Yuriy S. Dedkov

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.

Electronic and magnetic properties of the graphene–ferromagnet interface

This paper presents our work on the investigation of the surface structure and the electronic and magnetic properties of the graphene layer on the lattice-matched surface of a ferromagnetic material, Ni(111). Scanning tunneling microscopy imaging shows that perfectly ordered epitaxial graphene layers can be prepared by elevated temperature decomposition of hydrocarbons, with domains larger than the terraces of the underlying Ni(111). In some exceptional cases, graphene films do not show rotational alignment with the metal surface, leading to moire structures with small periodicities. We discuss the crystallographic structure of graphene with respect to the Ni(111) surface relying both on experimental results and on recent theoretical studies. X-ray absorption spectroscopy investigations of empty valence-band states demonstrate the existence of interface states, which originate from the strong hybridization between the graphene π and Ni 3d valence-band states with the partial charge transfer of the spin-polarized electrons to the graphene π* unoccupied states. The latter leads to the appearance of an induced magnetic moment of carbon atoms in the graphene layer, which is unambiguously confirmed by both x-ray magnetic circular dichroism and spin-resolved photoemission. Further angle-resolved photoemission investigations indicate a strong interaction between graphene and Ni(111), showing considerable modification of the valence-band states of Ni and graphene due to strong hybridization. A detailed analysis of the Fermi surface of the graphene/Ni(111) system shows very good agreement between experimental and calculated two-dimensional maps of the electronic states around the Fermi level, supporting the idea of spin-filtering. We analyze our spectroscopic results relying on the currently available band structure calculations for the graphene/Ni(111) system and discuss the perspectives of the realization of graphene/ferromagnet-based devices.

Induced magnetism of carbon atoms at the graphene/Ni(111) interface

We report an element-specific investigation of electronic and magnetic properties of the graphene/Ni(111) system. Using x-ray magnetic circular dichroism, the occurrence of an induced magnetism of the carbon atoms in the graphene layer is observed. We attribute this magnetic moment to the strong hybridization between C π and Ni 3d valence band states. The net magnetic moment of carbon in the graphene layer is estimated to be in the range of 0.05–0.1 μB per atom.

Graphene-protected iron layer on Ni(111)

Here we report a photoemission study of the Fe intercalation underneath a graphene layer on Ni(111). The process of intercalation was monitored by means of x-ray photoemission of corresponding core levels as well as ultraviolet photoemission of the graphene-derived π states in the valence band. Thin fcc Fe layers (2–5 ML thickness) at the interface between a graphene capping layer and Ni(111) form epitaxial films passivated from the reactive environment.

Nucleation and growth of nickel nanoclusters on graphene Moiré on Rh(111)

Regularly sized Ni nanoclusters (NCs) have been grown on a graphene Moire on Rh(111). Using scanning tunneling microscopy, we determine that initial growth of Ni at 150 K leads to preferential nucleation of monodispersed NCs at specific sites of the Moire superstructure. However, a defined long-range ordering of NCs with increasing coverage is not observed. Room temperature Ni deposition leads to the formation of flat triangular-shaped islands which are well-matched to the Moire registry.

Structural and electronic properties of the graphene/Al/Ni(111) intercalation system

Decoupling of the graphene layer from the ferromagnetic substrate via intercalation of sp metal has recently been proposed as an effective way to realize a single-layer graphene-based spin-filter. Here, the structural and electronic properties of the prototype system, graphene/Al/Ni(111), are investigated via a combination of electron diffraction and spectroscopic methods. These studies are accompanied by state-of-the-art electronic structure calculations. The properties of this prospective Al-intercalation-like system and its possible implementations in future graphene-based devices are discussed.

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.

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).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 cites for molecules or metal clusters on graphene/Ir(111). ∗ Corresponding author. E-mail: Yuriy.Dedkov@specs.com 1 ar X iv :1 21 0. 16 02 v1 [ co nd -m at .m tr lsc i] 4 O ct 2 01 2 Graphene layers on metal surfaces have been attracting the attention of scientists since several decades, starting from middle of the 60s, when the catalytic properties of the closepacked surfaces of transition metals were in the focus of the surface science research [1–4]. The demonstration of the fascinating electronic properties of the free-standing graphene [5, 6], renewed the interest in the graphene/metal systems, which are considered as the main and the most perspective way for the large-scale preparation of high-quality graphene layers with controllable properties [7–10]. For this purpose single-crystalline as well as polycrystalline substrates of 3d− 5d metals can be used. One of the particularly exciting questions concerning the graphene/metal interface is the origin of the bonding mechanism in such systems [2–4, 11]. This graphene-metal puzzle is valid for both cases: graphene adsorption on metallic surfaces as well as for the opposite situation of the metal deposition on the free-standing or substrate-supported graphene. In the latter case the close-packed surfaces of 4d and 5d metals are often used as substrates [12, 13]. A graphene layer prepared on such surfaces, i. e. Ru(0001) [14–16], Rh(111) [13, 17, 18], Ir(111) [19, 20], or Pt(111) [21, 22], forms so-called moiré structures due to the relatively large lattice mismatch between graphene and metal substrates. As a consequence of the lattice mismatch the interaction strength between graphene and the metallic substrate is spatially modulated leading to the spatially periodic electronic structure. Such lateral graphene superlattices are known to exhibit selective absorption for organic molecules [23] or metal clusters [24]. Especially, the adsorption of different metals Ir, Ru, Au, or Pt on graphene/Ir(111) has been intensively studied showing a preferential nucleation around the so-called FCC or HCP high-symmetry positions within the moiré unit cell [12, 25]. In the subsequent works [25, 26] this site-selective adsorption was explained via local sp to sp rehybridization of carbon atoms with the bond formation between graphene and the cluster. However, a fully consistent description of the local electronic structure of graphene/Ir(111), the observed imaging contrast in scanning probe experiments and the bonding mechanism of molecules or clusters on it is still lacking, motivating the present research. Here we present the systematic studies of the graphene/Ir(111) system by means of density functional theory (DFT) calculations and scanning tunnelling and atomic force microscopy (STM and AFM) performed in constant current / constant frequency shift (CC / CFS) and constant height (CH) modes. The obtained results for the graphene/Ir(111) system allow to separate the topographic and electronic contributions in the imaging contrast in

Graphene on Rh(111): Scanning tunneling and atomic force microscopies studies

The electronic and crystallographic structure of the graphene/Rh(111) moire lattice is studied via combination of density-functional theory calculations and scanning tunneling and atomic force microscopy (STM and AFM). Whereas the principal contrast between hills and valleys observed in STM does not depend on the sign of applied bias voltage, the contrast in atomically resolved AFM images strongly depends on the frequency shift of the oscillating AFM tip. The obtained results demonstrate the perspectives of application atomic force microscopy/spectroscopy for the probing of the chemical contrast at the surface.

Graphene growth and properties on metal substrates

Graphene-metal interface as one of the interesting graphene-based objects attracts much attention from both application and fundamental science points of view. This paper gives a timely review of the recent experimental works on the growth and the electronic properties of the graphene-metal interfaces. This work makes a link between huge amount of experimental and theoretical data allowing one to understand the influence of the metallic substrate on the electronic properties of a graphene overlayer and how its properties can be modified in a controllable way. The further directions of studies and applications of the graphene-metal interfaces are discussed.