Marko Kralj

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.

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.

Al2O3-films on Ni3Al(111): a template for nanostructured cluster growth

In scanning tunnelling microscope images of thin Al2O3-films grown on Ni3Al(111) at 1000 K two super-lattices with periodicities of 2.6 and 4.5 nm, respectively, can be identified. These well-ordered nanostructures can be used as nucleation centres for metal particle growth. It can be shown that both nanostructures act as a template for the fabrication of ordered assemblies of metal clusters by mere physical vapour deposition. The degree of ordering of these nanostructures is largely dependent on the metal deposited. Here we report on the growth of Cu, Ag, Au, Mn, and V clusters on the Al2O3-films. The best results as far as ordering of the clusters is concerned was reached for V deposition at 550 K, which resulted in a nearly perfect hexagonal array of clusters with a spacing of 2.6 nm.

The Backside of Graphene: Manipulating Adsorption by Intercalation

The ease by which graphene is affected through contact with other materials is one of its unique features and defines an integral part of its potential for applications. Here, it will be demonstrated that intercalation, the insertion of atomic layers in between the backside of graphene and the supporting substrate, is an efficient tool to change its interaction with the environment on the frontside. By partial intercalation of graphene on Ir(111) with Eu or Cs we induce strongly n-doped graphene patches through the contact with these intercalants. They coexist with nonintercalated, slightly p-doped graphene patches. We employ these backside doping patterns to directly visualize doping induced binding energy differences of ionic adsorbates to graphene through low-temperature scanning tunneling microscopy. Density functional theory confirms these binding energy differences and shows that they are related to the graphene doping level.

Growth of copper and vanadium on a thin Al2O3-film on Ni3Al(111)

Abstract The growth of different metals on thin Al2O3-films on Ni3Al(111) was investigated using scanning tunneling microscopy (STM). These thin alumna films are well ordered showing two superstructures, which appear in the STM images at different bias voltages. These superstructures, with periodicities of 2.6 and 4.5 nm, respectively, are shown here to govern the nucleation of the deposited metals. Copper clusters grow on these nucleation centers only at room temperature. Higher temperatures lead to an increase of the cluster size and the loss of order. In turn, vanadium forms ordered cluster arrays at room and higher temperature. Due to the stronger metal–oxide interaction compared to copper vanadium forms smaller clusters at low and high coverages, which do not show any ripening after annealing. Based on these observations, Al2O3-films on Ni3Al(111) prove to be an interesting template for the fabrication of periodic cluster arrays.

Mapping image potential states on graphene quantum dots.

Free-electron-like image potential states are observed in scanning tunneling spectroscopy on graphene quantum dots on Ir(111) acting as potential wells. The spectrum strongly depends on the size of the nanostructure as well as on the spatial position on top, indicating lateral confinement. Analysis of the substructure of the first state by the spatial mapping of the constant energy local density of states reveals characteristic patterns of confined states. The most pronounced state is not the ground state, but an excited state with a favorable combination of the local density of states and parallel momentum transfer in the tunneling process. Chemical gating tunes the confining potential by changing the local work function. Our experimental determination of this work function allows us to deduce the associated shift of the Dirac point.

Trapping surface electrons on graphene layers and islands

(Received 9 September 2011; revised manuscript received 26 January 2012; published 13 February 2012)We report the use of time- and angle-resolved two-photon photoemission to map the bound, unoccupiedelectronic structure of the weakly coupled graphene/Ir(111) system. The energy, dispersion, and lifetime of thelowest three image-potential states are measured. In addition, the weak interaction between Ir and graphenepermits observation of resonant transitions from an unquenched Shockley-type surface state of the Ir substrateto graphene/Ir image-potential states. The image-potential-state lifetimes are comparable to those of midgapclean metal surfaces. Evidence of localization of the excited electrons on single-atom-layer graphene islands isprovided by coverage-dependent measurements.DOI: 10.1103/PhysRevB.85.081402 PACS number(s): 73

Europium underneath graphene on Ir(111): Intercalation mechanism, magnetism, and band structure

The intercalation of Eu underneath Gr on Ir(111) is comprehensively investigated by microscopic, magnetic, and spectroscopic measurements, as well as by density functional theory. Depending on the coverage, the intercalated Eu atoms form either a (2×2) or a (3×3)R30∘ superstructure with respect to Gr. We investigate the mechanisms of Eu penetration through a nominally closed Gr sheet and measure the electronic structures and magnetic properties of the two intercalation systems. Their electronic structures are rather similar. Compared to Gr on Ir(111), the Gr bands in both systems are essentially rigidly shifted to larger binding energies resulting in n doping. The hybridization of the Ir surface state S1 with Gr states is lifted, and the moire superperiodic potential is strongly reduced. In contrast, the magnetic behavior of the two intercalation systems differs substantially, as found by x-ray magnetic circular dichroism. The (2×2) Eu structure displays plain paramagnetic behavior, whereas for the (3×3)R30∘ structure the large zero-field susceptibility indicates ferromagnetic coupling, despite the absence of hysteresis at 10 K. For the latter structure, a considerable easy-plane magnetic anisotropy is observed and interpreted as shape anisotropy.

Oscillatory electron-phonon coupling in ultra-thin silver films on V(100)

The temperature dependence of peak widths in high-resolution angle-resolved photoelectron spectroscopy from quantum well states in ultra-thin Ag films on V(100) has been used to determine the electron-phonon coupling constant, λ, for films of thickness 1-8 layers. A strong oscillatory variation in coupling strength is observed as a function of film thickness, peaking at a two layer film for which λ1.0. A simple theory incorporating interaction of the photo-hole with the thermal vibrations of the potential step at the adlayer-vacuum interface is shown to reproduce the main features of these results.

Finding the bare band: Electron coupling to two phonon modes in potassium-doped graphene on Ir(111)

We analyze renormalization of the pi band of n-doped epitaxial graphene on Ir(111) induced by electron-phonon coupling. Our procedure of extracting the bare band relies on recursive self-consistent refining of the functional form of the bare-band until the convergence. We demonstrate that the components of the self-energy, as well as the spectral intensity obtained from angle-resolved photoelectron spectroscopy (ARPES) show that the renormalization is due to the coupling to two distinct phonon excitations. From the velocity renormalization and an increase of the imaginary part of the self-energy we find the electron-phonon coupling constant to be ~0.2, which is in fair agreement with a previous study of the same system, despite the notable difference in the width of spectroscopic curves. Our experimental results also suggest that potassium intercalated between graphene and Ir(111) does not introduce any additional increase of the quasiparticle scattering rate.