In-plane orientation effects on the electronic structure, stability and Raman scattering of monolayer graphene on Ir(111)

We employ angle-resolved photoemission spectroscopy (ARPES) to investigate the electronic structures of two rotational variants of epitaxial, single-layer graphene on Ir(111). As grown, the more-abundant R0 variant is nearly charge-neutral, with strong hybridization between graphene and Ir bands near the Fermi level. The graphene Fermi surface and its replicas exactly coincide with Van Hove singularities in the Ir Fermi surface. Sublattice symmetry breaking introduces a small gap-inducing potential at the Dirac crossing, which is revealed by n-doping the graphene using K atoms. The energy gaps between main and replica bands (originating from the moir\'e interference pattern between graphene and Ir lattices) is shown to be non-uniform along the mini- zone boundary due to hybridization with Ir bands. An electronically mediated interaction is proposed to account for the stability of the R0 variant. The variant rotated 30{\deg} in-plane, R30, is p-doped as grown and K doping reveals no band gap at the Dirac crossing. No replica bands are found in ARPES measurements. Raman spectra from the R30 variant exhibit the characteristic phonon modes of graphene, while R0 spectra are featureless. These results show that the film/substrate interaction changes from chemisorption (R0) to physisorption (R30) with in-plane orientation. Finally, graphene-covered Ir has a work function lower than the clean substrate but higher than graphite.Comment: Manuscript plus 7 figure

Giant Spin-splitting in the Bi/Ag(111) Surface Alloy

Surface alloying is shown to produce electronic states with a very large spin-splitting. We discuss the long range ordered bismuth/silver(111) surface alloy where an energy bands separation of up to one eV is achieved. Such strong spin-splitting enables angular resolved photoemission spectroscopy to directly observe the region close to the band edge, where the density of states shows quasi-one dimensional behavior. The associated singularity in the local density of states has been measured by low temperature scanning tunneling spectroscopy. The implications of this new class of materials for potential spintronics applications as well as fundamental issues are discussed.Comment: 4 pages, 4 figure

Small scale rotational disorder observed in epitaxial graphene on SiC(0001)

Interest in the use of graphene in electronic devices has motivated an explosion in the study of this remarkable material. The simple, linear Dirac cone band structure offers a unique possibility to investigate its finer details by angle-resolved photoelectron spectroscopy (ARPES). Indeed, ARPES has been performed on graphene grown on metal substrates but electronic applications require an insulating substrate. Epitaxial graphene grown by the thermal decomposition of silicon carbide (SiC) is an ideal candidate for this due to the large scale, uniform graphene layers produced. The experimental spectral function of epitaxial graphene on SiC has been extensively studied. However, until now the cause of an anisotropy in the spectral width of the Fermi surface has not been determined. In the current work we show, by comparison of the spectral function to a semi-empirical model, that the anisotropy is due to small scale rotational disorder ($\sim\pm$ 0.15$^{\circ}$) of graphene domains in graphene grown on SiC(0001) samples. In addition to the direct benefit in the understanding of graphene's electronic structure this work suggests a mechanism to explain similar variations in related ARPES data.Comment: 5 pages, 4 figure

Highly p-doped graphene obtained by fluorine intercalation

We present a method for decoupling epitaxial graphene grown on SiC(0001) by intercalation of a layer of fluorine at the interface. The fluorine atoms do not enter into a covalent bond with graphene, but rather saturate the substrate Si bonds. This configuration of the fluorine atoms induces a remarkably large hole density of p \approx 4.5 \times 1013 cm-2, equivalent to the location of the Fermi level at 0.79 eV above the Dirac point ED .Comment: 4 pages, 2 figures, in print AP

Linearly dispersive bands at the onset of correlations in Kx_xC60_{60} films

Molecular crystals are a flexible platform to induce novel electronic phases. Due to the weak forces between molecules, intermolecular distances can be varied over relatively larger ranges than interatomic distances in atomic crystals. On the other hand, the hopping terms are generally small, which results in narrow bands, strong correlations and heavy electrons. Here, by growing K$_x$C$_{60}$ fullerides on hexagonal layered Bi$_2$Se$_3$, we show that upon doping the series undergoes a Mott transition from a molecular insulator to a correlated metal, and an in-gap state evolves into highly dispersive Dirac-like fermions at half filling, where superconductivity occurs. This picture challenges the commonly accepted description of the low energy quasiparticles as appearing from a gradual electron doping of the conduction states, and suggests an intriguing parallel with the more famous family of the cuprate superconductors. More in general, it indicates that molecular crystals offer a viable route to engineer electron-electron interactions.Comment: 5 pages, 4 figures. Accepted at Physical Review Researc

Tunable Electronic Structure in Gallium Chalcogenide van der Waals Compounds

Transition metal monochalcogenides comprise a class of two-dimensional materials with electronic band gaps that are highly sensitive to material thickness and chemical composition. Here, we explore the tunability of the electronic excitation spectrum in GaSe using angle-resolved photoemission spectroscopy. The electronic structure of the material is modified by $\textit{in-situ}$ potassium deposition as well as by forming GaS$_{x}$Se$_{1-x}$ alloy compounds. We find that potassium decouples the top-most tetra-layer of the GaSe unit cell, leading to a substantial change of the dispersion around the valence band maximum (VBM). The observed band dispersion of a single tetralayer is consistent with a transition from the direct gap character of the bulk to the indirect gap character expected for monolayer GaSe. Upon alloying with sulfur, we observe a phase transition from AB to $\text{AA}^{\prime}$ stacking. Alloying also results in a rigid energy shift of the VBM towards higher binding energies which correlates with a blue shift in the luminescence. The increase of the band gap upon sulfur alloying does not appear to change the dispersion or character of the VBM appreciably, implying that it is possible to engineer the gap of these materials while maintaining their salient electronic properties

Universal Mechanism of Band-Gap Engineering in Transition-Metal Dichalcogenides

Two-dimensional (2D) van-der-Waals semiconductors have emerged as a class of materials with promising device characteristics owing to the intrinsic bandgap. For realistic applications, the ideal is to modify the bandgap in a controlled manner by a mechanism that can be generally applied to this class of materials. Here, we report the observation of a universally tunable bandgap in the family of bulk 2H transition metal dichalcogenides (TMDs) by in situ surface doping of Rb atoms. A series of angle-resolved photoemission spectra unexceptionally shows that the bandgap of TMDs at the zone corners is modulated in the range of 0.8 ~ 2.0 eV, which covers a wide spectral range from visible to near infrared, with a tendency from indirect to direct bandgap. A key clue to understand the mechanism of this bandgap engineering is provided by the spectroscopic signature of symmetry breaking and resultant spin splitting, which can be explained by the formation of 2D electric dipole layers within the surface bilayer of TMDs. Our results establish the surface Stark effect as a universal mechanism of bandgap engineering based on the strong 2D nature of van-der-Waals semiconductors

Electronic structure of graphene on single crystal copper substrates

The electronic structure of graphene on Cu(111) and Cu(100) single crystals is investigated using low energy electron microscopy, low energy electron diffraction and angle resolved photoemission spectroscopy. On both substrates the graphene is rotationally disordered and interactions between the graphene and substrate lead to a shift in the Dirac crossing of $\sim$ -0.3 eV and the opening of a $\sim$ 250 meV gap. Exposure of the samples to air resulted in intercalation of oxygen under the graphene on Cu(100), which formed a ($\sqrt{2} \times 2\sqrt{2}$)R45$^{\rm o}$ superstructure. The effect of this intercalation on the graphene $\pi$ bands is to increase the offset of the Dirac crossing ($\sim$ -0.6 eV) and enlarge the gap ($\sim$ 350 meV). No such effect is observed for the graphene on Cu(111) sample, with the surface state at $\Gamma$ not showing the gap associated with a surface superstructure. The graphene film is found to protect the surface state from air exposure, with no change in the effective mass observed