Electrostatic Interaction across a Single-Layer Carbon Shell.

Ions inside of fullerene molecules are model systems for the study of the electrostatic interaction across a single layer of carbon. For TbSc2N@C80 on h-BN/Ni(111), we observe with high-resolution X-ray photoelectron spectroscopy a splitting of the C 1s core level. The data may be explained quantitatively with density functional theory. The correlation of the C 1s eigenvalues and the Coulomb potential of the inside ions at the corresponding carbon sites indicates incomplete screening of the electric field due to the endohedral ions. The screening comprises anisotropic charge transfer to the carbon atoms and their polarization. This behavior is essential for the ordering of endohedral single-molecule magnets and is expected to occur in any single-layer material.

Fermi surface map of large-scale single-orientation graphene on SiO2.

Large scale tetraoctylammonium-assisted electrochemical transfer of graphene grown on single-crystalline Ir(1 1 1) films by chemical vapour deposition is reported. The transferred samples are characterized in air with optical microscopy, Raman spectroscopy and four point transport measurements, providing the sheet resistance and the Hall carrier concentration. In vacuum we apply low energy electron diffraction and photoelectron spectroscopy that indicate transferred large-scale single orientation graphene. Angular resolved photoemission reveals a Fermi surface and a Dirac point energy which are consistent with charge neutral graphene.

Cluster-size dependent internal dynamics and magnetic anisotropy of Ho ions in HoM2N@C80 and Ho2MN@C80 families (M = Sc, Lu, Y).

The paramagnetic NMR study of HoM2N@C80-Ih and Ho2MN@C80-Ih nitride cluster fullerenes (M = Sc, Lu, Y) reveals strong dependence of Ho-induced paramagnetic shifts (δ(para)) in (13)C NMR spectra on the size of the diamagnetic metal in the cluster. In particular, the δ(para) value in HoY2N@C80 is almost doubled in comparison to that in HoSc2N@C80. X-ray magnetic circular dichroism studies show that all Ho-nitride cluster fullerenes have the same magnetic ground state of Ho(3+). Point-charge ligand-field splitting calculations show that the increase of the M(3+) radius in going from Sc to Y results in a considerable increase of the energy splitting between different Jz states. This leads to a 19% higher magnetic anisotropy of Ho(3+) in HoY2N@C80 than in HoSc2N@C80 at 300 K. Variations of the molecular geometry and cluster dynamics with the size of the cluster are found to have even greater influence on δ(para) values. This work shows that the magnetic properties of the species confined inside the fullerene cages can be tuned using the geometrical factors such as the cluster and the cage size.

High quality single atomic layer deposition of hexagonal boron nitride on single crystalline Rh(111) four-inch wafers.

The setup of an apparatus for chemical vapor deposition (CVD) of hexagonal boron nitride (h-BN) and its characterization on four-inch wafers in ultra high vacuum (UHV) environment is reported. It provides well-controlled preparation conditions, such as oxygen and argon plasma assisted cleaning and high temperature annealing. In situ characterization of a wafer is accomplished with target current spectroscopy. A piezo motor driven x-y stage allows measurements with a step size of 1 nm on the complete wafer. To benchmark the system performance, we investigated the growth of single layer h-BN on epitaxial Rh(111) thin films. A thorough analysis of the wafer was performed after cutting in atmosphere by low energy electron diffraction, scanning tunneling microscopy, and ultraviolet and X-ray photoelectron spectroscopies. The apparatus is located in a clean room environment and delivers high quality single layers of h-BN and thus grants access to large area UHV processed surfaces, which had been hitherto restricted to expensive, small area single crystal substrates. The facility is versatile enough for customization to other UHV-CVD processes, e.g., graphene on four-inch wafers.

Note: An ion source for alkali metal implantation beneath graphene and hexagonal boron nitride monolayers on transition metals.

The construction of an alkali-metal ion source is presented. It allows the acceleration of rubidium ions to an energy that enables the penetration through monolayers of graphene and hexagonal boron nitride. Rb atoms are sublimated from an alkali-metal dispenser. The ionization is obtained by surface ionization and desorption from a hot high work function surface. The ion current is easily controlled by the temperature of ionizer. Scanning Tunneling Microscopy measurements confirm ion implantation.

Rare-earth surface alloying: a new phase for GdAu2.

Surface alloying is a powerful way of varying physical and chemical properties of metals, for a number of applications from catalysis to nuclear and green technologies. Surfaces offer many degrees of freedom, giving rise to new phases that do not have a bulk counterpart. However, the atomic characterization of distinct surface compounds is a major task, which demands powerful experimental and theoretical tools. Here we illustrate the process for the case of a GdAu2 surface phase of extraordinary crystallinity. The combined use of surface-sensitive techniques and state-of-the-art ab initio calculations disentangles its atomic and electronic properties. In particular, the stacking of the surface layers allows for gadolinium's natural ferromagnetic state, at variance with the bulk phase, where frustration leads to antiferromagnetic interlayer coupling.

Structure determination of the coincidence phase of graphene on Ru(0001).

The structure of the commensurate (23x23) phase of graphene on Ru(0001) has been analyzed by quantitative low-energy electron diffraction (LEED)-I(V) analysis and density-functional theory calculations. The I(V) analysis uses Fourier components as fitting parameters to determine the vertical corrugation and the lateral relaxation of graphene and the top Ru layers. Graphene is shown to be strongly corrugated by 1.5 A with a minimum C-Ru distance of 2.1 A. Additionally, lateral displacements of C atoms and a significant buckling in the underlying Ru layers are observed, indicative for strong local C-Ru interactions.

Graphene based quantum dots.

Laterally localized electronic states are identified on a single layer of graphene on ruthenium by low temperature scanning tunneling spectroscopy (STS). The individual states are separated by 3 nm and comprise regions of about 90 carbon atoms. This constitutes a highly regular quantum dot-array with molecular precision. It is evidenced by quantum well resonances (QWRs) with energies that relate to the corrugation of the graphene layer. The dI/dV conductance spectra are modeled by a layer height dependent potential-well with a delta-function potential that describes the barrier for electron penetration into graphene. The resulting QWRs are strongest and lowest in energy on the isolated 'hill' regions with a diameter of 2 nm, where the graphene is decoupled from the surface.

Advanced photoelectric effect experiment beamline at Elettra: A surface science laboratory coupled with Synchrotron Radiation.

We report the main characteristics of the advanced photoelectric effect experiments beamline, operational at Elettra storage ring, featuring a fully independent double branch scheme obtained by the use of chicane undulators and able to keep polarization control in both linear and circular mode. The paper describes the novel technical solutions adopted, namely, (a) the design of a quasiperiodic undulator resulting in optimized suppression of higher harmonics over a large photon energy range (10-100 eV), (b) the thermal stability of optics under high heat load via cryocoolers, and (c) the end station interconnected setup allowing full access to off-beam and on-beam facilities and, at the same time, the integration of users' specialized sample growth chambers or modules.

Graphene on Ru(0001): a 25 x 25 supercell.

The structure of a single layer of graphene on Ru(0001) has been studied using surface x-ray diffraction. A surprising superstructure containing 1250 carbon atoms has been determined, whereby 25 x 25 graphene unit cells lie on 23 x 23 unit cells of Ru. Each supercell contains 2 x 2 crystallographically inequivalent subcells caused by corrugation. Strong intensity oscillations in the superstructure rods demonstrate that the Ru substrate is also significantly corrugated down to several monolayers and that the bonding between graphene and Ru is strong and cannot be caused by van der Waals bonds. Charge transfer from the Ru substrate to the graphene expands and weakens the C-C bonds, which helps accommodate the in-plane tensile stress. The elucidation of this superstructure provides important information in the potential application of graphene as a template for nanocluster arrays.

Probing enantioselectivity with x-ray photoelectron spectroscopy and density functional theory.

The enantioselectivity of gold is investigated by x-ray photoelectron spectroscopy (XPS) and density functional theory (DFT). Cysteine molecules on a chiral Au(17 11 9);{S} surface show enantiospecific core level binding energies in the amino and in the thiol group. The sign and order of magnitude of the XPS core level shifts is reproduced by DFT. Identical preparations of D- and L-cysteine layers lead to D-cysteine molecules in the pure NH2 form, while a small portion of L-cysteine molecules maintains a hydrogen rich amino group (NH3). This implies enantiospecific adsorption reaction pathways and is consistent with DFT that indicates an activated hydrogen abstraction reaction from the amino group, which is downhill for D-cysteine.

Chiral recognition of organic molecules by atomic kinks on surfaces.

Two distinct non-mirror-symmetric conformations of D- and L-cysteine were found after adsorption on Au(17 11 9)S. This demonstrates chiral heterorecognition, i.e., enantioselectivity of S kinks on vicinal Au(111). The structures as determined by angle scanned x-ray photoelectron diffraction agree well with those from density functional theory calculations. The calculations predict adsorption energies of approximately 2 eV where D-cysteine binds 140 meV stronger than L-cysteine. The classical three point contact model for molecular recognition fails to explain these findings.

Electron coherence in a melting lead monolayer.

We used angle-resolved photoemission spectroscopy to measure the electronic dispersion and single-particle spectral function in a liquid metal. A lead monolayer supported on a copper (111) surface was investigated as the temperature was raised through the melting transition of the film. Electron spectra and momentum distribution maps of the liquid film revealed three key features of the electronic structure of liquids: the persistence of a Fermi surface, the filling of band gaps, and the localization of the wave functions upon melting. Distinct coherence lengths for different sheets of the Fermi surface were found, indicating a strong dependence of the localization lengths on the character of the constituent atomic wave functions.

Localization of surface states in disordered step lattices.

The character of the surface state wave function on regularly stepped Cu(111) is reinvestigated. It is shown that the qualitative change at terrace lengths around 17 A observed previously by Ortega et al. [Phys. Rev. Lett. 84, 6110 (2000)]] must necessarily be described as a change from a propagating superlattice state to a terrace-confined quasi-one-dimensional state. This reconciles previous, apparently contradictory experimental results and sheds new light on the behavior of nearly free electrons in nanostructures. Possible mechanisms driving the localization are discussed on the basis of the surface state bulk penetration depth, which has been measured in both regimes.

Step-lattice-induced band-gap opening at the fermi level.

The interaction of the Shockley surface state with the step lattice of vicinal Cu(111) leads to the formation of an electronic superlattice state. On Cu(443), where the average terrace length forms a "shape resonance" with the Fermi wavelength, we find a step-lattice-induced band-gap opening at the Fermi level. A gap magnitude >200 meV is inferred from high resolution photoemission experiments and line shape analysis. The corresponding energy gain with respect to a gapless case is approximately 11 meV/unit cell, and is a substantial contribution to the stabilization of the step lattice.

Optical recognition of atomic steps on surfaces.

Visible and UV light spectra display striking differences in optical reflectivity for the two types of monatomic steps on copper (111) surfaces. Electronic structure calculations trace these differences to the specific contributions of p(axially) and p(radially) local densities of states, parallel and perpendicular to the steps, of the distinctly coordinated corner atoms. The local origin of the spectral reflectance anisotropy is further corroborated by experiments on Cu(111) surfaces with varying step densities. Site specificity of the electronic structure of atoms in low coordinated sites on Cu(111) vicinals is thus revealed by reflectance anisotropy spectroscopy which can thereby detect step atom densities down to 10(13) atoms/cm(2).

Quenching of majority-channel quasiparticle excitations in cobalt.

The low-energy electronic excitations in cobalt are studied by a theoretical method that includes many-body effects and a realistic description of the band structure. Angle-resolved photoemission spectra measured on a thick film of hexagonal close-packed Co on Cu(111) agree well with calculated spectral functions. Because of many-body effects no sharp quasiparticle peaks exist for binding energies larger than 2 eV and in this energy region the spectrum is essentially incoherent. The many-body corrections are much stronger in the majority-spin channel and drastically affect the spin polarization of the spectra.

Tailoring confining barriers for surface states by step decoration: CO /vicinal Cu(111).

The influence of CO adsorption on the Shockley type surface state on vicinal Cu(111) surfaces is investigated using angle resolved photoemission. As the steps are decorated with CO the surface state shifts to higher binding energies, which is opposite to the known behavior on flat Cu(111). This is described within a one-dimensional potential model in which clean steps represent repulsive barriers and decorated steps become attractive wells. From the coverage dependence the integrated CO well potential can be quantified. It is U(CO)a = -2.9 eV A on both Cu(332) and Cu(221) surfaces. Density functional calculations reveal that this attractive potential is due to the very local charge transfer from the Cu step atom to the adsorbed molecule.

Atomically resolved images from near node photoelectron holography experiments on Al(111).

Szöke's concept for electron holography is hampered by forward scattering that dominates electron diffraction from electron point sources below the surface top layer. Forward scattering was proposed to be suppressed if the anisotropic nature of the electron source wave is exploited [T. Greber and J. Osterwalder, Chem. Phys. Lett. 256, 653 (1996)]. Experiments show a strong suppression of forward scattering in Al(111) if Al 2s photoelectrons (E(kin) = 952 eV) are measured near the nodal plane of the outgoing p wave. The holographic reconstruction from such diffraction data provides three dimensional images of atomic sites in unit cells with a size of more than 10 A.