The electronic structure of Ca-intercalated superconducting graphite CaC6

We have measured Ca-intercalated graphite superconductor CaC₆ (T_c = 11.2 K) by soft X-ray photoemission spectroscopy in order to understand the electronic structure. For the valence band, we observed several structures that correspond to those of calculated density of states with the partial density of states of Ca 3d at the Fermi level (E_F). We also observed core level spectra that are a very large asymmetric Ca 2p and asymmetric C 1s for CaC₆, suggesting the existence of conduction electrons derived from Ca 3d and a charge transfer from Ca to graphene layer. These results provide spectroscopic evidence for PDOS of Ca 3d at E_F. From a comparison of electronic structure of CaC₆ and other graphite intercalation compounds (GICs), we found the difference between CaC₆ and other superconducting GICs, which provides deeper understanding of the superconductivity of CaC₆.     

Graphite,Graphene, and the Flat Band Superconductivity

Superconductivity has been observed in bilayer graphene [1, 2]. The main factor that determines the mechanism of the formation of this superconductivity is the “magic angle” of twist of two graphene layers, at which the electronic band structure becomes nearly flat. The specific role played by twist and by the band flattening has been earlier suggested for explanations of the signatures of room-temperature superconductivity observed in the highly oriented pyrolytic graphite (HOPG), when the quasi two-dimensional interfaces between the twisted domains are present. The interface contains the periodic array of misfit dislocations (analogs of the boundaries of the unit cell of the Moiré superlattice in bilayer graphene), which provide the possible source of the flat band. This demonstrates that it is high time for combination of the theoretical and experimental efforts in order to reach the reproducible room-temperature superconductivity in graphite or in similar real or artificial materials.     

Nonadiabatic channels in the superconducting pairing of fullerides

We show the intrinsic inconsistency of the conventional phonon mediated theory of superconductivity in relation to the observed properties of Rb3C60. The recent, highly accurate measurement of the carbon isotope coefficient alpha(C) = 0.21, together with the high value of T(c) (30 K) and the very small Fermi energy E(F) (0.25 eV), unavoidably implies the opening of nonadiabatic channels in the superconducting pairing. We estimate these effects and show that they are actually the key elements for the high value of T(c) in these materials compared to the very low values of graphite intercalation compounds.     

Superconductivity of bulk CaC6

We have obtained bulk samples of the graphite intercalation compound, CaC6, by a novel method of synthesis from highly oriented pyrolytic graphite. The crystal structure has been completely determined showing that it is the only member of the MC6, metal-graphite compounds that has rhombohedral symmetry. We have clearly shown the occurrence of superconductivity in the bulk sample at 11.5 K, using magnetization measurements.     

First-principles study of Li-intercalated carbon nanotube ropes

We studied Li-intercalated carbon nanotube ropes by first-principles methods. Results show charge transfer between Li and C and small structural deformation due to intercalation. Both the interior of the nanotube and the interstitial space are susceptible for intercalation. The Li intercalation potential of a single-walled nanotube rope is comparable to that of graphite and almost independent of the Li density up to around LiC2, as observed in recent experiments. This density is significantly higher than that of Li-intercalated graphite, making the nanorope a promising candidate for the anode material in battery applications.     

Intercalation of graphite and hexagonal boron nitride by lithium

Although graphite and hexagonal form of BN (h-BN) are isoelectronic and have very similar lattice structures, it has been very difficult to intercalate h-BN while there are hundreds of intercalation compounds of graphite. We have done a comparative first principles investigation of lithium intercalation of graphite and hexagonal boron nitride to provide clues for the difficulty of h-BN intercalation. In particular lattice structure, cohesive energy, formation enthalpy, charge transfer and electronic structure of both intercalation compounds are calculated in the density functional theory framework with local density approximation to the exchange-correlation energy. The calculated formation enthalpy of the considered forms of Li intercalated h-BN is found to be positive which rules out h-BN intercalation without externally supplied energy. Also, the Li(BN)₃ form of Li-intercalated h-BN is found to have a large electronic density of states at the Fermi level and an interlayer state that crosses Fermi level at the zone center; these properties make it an interesting material to investigate the role of interlayer states in the superconductivity of alkali intercalated layered structures. The most pronounced change in the charge distribution of the intercalated compounds is found to be charge transfer from the planar σ states to the π states.     

Phonon dispersion of quasi-freestanding graphene on Pt(111)

High-resolution electron energy loss spectroscopy has been used to probe phonon dispersion in quasi-freestanding graphene epitaxially grown on Pt(111). Loss spectra clearly show different dispersing features related to both acoustic and optical phonons. The present results have been compared with graphene systems which strongly interact with the substrate, i.e. the nearly-flat monolayer graphene (MLG)/Ni(111) and the corrugated MLG/Ru(0001). We found that the phonon dispersion of graphene/Pt(111) reproduces well the behavior of pristine graphite. This could be taken as an indication of the negligible interaction between the graphene sheet and the underlying Pt substrate. The softening of out-of-plane modes observed for interacting graphene/metal interfaces does not occur for the nearly-free-standing graphene/Pt(111).     

Rashba effect in the graphene/ni(111) system

We report on angle-resolved photoemission studies of the electronic pi states of high-quality epitaxial graphene layers on a Ni(111) surface. In this system the electron binding energy of the pi states shows a strong dependence on the magnetization reversal of the Ni film. The observed extraordinarily large energy shift up to 225 meV of the graphene-derived pi band peak position for opposite magnetization directions is attributed to a manifestation of the Rashba interaction between spin-polarized electrons in the pi band and the large effective electric field at the graphene/Ni interface. Our findings show that an electron spin in the graphene layer can be manipulated in a controlled way and have important implications for graphene-based spintronic devices.     

Pairing symmetry of superconducting graphene

The possibility of intrinsic superconductivity in alkali-coated graphene monolayers has been recently suggested theoretically. Here, we derive the possible pairing symmetries of a carbon honeycomb lattice and discuss their phase diagram. We also evaluate the superconducting local density of states (LDOS) around an isolated impurity. This is directly related to scanning tunneling microscopy experiments, and may evidence the occurrence of unconventional superconductivity in graphene.     

Inverted V-shaped evolution of superconducting temperature in SrBC under pressure

Based on density functional first-principles calculations and anisotropic Eliashberg equations, we have investigated the electronic structure, lattice dynamics, and phonon-mediated superconductivity in newly synthesized layered compound Sr BC under pressure. Different from Li BC and Mg B2, our calculations surprisingly reveal that Sr BC is isotropic in compressibility, due to the accumulation of substantial electrons in the interstitial region. We find that the Sr phonons strongly couple with B-2 pz orbital and the interstitial states, giving rise to a two-gap superconductivity in Sr BC, whose transition temperature shows an inverted V-shaped dependence on pressure. The maximal transition temperature is about 22 K at50 GPa. On both sides of 50 GPa, the transition temperature exhibits quasi-linear variation with positive and negative slopes, respectively. Such a variation of transition temperature is infrequent among phonon-mediated superconductors. The competition between enhanced electron–phonon matrix element and hardened phonons plays an essential role in governing the behavior of the critical temperature.     

Sodium Intercalation of Graphene Films on Re( $$10\bar 10$$ 10 1 ¯ 0 )

It is shown that during low-temperature (300–500 K) intercalation of sodium atoms into thin multilayer graphene and graphite films on rhenium the first graphene layer plays the role of a trap to which atoms coming on the surface diffuse through a graphite film. The intercalation phase of the interlayer space in the graphite bulk is actively filled at a sodium atoms concentration under the first graphene layer close to the maximum possible (2 ± 0.5) × 10¹⁴ cm^–2. This phase capacity is proportional to the graphite film thickness that can be varied in this work from one graphene layer to ~50 atomic layers. The diffusion energy E _d of Na atoms through the graphite film was estimated to be E _d ≈ 1.4 eV.

     

Effect of the superconducting transition on phonon energies and lifetimes in lead

We have performed a high-resolution inelastic neutron scattering study of certain transverse phonons in lead. We find that neither the energies nor the linewidths change appreciably with the onset of superconductivity. This finding contradicts a recent experimental report, but is in accord with theoretical expectations.     

Two-dimensional phonon transport in graphene

Properties of phonons-quanta of the crystal lattice vibrations-in graphene have recently attracted significant attention from the physics and engineering communities. Acoustic phonons are the main heat carriers in graphene near room temperature, while optical phonons are used for counting the number of atomic planes in Raman experiments with few-layer graphene. It was shown both theoretically and experimentally that transport properties of phonons, i.e. energy dispersion and scattering rates, are substantially different in a quasi-two-dimensional system such as graphene compared to the basal planes in graphite or three-dimensional bulk crystals. The unique nature of two-dimensional phonon transport translates into unusual heat conduction in graphene and related materials. In this review, we outline different theoretical approaches developed for phonon transport in graphene, discuss contributions of the in-plane and cross-plane phonon modes, and provide comparison with available experimental thermal conductivity data. Particular attention is given to analysis of recent results for the phonon thermal conductivity of single-layer graphene and few-layer graphene, and the effects of the strain, defects, and isotopes on phonon transport in these systems.     

Temperature-dependent localized excitations of doped carriers in superconducting diamond

Laser-excited photoemission spectroscopy is used to show that the doped carriers in metallic or superconducting diamond couple strongly to the lattice via high-energy (approximately 150 meV) optical phonons, with direct observations of localized Franck-Condon multiphonon sidebands appearing as Fermi-edge replicas. It exhibits a temperature-dependent spectral weight transfer from higher to lower energy sidebands and zero-phonon Fermi-edge states. The quantified coupling strength shows a systematic increase on lowering temperature, implicating its relation to the normal state transport and superconductivity.     

Model of an exotic chiral superconducting phase in a graphene bilayer

We theoretically demonstrate the formation of a new type of unconventional superconductivity in graphene materials, which exhibits a gapless property. The studied superconductivity is based on an interlayer pairing of chiral electrons in bilayer graphene, which results in an exotic s-wave spin-triplet condensate order with anomalous thermodynamic properties. These include the possibility of a temperature-induced condensation causing an increase of the pairing gap with increasing temperature and an entropy of the stable superconducting state which can be higher than its value in the normal state. Our study reveals the analogy of the interlayer superconductivity in graphene materials to the color superconductivity in dense quark matter and the gapless pairing states in nuclear matter and ultracold atomic gases.     

三层石墨烯及其n型和p型插层化合物的制备和拉曼光谱表征

我们利用微机械剥离方法制备了三层石墨烯.在此基础上,利用两室气体传输法,以三氯化铁和钾为化学掺杂剂,成功合成了三层石墨烯的一阶p型和n型插层化合物.三层石墨烯的高分辨率拉曼光谱具有独特的2D谱峰线形,该线形可以用作指纹来鉴别三层石墨烯.三层石墨烯一阶插层化合物的拉曼光谱表明,三氯化铁和钾的插层掺杂使得三层石墨烯的层间耦...     

Moiré flat bands of twisted few-layer graphite

We report that the twisted few layer graphite (tFL-graphite) is a new family of moiré heterostructures (MHSs), which has richer and highly tunable moiré flat band structures entirely distinct from all the known MHSs. A tFL-graphite is composed of two few-layer graphite (Bernal stacked multilayer graphene), which are stacked on each other with a small twisted angle. The moiré band structure of the tFL-graphite strongly depends on the layer number of its composed two van der Waals layers. Near the magic angle, a tFL-graphite always has two nearly flat bands coexisting with a few pairs of narrowed dispersive (parabolic or linear) bands at the Fermi level, thus, enhances the DOS at E_F . This coexistence property may also enhance the possible superconductivity as been demonstrated in other multiband superconductivity systems. Therefore, we expect strong multiband correlation effects in tFL-graphite. Meanwhile, a proper perpendicular electric field can induce several isolated nearly flat bands with nonzero valley Chern number in some simple tFL-graphites, indicating that tFL-graphite is also a novel topological flat band system.     

Free graphene films obtained from thermally expanded graphite

A method of obtaining free graphene films using intercalation and subsequent thermal expansion of crystalline graphite is suggested. Thermally expanded graphite prepared by microwave irradiation is examined under a scanning electron microscope. It is found that it contains fragments of free graphene films. The conclusion is drawn that this method is promising for obtaining graphene suitable for experimental research.     

Intercalation of metals and silicon at the interface of epitaxial graphene and its substrates

Intercalations of metals and silicon between epitaxial graphene and its substrates are reviewed. For metal intercala- tion, seven different metals have been successfully intercalated at the interface of graphene/Ru（O001） and form different intercalated structures. Meanwhile, graphene maintains its original high quality after the intercalation and shows features of weakened interaction with the substrate. For silicon intercalation, two systems, graphene on Ru（O001） and on Ir（l I 1）, have been investigated. In both cases, graphene preserves its high quality and regains its original superlative properties after the silicon intercalation. More importantly, we demonstrate that thicker silicon layers can be intercalated at the interface, which allows the atomic control of the distance between graphene and the metal substrates. These results show the great potential of the intercalation method as a non-damaging approach to decouple epitaxial graphene from its substrates and even form a dielectric layer for future electronic applications.     

Structural preablation dynamics of graphite observed by ultrafast electron crystallography

By means of time-resolved electron crystallography, we report direct observation of the structural dynamics of graphite, providing new insights into the processes involving coherent lattice motions and ultrafast graphene ablation. When graphite is excited by an ultrashort laser pulse, the excited carriers reach their equilibrium in less then one picosecond by transferring heat to a subset of strongly coupled optical phonons. The time-resolved diffraction data show that on such a time scale the crystal undergoes a contraction whose velocity depends on the excitation fluence. The contraction is followed by a large expansion which, at sufficiently high fluence, leads to the ablation of entire graphene layers, as recently predicted theoretically.