D. Marchenko

Tunable Band Gap in Hydrogenated Quasi-Free-Standing Graphene

We show by angle-resolved photoemission spectroscopy that a tunable gap in quasi-free-standing monolayer graphene on Au can be induced by hydrogenation. The size of the gap can be controlled via hydrogen loading and reaches approximately 1.0 eV for a hydrogen coverage of 8%. The local rehybridization from sp(2) to sp(3) in the chemical bonding is observed by X-ray photoelectron spectroscopy and X-ray absorption and allows for a determination of the amount of chemisorbed hydrogen. The hydrogen induced gap formation is completely reversible by annealing without damaging the graphene. Calculations of the hydrogen loading dependent core level binding energies and the spectral function of graphene are in excellent agreement with photoemission experiments. Hydrogenation of graphene gives access to tunable electronic and optical properties and thereby provides a model system to study hydrogen storage in carbon materials.

Giant Rashba splitting in graphene due to hybridization with gold

Graphene in spintronics is predominantly considered for spin current leads of high performance due to weak intrinsic spin-orbit coupling of the graphene π electrons. Externally induced large spin-orbit coupling opens the possibility of using graphene in active elements of spintronic devices such as the Das-Datta spin field-effect transistor. Here we show that Au intercalation at the graphene-Ni interface creates a giant spin-orbit splitting (~100 meV) of the graphene Dirac cone up to the Fermi energy. Photoelectron spectroscopy reveals the hybridization with Au 5d states as the source for this giant splitting. An ab initio model of the system shows a Rashba-split spectrum around the Dirac point of graphene. A sharp graphene-Au interface at the equilibrium distance accounts for only ~10 meV spin-orbit splitting and enhancement is due to the Au atoms in the hollow position that get closer to graphene and do not break the sublattice symmetry.Graphene in spintronics [1] has so far primarily meant spin current leads of high performance because the intrinsic spin-orbit coupling of its π electrons is very weak [2–4]. If a large spin-orbit coupling could be created by a proximity effect, the material could also form active elements of a spintronic device such as the Das-Datta spin field-effect transistor [5], however, metal interfaces often compromise the band dispersion of massless Dirac fermions [6]. Our measurements show that Au intercalation at the graphene-Ni interface creates a giant spin-orbit splitting (∼ 100 meV) in the graphene Dirac cone up to the Fermi energy. Photoelectron spectroscopy reveals hybridization with Au5d states as the source for the giant spin-orbit splitting. An ab initio model of the system shows a Rashba-split dispersion with the analytically predicted gapless band topology around the Dirac point of graphene and indicates that a sharp graphene-Au interface at equilibrium distance will account for only ∼ 10 meV spin-orbit splitting. The ab initio calculations suggest an enhancement due to Au atoms that get closer to the graphene and do not violate the sublattice symmetry.

Dirac cone protected by non-symmorphic symmetry and three-dimensional Dirac line node in ZrSiS

Materials harbouring exotic quasiparticles, such as massless Dirac and Weyl fermions, have garnered much attention from physics and material science communities due to their exceptional physical properties such as ultra-high mobility and extremely large magnetoresistances. Here, we show that the highly stable, non-toxic and earth-abundant material, ZrSiS, has an electronic band structure that hosts several Dirac cones that form a Fermi surface with a diamond-shaped line of Dirac nodes. We also show that the square Si lattice in ZrSiS is an excellent template for realizing new types of two-dimensional Dirac cones recently predicted by Young and Kane. Finally, we find that the energy range of the linearly dispersed bands is as high as 2 eV above and below the Fermi level; much larger than of other known Dirac materials. This makes ZrSiS a very promising candidate to study Dirac electrons, as well as the properties of lines of Dirac nodes.

Hydrogenation, purification, and unzipping of carbon nanotubes by reaction with molecular hydrogen: road to graphane nanoribbons.

Reaction of single-walled carbon nanotubes (SWNTs) with hydrogen gas was studied in a temperature interval of 400-550 °C and at hydrogen pressure of 50 bar. Hydrogenation of nanotubes was observed for samples treated at 400-450 °C with about 1/3 of carbon atoms forming covalent C-H bonds, whereas hydrogen treatment at higher temperatures (550 °C) occurs as an etching. Unzipping of some SWNTs into graphene nanoribbons is observed as a result of hydrogenation at 400-550 °C. Annealing in hydrogen gas at elevated conditions for prolonged periods of time (72 h) is demonstrated to result also in nanotube opening, purification of nanotubes from amorphous carbon, and removal of carbon coatings from Fe catalyst particles, which allows their complete elimination by acid treatment.

Tolerance of topological surface states towards magnetic moments: Fe on Bi2Se3.

We study the effect of Fe impurities deposited on the surface of the topological insulator Bi(2)Se(3) by means of core-level and angle-resolved photoelectron spectroscopy. The topological surface state reveals surface electron doping when the Fe is deposited at room temperature and hole doping with increased linearity when deposited at low temperature (~8 K). We show that in both cases the surface state remains intact and gapless, in contradiction to current belief. Our results suggest that the surface state can very well exist at functional interfaces with ferromagnets in future devices.

Ir(111) surface state with giant Rashba splitting persists under graphene in air.

Spin currents which allow for a dissipationless transport of information can be generated by electric fields in semiconductor heterostructures in the presence of a Rashbatype spin-orbit coupling. The largest Rashba effects occur for electronic surface states of metals but these cannot exist but under ultrahigh vacuum conditions. Here, we reveal a giant Rashba effect (αR ≈ 1.5 · 10 −10 eVm) on a surface state of Ir(111). We demonstrate that its spin splitting and spin polarization remain unaffected when Ir is covered with graphene. The graphene protection is, in turn, sufficient for the spinsplit surface state to survive in ambient atmosphere. We discuss this result along with evidences for a topological protection of the surface state.

Negligible Surface Reactivity of Topological Insulators Bi2Se3 and Bi2Te3 towards Oxygen and Water

The long-term stability of functional properties of topological insulator materials is crucial for the operation of future topological insulator based devices. Water and oxygen have been reported to be the main sources of surface deterioration by chemical reactions. In the present work, we investigate the behavior of the topological surface states on Bi2X3 (X = Se, Te) by valence-band and core level photoemission in a wide range of water and oxygen pressures both in situ (from 10(-8) to 0.1 mbar) and ex situ (at 1 bar). We find that no chemical reactions occur in pure oxygen and in pure water. Water itself does not chemically react with both Bi2Se3 and Bi2Te3 surfaces and only leads to slight p-doping. In dry air, the oxidation of the Bi2Te3 surface occurs on the time scale of months, in the case of Bi2Se3 surface of cleaved crystal, not even on the time scale of years. The presence of water, however, promotes the oxidation in air, and we suggest the underlying reactions supported by density functional calculations. All in all, the surface reactivity is found to be negligible, which allows expanding the acceptable ranges of conditions for preparation, handling and operation of future Bi2X3-based devices.

Observation of quantum-tunnelling-modulated spin texture in ultrathin topological insulator Bi2Se3 films

Understanding the spin-texture behaviour of boundary modes in ultrathin topological insulator films is critically essential for the design and fabrication of functional nanodevices. Here, by using spin-resolved photoemission spectroscopy with p-polarized light in topological insulator Bi2Se3 thin films, we report tunnelling-dependent evolution of spin configuration in topological insulator thin films across the metal-to-insulator transition. We report a systematic binding energy- and wavevector-dependent spin polarization for the topological surface electrons in the ultrathin gapped-Dirac-cone limit. The polarization decreases significantly with enhanced tunnelling realized systematically in thin insulating films, whereas magnitude of the polarization saturates to the bulk limit faster at larger wavevectors in thicker metallic films. We present a theoretical model that captures this delicate relationship between quantum tunnelling and Fermi surface spin polarization. Our high-resolution spin-based spectroscopic results suggest that the polarization current can be tuned to zero in thin insulating films forming the basis for a future spin-switch nanodevice.

Giant Rashba‐Type Spin Splitting in Ferroelectric GeTe(111)

Photoelectron spectroscopy in combination with piezoforce microscopy reveals that the helicity of Rashba bands is coupled to the nonvolatile ferroelectric polarization of GeTe(111). A novel surface Rashba band is found and fingerprints of a bulk Rashba band are identified by comparison with density functional theory calculations.

Tunable Fermi level and hedgehog spin texture in gapped graphene

Spin and pseudospin in graphene are known to interact under enhanced spin–orbit interaction giving rise to an in-plane Rashba spin texture. Here we show that Au-intercalated graphene on Fe(110) displays a large (∼230 meV) bandgap with out-of-plane hedgehog-type spin reorientation around the gapped Dirac point. We identify two causes responsible. First, a giant Rashba effect (∼70 meV splitting) away from the Dirac point and, second, the breaking of the six-fold graphene symmetry at the interface. This is demonstrated by a strong one-dimensional anisotropy of the graphene dispersion imposed by the two-fold-symmetric (110) substrate. Surprisingly, the graphene Fermi level is systematically tuned by the Au concentration and can be moved into the bandgap. We conclude that the out-of-plane spin texture is not only of fundamental interest but can be tuned at the Fermi level as a model for electrical gating of spin in a spintronic device.