A. M. Shikin

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.

Synthesis of a weakly bonded graphite monolayer on Ni(111) by intercalation of silver

Silver has been successfully intercalated underneath a monolayer of graphite (MG) adsorbed on Ni(111) by deposition on the MG/Ni(111) surface at room temperature and subsequent annealing to 350-400 °C. The surface phonon dispersion of the MG/Ag/Ni(111) system has been measured in the direction of the Brillouin zone using high resolution electron energy loss spectroscopy. The dispersion curves were found to be almost identical to those of bulk graphite, which is in contrast to the softened graphite-like phonon modes observed for the MG/Ni(111) system. This suggests that the stiffening of the phonon modes induced by silver intercalation is caused by a weaker interaction of the states of graphite with the substrate. These results demonstrate that a weakly bonded graphite monolayer, whose chemical properties are very similar to those of bulk graphite and which is stable up to 400 °C, can be synthesized in situ on Ni(111) after intercalation of silver.

Formation of quasi-free graphene on the Ni(111) surface with intercalated Cu, Ag, and Au layers

This paper reports on a study by angle-resolved photoelectron and low-energy electron energy loss spectroscopy of graphene monolayers, which are produced by propylene cracking on the Ni(111) surface, followed by intercalation of Cu, Ag, and Au atoms between the graphene monolayer and the substrate, for various thicknesses of deposited metal layers and annealing temperatures. It has been shown that the spectra of valence-band π states and of phonon vibrational modes measured after intercalation become similar to those characteristic of single-crystal graphite with weak interlayer coupling. Despite the strong coupling of the graphene monolayer to the substrate becoming suppressed by intercalation of Cu and Ag atoms, the π state branch does not reach at the K point of the Brillouin zone the Fermi level, with the graphene coating itself breaking up partially to form graphene domains. At the same time after intercalation of Au atoms, the electronic band structure approaches the closest to that of isolated graphene, with linear π-state dispersion near the K point of the Brillouin zone, and the point of crossing of the filled, (π), with empty, (π*), states lying in the region of the Fermi level, which makes this system a promising experimental model of the quasi-free graphene monolayer.

Modification of the surface phonon dispersion of a graphite monolayer adsorbed on Ni(111) caused by intercalation of Yb, Cu and Ag

Abstract The surface phonon dispersion of a monolayer of graphite (MG) on Ni(111) has been measured in the ΓK direction of the Brillouin zone by means of high-resolution electron energy-loss spectroscopy (HREELS). The phonon dispersion relations of the MG/Ni(111) system and those obtained after intercalation of Yb are characterized by graphite-like phonon modes, softened due to the strong interaction with the Ni substrate. In the case of Cu and Ag intercalation, in contrast, the corresponding surface dispersion curves are very similar to those of bulk graphite. Calculations of the surface phonon dispersion based on a force constant model revealed that the force constants related to vertical motion in the MG are very much more affected after intercalation than those related to horizontal vibrations. This demonstrates that the stiffening observed after Cu and Ag intercalation is caused by a weaker interaction of the graphite layer with the Ni substrate.

Intercalation of silver atoms under a graphite monolayer on Ni(111)

The process of silver intercalation under a graphite monolayer (GM) grown on the (111) nickel single-crystal face, GM/Ni(111), is studied. The experiments were conducted in ultrahigh vacuum. The systems were formed in situ in a vacuum chamber under direct monitoring of each stage in the formation of the systems by angle-resolved UV photoelectron spectroscopy and LEED. The possibility of silver intercalation in the GM/Ni(111) system was studied in the course of deposition of various amounts of the metal on the given subject with subsequent heat treatment. It was established that the process occurs optimally under cyclic alternation of the operations of adsorbate (Ag) deposition on the GM/Ni(111) surface and subsequent annealing of the system. In the intermediate stages of GM/Ag/Ni(111) formation, the GM on Ni(111) was found to exist in two phases. Ag intercalation under a graphite monolayer on Ni(111) at room temperature was verified.

Atmospheric stability and doping protection of noble-metal intercalated graphene on Ni(111)

It has recently been demonstrated that pentacene can serve as protection layer for graphene on SiC preserving the unique E(k) band dispersion after exposure to atmosphere and subsequent annealing in vacuum. We confirm the stability of the ideal graphene band dispersion but without any protection layer. We demonstrate this by angle-resolved photoemission for graphene on Ni(111) intercalated by a Au monolayer. Exposure to air does not carbidize or oxidize the Ni substrate or open an apparent gap in the graphene. Its doping state is not affected and the Rashba-type spin-orbit effect on the graphene π state is preserved.

Spin–Orbit Coupling Induced Gap in Graphene on Pt(111) with Intercalated Pb Monolayer

Graphene is one of the most promising materials for nanoelectronics owing to its unique Dirac cone-like dispersion of the electronic state and high mobility of the charge carriers. However, to facilitate the implementation of the graphene-based devices, an essential change of its electronic structure, a creation of the band gap should controllably be done. Brought about by two fundamentally different mechanisms, a sublattice symmetry breaking or an induced strong spin-orbit interaction, the band gap appearance can drive graphene into a narrow-gap semiconductor or a 2D topological insulator phase, respectively, with both cases being technologically relevant. The later case, characterized by a spin-orbit gap between the valence and conduction bands, can give rise to the spin-polarized topologically protected edge states. Here, we study the effect of the spin-orbit interaction enhancement in graphene placed in contact with a lead monolayer. By means of angle-resolved photoemission spectroscopy, we show that intercalation of the Pb interlayer between the graphene sheet and the Pt(111) surface leads to formation of a gap of ∼200 meV at the Dirac point of graphene. Spin-resolved measurements confirm the splitting to be of a spin-orbit nature, and the measured near-gap spin structure resembles that of the quantum spin Hall state in graphene, proposed by Kane and Mele [ Phys. Rev. Lett. 2005 , 95 , 226801 ]. With a bandstructure tuned in this way, graphene acquires a functionality going beyond its intrinsic properties and becomes more attractive for possible spintronic applications.

The graphene/Au/Ni interface and its application in the construction of a graphene spin filter.

A modification of the contact of graphene with ferromagnetic electrodes in a model of the graphene spin filter allowing restoration of the graphene electronic structure is proposed. It is suggested for this aim to intercalate into the interface between the graphene and the ferromagnetic (Ni or Co) electrode a Au monolayer to block the strong interaction between the graphene and Ni (Co) and, thus, prevent destruction of the graphene electronic structure which evolves in direct contact of graphene with Ni (Co). It is also suggested to insert an additional buffer graphene monolayer with the size limited by that of the electrode between the main graphene sheet providing spin current transport and the Au/Ni electrode injecting the spin current. This will prevent the spin transport properties of graphene from influencing contact phenomena and eliminate pinning of the graphene electronic structure relative to the Fermi level of the metal, thus ensuring efficient outflow of injected electrons into the graphene. The role of the spin structure of the graphene/Au/Ni interface with enhanced spin-orbit splitting of graphene π states is also discussed, and its use is proposed for additional spin selection in the process of the electron excitation.

The role of the covalent interaction in the formation of the electronic structure of Au- and Cu-intercalated graphene on Ni(111)

A study is reported of the role played by covalent interaction in the coupling of graphene formed on Ni(111) to the Ni substrate and after intercalation of Au and Cu monolayers underneath the graphene. Covalent interaction of the graphene π states with d states of the underlying metal (Ni, Au, Cu) has been shown to bring about noticeable distortion of the dispersion relations of the graphene electronic π states in the region of crossing with d states, which can be described in terms of avoided-crossing effects and formation of bonding and antibonding d-π states. The overall graphene coupling to a substrate is mediated by the energy and occupation of the hybridized states involved. Because graphene formed directly on the Ni(111) surface has only bonding-type occupied states, the coupling to the substrate is very strong. Interaction with intercalated Au and Cu layers makes occupation of states of the antibonding and bonding types comparable, which translates into a weak resultant overall coupling of graphene to the substrate. As a result, after intercalation of Au atoms, the electronic structure becomes similar to that of quasi-free-standing graphene, with linear dispersion of π states at the K point of the Brillouin zone and the Dirac point localized close to the Fermi level. Intercalation of Cu atoms under the graphene monolayer results, besides generation of covalent interaction, in a slight charge transport, with a partial occupation of the previously unoccupied π* states and the Dirac point shifted by 0.35 eV toward increasing binding energy.

Surface spin-polarized currents generated in topological insulators by circularly polarized synchrotron radiation and their photoelectron spectroscopy indication

A new method for generating spin-polarized currents in topological insulators has been proposed and investigated. The method is associated with the spin-dependent asymmetry of the generation of holes at the Fermi level for branches of topological surface states with the opposite spin orientation under the circularly polarized synchrotron radiation. The result of the generation of holes is the formation of compensating spin-polarized currents, the value of which is determined by the concentration of the generated holes and depends on the specific features of the electronic and spin structures of the system. The indicator of the formed spin-polarized current can be a shift of the Fermi edge in the photoelectron spectra upon photoexcitation by synchrotron radiation with the opposite circular polarization. The topological insulators with different stoichiometric compositions (Bi1.5Sb0.5Te1.8Se1.2 and PbBi2Se2Te2) have been investigated. It has been found that there is a correlation in the shifts and generated spin-polarized currents with the specific features of the electronic spin structure. Investigations of the graphene/Pt(111) system have demonstrated the possibility of using this method for other systems with a spin-polarized electronic structure.