www.chemie.fu-berlin.de/velena/research/graphene.

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Theoretical study of graphene functionalization: DFT- and wavefunction-based approaches

(in cooperation with Yu. S. Dedkov and K. Horn)

Graphene is a single layer of carbon atoms arranged on a honeycomb structure with two crystallographically equivalent atoms in its primitive unit cell (for the recent review of experimental and theoretical achievements in this eld see Refs. [1, 2]). The sp2 hybridization between one s orbital and two p orbitals leads to a trigonal planar structure with a formation of a bond between carbon atoms that are separated by 1.42 A. These bands have a lled shell and, hence, form a deep valence band. The unaffected p orbital, which is perpendicular to the planar structure, can bind covalently with neighboring carbon atoms, leading to the formation of a band. Since each p orbital has one extra electron, the band is half lled. The and bands touch in a single point at the Fermi energy (EF ) at the corner of the Brillouin zone, and close to this so-called Dirac point the bands display a linear dispersion and form perfect Dirac cones.Thus, undoped graphene is a semimetal (zero-gap semiconductor). The linear dispersion of the bands results in quasiparticles with zero mass, so-called Dirac fermions. Single sheets of graphene turn out to have a very high electron mobility that manifests itself in a variety of spectacular transport phenomena such as a minimum conductivity, anomalous quantum Hall effect (QHE), bipolar supercurrent, and room-temperature QHE. Being the consequence of the relativistic nature of Dirac fermions, these unusual properties render graphene a promising candidate for applications based on ballistic transport like the eld effect transistor and in future spintronics applications.

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Theoretically graphene is often treated as a free-standing two-dimensional sheet. Although sometimes this appears to be a reasonable model for describing observed properties, in many experimental situations there is deviation from this ideal behavior because of physical contact with the environment. While EF of free-standing graphene coincides with the conical points, adsorption on substrates or interaction with different molecules can alter its electronic properties signicantly. One of the nowadays used ways to prepare substrate-supported graphene is its synthesis on metallic substrates. The variable interaction strength depending on the support is an interesting feature of the graphene on metal systems. Metals, for which experimental data are available, seem to belong to two completely separate classes: the rst one in which graphene is chemisorbed and the second one in which it is physisorbed [3]. Of course, the strength of the binding affects the electronic structure of the system. In physisorbed graphene the conical points in the graphene band structure are preserved but small charge transfer to or from the metal substrate shifts the Fermi level. Its shift upward (downward) with respect to the conical point means that electrons (holes) are donated by the metal to graphene, making the latter n-type (p-type) doped. In the case of chemisorption, the strong graphene-metal bonding interaction destroys the conical points leading to more complicated picture. Recently, in cooperation with experimental group (Prof. K. Horn, FHI Berlin) investigations of the lattice-matched interface between graphene and ferromagnetic Ni(111) surface were performed by means of angle-resolved photoemission, x-ray magnetic circular dichroism (XMCD), and density functional theory (DFT) [4]. We observed noticeable modications of the graphene and nickel band structure as compared with clean Ni(111) slab and graphene ones. XMCD as well as DFT reveals an induced magnetic moment of the carbon atoms in the graphene layer aligned parallel to the Ni 3d magnetization. Now our joint experimental-theoretical work is directed towards study of small molecules adsorption on the graphene layer epitaxially grown on ferromagnetic surfaces. Here, from the theoretical side, the combination of DFT and wave-function-based methods will be applied in order to obtain the detailed information for these systems.
[1] A. H. Castro Neto, F. Guinea, N. M. R. Peres, K. S. Novoselov and A. K. Geim, Rev. Mod. Phys., 81, 109 (2009). [2] A. K. Geim, Science, 324, 1530 (2009). [3] J. Wintterlin, M.-L. Bocquet, Surf. Sci. 603, 1841 (2009). [4] M. Weser, Y. Rehder, K. Horn, M. Sicot, M. Fonin, A. B. Preobrajenski, E. N. Voloshina, E. Goering, and Yu. S. Dedkov, Appl. Phys. Lett. 96, 012504 (2010).