Understanding the growth mechanism of graphene on Ge/Si(001) surfaces.

The practical difficulties to use graphene in microelectronics and optoelectronics is that the available methods to grow graphene are not easily integrated in the mainstream technologies. A growth method that could overcome at least some of these problems is chemical vapour deposition (CVD) of graphene directly on semiconducting (Si or Ge) substrates. Here we report on the comparison of the CVD and molecular beam epitaxy (MBE) growth of graphene on the technologically relevant Ge(001)/Si(001) substrate from ethene (C2H4) precursor and describe the physical properties of the films as well as we discuss the surface reaction and diffusion processes that may be responsible for the observed behavior. Using nano angle resolved photoemission (nanoARPES) complemented by transport studies and Raman spectroscopy as well as density functional theory (DFT) calculations, we report the direct observation of massless Dirac particles in monolayer graphene, providing a comprehensive mapping of their low-hole doped Dirac electron bands. The micrometric graphene flakes are oriented along two predominant directions rotated by 30° with respect to each other. The growth mode is attributed to the mechanism when small graphene "molecules" nucleate on the Ge(001) surface and it is found that hydrogen plays a significant role in this process.

Structural and electronic properties of epitaxial multilayer h-BN on Ni(111) for spintronics applications.

Hexagonal boron nitride (h-BN) is a promising material for implementation in spintronics due to a large band gap, low spin-orbit coupling, and a small lattice mismatch to graphene and to close-packed surfaces of fcc-Ni(111) and hcp-Co(0001). Epitaxial deposition of h-BN on ferromagnetic metals is aimed at small interface scattering of charge and spin carriers. We report on the controlled growth of h-BN/Ni(111) by means of molecular beam epitaxy (MBE). Structural and electronic properties of this system are investigated using cross-section transmission electron microscopy (TEM) and electron spectroscopies which confirm good agreement with the properties of bulk h-BN. The latter are also corroborated by density functional theory (DFT) calculations, revealing that the first h-BN layer at the interface to Ni is metallic. Our investigations demonstrate that MBE is a promising, versatile alternative to both the exfoliation approach and chemical vapour deposition of h-BN.

Understanding the origin of band gap formation in graphene on metals: graphene on Cu/Ir(111).

Understanding the nature of the interaction at the graphene/metal interfaces is the basis for graphene-based electron- and spin-transport devices. Here we investigate the hybridization between graphene- and metal-derived electronic states by studying the changes induced through intercalation of a pseudomorphic monolayer of Cu in between graphene and Ir(111), using scanning tunnelling microscopy and photoelectron spectroscopy in combination with density functional theory calculations. We observe the modifications in the band structure by the intercalation process and its concomitant changes in the charge distribution at the interface. Through a state-selective analysis of band hybridization, we are able to determine their contributions to the valence band of graphene giving rise to the gap opening. Our methodology reveals the mechanisms that are responsible for the modification of the electronic structure of graphene at the Dirac point, and permits to predict the electronic structure of other graphene-metal interfaces.

Specific many-electron effects in X-ray spectra of simple metals and graphene.

In this work the influence of many-electron effects on the shape of characteristic X-ray emission bands of the simple metals Mg and Al is examined by means of ab initio calculations and semi-empirical models. These approaches are also used for the analysis of C K-emission and absorption spectra of graphene. Both the dynamical screening of the core vacancy and the Auger-effect in the valence band (VB) have been taken into account. Dynamical screening of the core vacancy by valence electrons (the so-called MND effect) is considered ab initio in the framework of density functional theory. The Auger effect in the VB was taken into account within a semi-empirical method, approximating the quadratic dependence of the VB hole level width on the difference between the level energy and the Fermi energy. All theoretical spectra are in very good agreement with available experimental data.

Electronic structure and imaging contrast of graphene moiré on metals.

Realization of graphene moiré superstructures on the surface of 4d and 5d transition metals offers templates with periodically modulated electron density, which is responsible for a number of fascinating effects, including the formation of quantum dots and the site selective adsorption of organic molecules or metal clusters on graphene. Here, applying the combination of scanning probe microscopy/spectroscopy and the density functional theory calculations, we gain a profound insight into the electronic and topographic contributions to the imaging contrast of the epitaxial graphene/Ir(111) system. We show directly that in STM imaging the electronic contribution is prevailing compared to the topographic one. In the force microscopy and spectroscopy experiments we observe a variation of the interaction strength between the tip and high-symmetry places within the graphene moiré supercell, which determine the adsorption sites for molecules or metal clusters on graphene/Ir(111).

Electronic structure and magnetic properties of the graphene/Fe/Ni111 intercalation-like system.

The electronic structure and magnetic properties of the graphene/Fe/Ni(111) system were investigated via combination of the density functional theory calculations and electron-spectroscopy methods. This system was prepared via intercalation of thin Fe layers (1 ML) underneath graphene on Ni(111) and its inert properties were verified by means of photoelectron spectroscopy. Intercalation of iron in the space between graphene and Ni(111) changes drastically the magnetic response from the graphene layer that is explained by the formation of the highly spin-polarized 3d(z(2)) quantum-well state in the thin iron layer.

Charge transport in proteins probed by resonant photoemission.

The degrees of charge localization in the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) of the bacterial surface layer protein of Bacillus sphaericus NCTC 9602 were studied by resonant photoemission. In agreement with a charge transport hopping mechanism that involves torsional motions of the peptide backbone, the lifetime of electrons excited into the LUMO was found to be approximately 100 fs.

Method of measurements with random perturbation: application in photoemission experiments.

We report on an application of a simultaneous perturbation stochastic approximation (SPSA) algorithm to filtering systematic noise (SN) with nonzero mean value in photoemission data. In our analysis, we have used a series of 50 single-scan photoemission spectra of W(110) surface where different SNs were added. It was found that the SPSA-evaluated spectrum is in good agreement with the spectrum measured without SN. On the basis of our results, a wide application of SPSA algorithm for evaluation of experimental data is anticipated.

Rashba effect in the graphene/ni(111) system.

We report on angle-resolved photoemission studies of the electronic pi states of high-quality epitaxial graphene layers on a Ni(111) surface. In this system the electron binding energy of the pi states shows a strong dependence on the magnetization reversal of the Ni film. The observed extraordinarily large energy shift up to 225 meV of the graphene-derived pi band peak position for opposite magnetization directions is attributed to a manifestation of the Rashba interaction between spin-polarized electrons in the pi band and the large effective electric field at the graphene/Ni interface. Our findings show that an electron spin in the graphene layer can be manipulated in a controlled way and have important implications for graphene-based spintronic devices.

YCo2: intrinsic magnetic surface of a paramagnetic bulk material.

Here we report on results of a spin-resolved photoelectron spectroscopic (SRPES) study of YCo2 thin films (150 A-thick) grown on a W(110) substrate. The films were prepared by co-deposition of stoichiometric amounts of Y and Co onto a clean W surface followed by thermal annealing leading to (2x2) overstructure with respect to W(110) in the low-energy electron diffraction pattern indicated formation of a structurally ordered YCo2(111) surface. While no clear spin asymmetry was observed for bulk-sensitive SRPES data taken at hnu=1253.6 eV, the more surface-sensitive SRPES data obtained at hnu=21.2 eV photon energy revealed a clear spin-asymmetry probing the validity of the recent theoretical prediction.

Magnetite: a search for the half-metallic state.

We present a detailed study of the spin-dependent electronic structure of thin epitaxial magnetite films of different crystallographic orientations. Using spin- and angle-resolved photoelectron spectroscopy at room temperature, we determine for epitaxial Fe(3)O(4)(111) films a maximum spin polarization value of -(80 ± 5)% near E(F). The spin-resolved photoelectron spectra for binding energies between 1.5 eV and E(F) show good agreement with the spin-split band structure from density functional theory (DFT) calculations which predict an overall energy gap in the spin-up electron bands in high symmetry directions, thus providing evidence for the half-metallic ferromagnetic state of Fe(3)O(4) in the [111] direction. In the case of the Fe(3)O(4)(100) surface, both the spin-resolved photoelectron spectroscopy experiments and the DFT density of states give evidence for a half-metal to metal transition: the measured spin polarization of about -(55 ± 10)% at E(F) and the theoretical value of -40% are significantly lower than the -100% predicted by local spin density approximation (LSDA) calculations for the bulk magnetite crystal as well as the -(80 ± 5)% obtained for the Fe(3)O(4)(111) films. The experimental findings were corroborated by DFT calculations as due to a surface reconstruction leading to the electronic states in the majority-spin band gap and thus to the reduced spin polarization.

Wave-vector conservation upon hybridization of 4f and valence-band states observed in photoemission spectra of a Ce monolayer on W(110).

Angle-resolved resonant photoemission data for a hexagonally ordered monolayer of Ce on W(110) are presented. The spectra reveal a splitting of the 4f(0) ionization peak around a point in k space where a degeneracy with a valence-band state is expected. The phenomenon is described within a simple approach to the periodic Anderson model. It is found that the Ce 4f state forms a band and hybridization predominantly occurs between the 4f and the valence-band states at the same wave vector.