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 electronic structure of graphene by intercalation of iron and silicon atoms

The ab initio calculations of the electronic structure of low-dimensional graphene–iron–nickel and graphene–silicon–iron systems were carried out using the density functional theory. For the graphene–Fe–Ni(111) system, band structures for different spin projections and total densities of valence electrons are determined. The energy position of the Dirac cone caused by the p _z states of graphene depends weakly on the number of iron layers intercalated into the interlayer gap between nickel and graphene. For the graphene–Si–Fe(111) system, the most advantageous positions of silicon atoms on iron are determined. The intercalation of silicon under graphene leads to a sharp decrease in the interaction of carbon atoms with the substrate and largely restores the electronic properties of free graphene.

     

Modification of induced spin-orbit splitting of the π states of graphene during the joint intercalation of Bi and noble metals

The effect of intercalation of Bi atoms and the joint intercalation of atoms of Bi and noble metals (Au, Cu) on the spin and electron structure of graphene formed on Ni(111) is investigated by angle and spin-resolved PES. It is shown that the spin-orbit splitting of π states of graphene of 20–30 meV is observed for the joint intercalation of Bi and Au.     

Structure and stability of clusters on metal surfaces

Small clusters of 3d metals Ni/Ni(001), Cu/Cu(001), 4d-Pd/Pd(001), Ag/Ag(001), 5d-Pt/Pt(001), and Au/Au(001) are investigated by semiempirical methods using multiparticle interatomic interaction potentials. It is shown that the same magic numbers (4, 6, and 9) are characteristic for all metals indicated; these numbers are determined by the symmetry characteristics of the clusters, related to the morphology of the fcc (001) substrate. It is shown for Pt/Pt(111) that small clusters of seven, ten, and more atoms are stable for the fcc (111) surface. This confirms that the magic numbers are associated with the symmetry of the clusters. Fiz. Tverd. Tela (St. Petersburg) 41, 1329–1334 (July 1999)     

Electronic structure of the Au-intercalated graphene/Ni(111) surface

We report the electronic structure of the Au-intercalated graphene/Ni(111) surface using angle-resolved photoemission spectroscopy and low energy electron diffraction. The graphene/Ni(111) shows no Dirac cone near the Fermi level and a relatively broad C 1s core level spectrum probably due to the broken sublattice symmetry in the graphene on the Ni(111) substrate. When Au atoms are intercalated between them, the characteristic Dirac cone is completely recovered near the Fermi level and the C 1s spectrum becomes sharper with the appearance of a 10?×?10 superstructure. The fully Au-intercalated graphene/Ni(111) surface shows a p-type character with a hole pocket of ～0.034?Å^?1 diameter at the Fermi level. When the surface is doped with Na and K, a clear energy gap of ～0.4?eV is visible irrespective of alkali metal.     

Transport properties of graphene/metal planar junction

The transport properties of graphene/metal (Cu(111), Al(111), Ag(111), and Au(111)) planar junction are investigated using the first-principles nonequilibrium Green's function method. The planar junction induce second transmission minimum (TM2) below the Fermi level due to the existence of the Dirac point of clamped graphene. Interestingly, no matter the graphene is p- or n-type doped by the metal substrate, the TM2 always locates below the Fermi level. We find that the position of the TM2 is not only determined by the doping effect of metal lead on the graphene, but also influenced by the electrostatic potential of the metal substrate and the work function difference between the clamped and suspended graphene.     

Formation of a quasi-free-standing graphene with a band gap at the dirac point by Pb atoms intercalation under graphene on Re(0001)

The control of the graphene electronic structure is one of the most important problems in modern condensed matter physics. The graphene monolayer synthesized on the Re(0001) surface and then subjected to the intercalation of Pb atoms is studied by angle-resolved photoelectron spectroscopy and low-energy electron diffraction. The intercalation of Pb atoms under graphene takes place when the substrate is annealed above 500°C. As a result of the intercalation of Pb atoms, graphene becomes quasi-free-standing and a local band gap appears at the Dirac point. The band gap changes with the substrate temperature during the formation of the graphene/Pb/Re(0001) system. The band gap is 0.3 eV at an annealing temperature of 620°C and it increases up to 0.4 eV upon annealing at 830°C. Based on our data, we conclude that the band gap is mainly caused by the hybridization of the graphene π state with the rhenium 5d states located near the Dirac point of the graphene π state.     

On the charge transfer in the “single-sheet graphene-intercalated metal layer-SiC substrate” system

The proposed scheme for the consideration of charge transfer in the three-layer Gr/Me/SiC system (where Gr is a single-sheet graphene, Me is an intercalated metal layer, and SiC is a substrate) contains three stages. At the first stage, a metal monolayer adsorbed on silicon carbide is considered and the charge of adatoms in this monolayer is calculated. At the second stage, the shift of the Dirac point of free-standing single-layer graphene in an electrostatic field induced by charged adatoms of the monolayer is estimated. At the third stage, a weak interaction between Me/SiC and free-standing graphene is included, which allows electrons to tunnel but does not significantly distort the density of states of free-standing graphene. Estimations are performed for n- and p-type 6H-SiC(0001) substrates and Cu, Ag, and Au layers. The charge state of the graphene sheet and the shift of the Dirac point with respect to the Fermi level of the system are calculated. A comparison with the available experimental and theoretical results shows that the proposed scheme works quite satisfactorily.     

Graphene on Ir(111): physisorption with chemical modulation

The nonlocal van der Waals density functional approach is applied to calculate the binding of graphene to Ir(111). The precise agreement of the calculated mean height h = 3.41 ? of the C atoms with their mean height h = (3.38±0.04) ? as measured by the x-ray standing wave technique provides a benchmark for the applicability of the nonlocal functional. We find bonding of graphene to Ir(111) to be due to the van der Waals interaction with an antibonding average contribution from chemical interaction. Despite its globally repulsive character, in certain areas of the large graphene moiré unit cell charge accumulation between Ir substrate and graphene C atoms is observed, signaling a weak covalent bond formation.     

Band structure and many body effects in graphene

We have determined the electronic bandstructure of clean and potassium-doped single layer graphene, and fitted the graphene π bands to a one- and three-near-neighbor tight binding model. We characterized the quasiparticle dynamics using angle resolved photoemission spectroscopy. The dynamics reflect the interaction between holes and collective excitations, namely plasmons, phonons, and electron-hole pairs. Taking the topology of the bands around the Dirac energy for n-doped graphene into account, we compute the contribution to the scattering lifetimes due to electron-plasmon and electron phonon coupling.     

金属衬底上高质量大面积石墨烯的插层及其机制

石墨烯作为一种新型二维材料,因其优异的性质,在科学和应用领域具有非常重要的意义.而其超高的载流子迁移率、室温量子霍尔效应等,使其在信息器件领域备受关注.如何获得高质量并且与当代硅基工艺兼容的石墨烯功能器件,是未来将石墨烯应用于电子学领域的关键.近年来,研究人员发展了一种在外延石墨烯和金属衬底之间实现硅插层的技术,将金属表面外延石墨烯高质量、大面积的特点与当代硅基工艺结合起来,实现了无需转移且无损地将高质量石墨烯置于半导体之上.通过系统的实验研究并结合理论计算,揭示了插层过程包含四个主要阶段:诱导产生缺陷、异质原子插层、石墨烯自我修复和异质原子扩散成膜,并证实了这一插层机制的普适性.拉曼和角分辨光电子能谱实验结果表明,插层后的石墨烯恢复了本征特性,接近自由状态.此外,还实现了多种单质元素的插层.不同种类的原子形成不同的插层结构,从而构成了多种石墨烯/插层异质结.这为调控石墨烯的性质提供了实验基础,也展现了该插层技术的普适性.     

第一性原理研究氧在Ni(111)表面上的吸附能及功函数

采用基于密度泛函理论（DFT）广义梯度近似（GGA）下的第一性原理方法系统地研究了不同覆盖度下O在Ni（111）表面的吸附特性.计算结果表明,O在Ni（111）表面的稳定吸附位为三重面心立方（fcc）洞位,吸附能随着覆盖度的增加而减小,O诱导Ni（111）表面功函数的变化量与覆盖度成近线性关系,并随着覆盖度的增加而增大.同时,通过对电子密度和分波态密度的分析发现：O在Ni（111）表面的吸附使得Ni表面电子向O原子转移,形成表面偶极矩,导致功函数增加;表面Ni原子的3d轨道和O的2p轨道通过耦合、杂化作用形成成键态和反键态,而反键态几乎不被占据,因而O—Ni键相互作用比较强,吸附能较大. 关键词： 表面吸附 密度泛函理论 吸附能 功函数     

Energy of bonding an adsorbed atom with a single-layer graphene

The change in the local density of states δρ _g of a single-sheet graphene due to adsorption of a single atom has been calculated in the framework of the M model proposed earlier. The dependence of the local density of states δρ _g on the position of the adatom energy level ɛ _a with respect to the Dirac point and other parameters of the problem has been analyzed. It has been shown that the largest changes in the local density of states δρ _g are caused by adatoms with the ɛ _a levels lying in the vicinity of the Dirac point, so that the minimum density of states of graphene remains equal to zero. An analytical expression has been derived for the energy of bonding W _ads of the adatom with graphene. The obtained estimates of the bonding energy W _ads in the weak and strong adatom-substrate bonding regimes are presented. Atoms of alkali metals and halogens have been considered as specific adsorbates.     

Graphene on ordered Ni-alloy surfaces formed by metal (Sn,Al) intercalation between graphene/Ni(111)

Deposition and intercalation of Al and Sn on Ni(111) supported graphene is investigated by Auger electron spectroscopy, low energy electron diffraction, and scanning tunneling microscopy. Al intercalates at ~ 200 °C while Sn intercalates at ~ 350 °C, indicating that the intercalation process is element specific. Both Al and Sn alloy with the Ni-substrate at higher annealing temperatures and form ordered alloy surfaces and surface alloys, respectively. Sn forms a (√3 × √3) R30° surface alloy by substituting surface Ni-atoms with Sn and thus the alloy maintains the same good lattice match with graphene as for Ni(111). Both Sn and Al are interacting weakly with graphene and can therefore be used to decouple graphene from the strongly interacting Ni substrate.     

Wave-function mapping of graphene quantum dots with soft confinement

Using low-temperature scanning tunneling spectroscopy, we map the local density of states of graphene quantum dots supported on Ir(111). Because of a band gap in the projected Ir band structure around the graphene K point, the electronic properties of the QDs are dominantly graphenelike. Indeed, we compare the results favorably with tight binding calculations on the honeycomb lattice based on parameters derived from density functional theory. We find that the interaction with the substrate near the edge of the island gradually opens a gap in the Dirac cone, which implies soft-wall confinement. Interestingly, this confinement results in highly symmetric wave functions. Further influences of the substrate are given by the known moiré potential and a 10% penetration of an Ir surface resonance into the graphene layer.     

πNN Dynamics in pp → pp,pp →πd and πd →πd Processes Below 1 GeV

pp and πd scattering and pp →πd reaction processes at incident proton laboratory energies T _L ≤ 1 GeV are studied in the framework of πNN dynamics. For this purpose three-body calculations are performed with the πN interaction in the P ₁₁, P ₃₃, S ₁₁ and S ₃₁ states and NN forces in the ³ S ₁ -³ D ₁, ¹ S ₀, and ³ P ₂ states. In addition, the backward-going pion contribution at the πNΔ vertex, the πN-ρN coupling, the heavy-meson exchanges in the NN → NN driving term, and the effect of the off-shell structure in the πN-ρN P ₃₃ interaction are taken into account. Received March 28, 1994; revised July 29, 1994; accepted for publication August 31, 1994     

Formation and lithium doping of graphene on the surface of cobalt silicide

The intercalation of silicon under graphene on the Co(0001) surface, which is accompanied by the formation of a silicon solid solution in cobalt and by the formation of a surface crystalline Co₂Si phase, has been investigated using photoelectron spectroscopy. It has been shown that the formation of cobalt silicide leads to a substantial weakening of the hybridization of electronic states of graphene and cobalt and to the recovery of the Dirac spectrum of electronic states of graphene near the Fermi level. This has made it possible to investigate the electron doping of graphene on the cobalt silicide substrate upon deposition of lithium on its surface. It has been found that doping with lithium leads to a significant charge transfer onto graphene, and the electron concentration reaches 3.1 × 10¹⁴ cm^?2. Moreover, the specific form of the Fermi surface creates favorable conditions for the enhancement of the electron-phonon coupling. As a result, the formed system can be considered as a candidate for the creation of superconductivity in single-layer graphene.     

Evolution of the electronic properties of transition metal nanoclusters on graphite surface

The electronic properties of nanoclusters of transition (Ni, Co, Cr) and noble (Au, Cu) metals deposited on the surface of highly oriented pyrolytic graphite (HOPG) are studied using the method of X-ray photoelectron spectroscopy. The laws of variation of a change ΔE _b in the binding energies of core-level electrons in the initial (ΔE _i) and final (ΔE _f) states of atoms in nanoclusters, the intrinsic widths γ of photoelectron lines, and their singularity indices α as functions of the metal cluster size d are determined. A qualitative difference in behavior of the ΔE _i(d) and α(d) values in metals of the two groups (Ni, Cr versus Co, Cu) is found. The values of the final-state energy (ΔE _f < 0) and the line width (Δγ > 0) in the clusters of all metals studied vary in a similar manner. It is shown that a significant contribution to E _i is due to a transfer of the valence-shell electrons at the cluster-substrate interface, which is caused by the contact potential difference. The value of an uncompensated charge per nanocluster is determined as a function of the cluster size and the number of atoms in the cluster. The behavior of ΔE _f(d) is controlled by the Coulomb energy of a charged cluster and by a decrease in the efficiency of electron screening, which is different in the metals studied. The broadening of photoelectron lines is determined by a spread of the cluster sizes and by lower electron screening in the final Fermi system. An asymmetry of the core-level electron spectra of nanoclusters can be explained using notions about the electron-hole pair excitation near the Fermi level. The effect of the structure of the density of electron states in the d band of transition metals on the asymmetry of photoelectron lines is considered and it is concluded that this structure near the Fermi level qualitatively changes with a decrease in the nanocluster size. The obtained results indicate that the behavior of the electron subsystem of clusters of the d-metals in a size range of 2–10 nm under consideration is close to the behavior of a normal Fermi system.     

Final-state effects in photoemission experiments from graphene on Ni(111)

Photon-energy dependent photoemission experiments using high harmonic radiation as a tunable photon source on epitaxially grown graphene on a Ni(111) substrate are presented. A resonance in the photoemission cross section for the σ and π states of graphene was observed and compared to a simple model for the determination of photoemission cross sections of free standing graphene, pointing out the role of the interaction of graphene with the nickel substrate.     

Electronic states on the surface of graphite

Graphite consists of graphene layers in an AB (Bernal) stacking arrangement. The introduction of defects can reduce the coupling between the top graphene layers and the bulk crystal producing new electronic states that reflect the degree of coupling. We employ low temperature high magnetic field scanning tunneling microscopy (STM) and spectroscopy (STS) to access these states and study their evolution with the degree of coupling. STS in magnetic field directly probes the dimensionality of electronic states. Thus two-dimensional states produce a discrete series of Landau levels while three-dimensional states form Landau bands providing a clear distinction between completely decoupled top layers and ones that are coupled to the substrate. We show that the completely decoupled layers are characterized by a single sequence of Landau levels with square-root dependence on field and level index indicative of massless Dirac fermions. In contrast weakly coupled bilayers produce special sequences reflecting the degree of coupling, and multilayers produce sequences reflecting the coexistence of massless and massive Dirac fermions. In addition we show that the graphite surface is soft and that an STM tip can be quite invasive when brought too close to the surface and that there is a characteristic tip-sample distance beyond which the effect of sample-tip interaction is negligible.