds calculated from the known primary structure of the bacterial surface protein. First interpretation of the PE spectrum of the occupied valence states is achieved on the basis of electronic density-of-states calculations performed for small peptides. It was found that mainly the pi clouds of the aromatic rings contribute to both the lowest unoccupied and the highest occupied molecular orbitals.

Electronic structure of regular bacterial surface layers.

We report photoemission and near-edge x-ray absorption fine structure measurements of the occupied and unoccupied valence electronic states of the regular surface layer of Bacillus sphaericus, which is widely used as the protein template for the fabrication of metallic nanostructures. The two-dimensional protein crystal shows a semiconductorlike behavior with a gap value of approximately 3.0 eV and the Fermi energy close to the bottom of the lowest unoccupied molecular orbital. We anticipate that these results will open up new possibilities for the electric addressability of biotemplated low-dimensional hybrid structures.