Mathieu G. Silly

Band Alignment and Minigaps in Monolayer MoS2-Graphene van der Waals Heterostructures

Two-dimensional layered MoS2 shows great potential for nanoelectronic and optoelectronic devices due to its high photosensitivity, which is the result of its indirect to direct band gap transition when the bulk dimension is reduced to a single monolayer. Here, we present an exhaustive study of the band alignment and relativistic properties of a van der Waals heterostructure formed between single layers of MoS2 and graphene. A sharp, high-quality MoS2-graphene interface was obtained and characterized by micro-Raman spectroscopy, high-resolution X-ray photoemission spectroscopy (HRXPS), and scanning high-resolution transmission electron microscopy (STEM/HRTEM). Moreover, direct band structure determination of the MoS2/graphene van der Waals heterostructure monolayer was carried out using angle-resolved photoemission spectroscopy (ARPES), shedding light on essential features such as doping, Fermi velocity, hybridization, and band-offset of the low energy electronic dynamics found at the interface. We show that, close to the Fermi level, graphene exhibits a robust, almost perfect, gapless, and n-doped Dirac cone and no significant charge transfer doping is detected from MoS2 to graphene. However, modification of the graphene band structure occurs at rather larger binding energies, as the opening of several miniband-gaps is observed. These miniband-gaps resulting from the overlay of MoS2 and the graphene layer lattice impose a superperiodic potential.

Formation of one-dimensional self-assembled silicon nanoribbons on Au(110)-(2 × 1)

We report results on the self-assembly of silicon nanoribbons (NRs) on the (2 × 1) reconstructed Au(110) surface under ultra-high vacuum conditions. Upon adsorption of 0.2 monolayer (ML) of silicon, the (2 × 1) reconstruction of Au(110) is replaced by an ordered surface alloy. Above this coverage, a new superstructure is revealed by low energy electron diffraction (LEED), which becomes sharper at 0.3 Si ML. This superstructure corresponds to Si nanoribbons all oriented along the [1¯10] direction as revealed by LEED and scanning tunneling microscopy (STM). STM and high-resolution photoemission spectroscopy indicate that the nanoribbons are flat and predominantly 1.6 nm wide. In addition, the silicon atoms show signatures of two chemical environments corresponding to the edge and center of the ribbons.

Epitaxial Graphene on 4H-SiC(0001) Grown under Nitrogen Flux: Evidence of Low Nitrogen Doping and High Charge Transfer

Nitrogen doping of graphene is of great interest for both fundamental research to explore the effect of dopants on a 2D electrical conductor and applications such as lithium storage, composites, and nanoelectronic devices. Here, we report on the modifications of the electronic properties of epitaxial graphene thanks to the introduction, during the growth, of nitrogen-atom substitution in the carbon honeycomb lattice. High-resolution transmission microscopy and low-energy electron microscopy investigations indicate that the nitrogen-doped graphene is uniform at large scale. The substitution of nitrogen atoms in the graphene planes was confirmed by high-resolution X-ray photoelectron spectroscopy, which reveals several atomic configurations for the nitrogen atoms: graphitic-like, pyridine-like, and pyrrolic-like. Angle-resolved photoemission measurements show that the N-doped graphene exhibits large n-type carrier concentrations of 2.6 × 10(13) cm(-2), about 4 times more than what is found for pristine graphene, grown under similar pressure conditions. Our experiments demonstrate that a small amount of dopants (<1%) can significantly tune the electronic properties of graphene by shifting the Dirac cone about 0.3 eV toward higher binding energies with respect to the π band of pristine graphene, which is a key feature for envisioning applications in nanoelectronics.

Internal Structure of InP/ZnS Nanocrystals Unraveled by High-Resolution Soft X-ray Photoelectron Spectroscopy

High-energy resolution photoelectron spectroscopy (DeltaE < 200 meV) is used to investigate the internal structure of semiconductor quantum dots containing low Z-contrast elements. In InP/ZnS core/shell nanocrystals synthesized using a single-step procedure (core and shell precursors added at the same time), a homogeneously alloyed InPZnS core structure is evidenced by quantitative analysis of their In3d(5/2) spectra recorded at variable excitation energy. When using a two-step method (core InP nanocrystal synthesis followed by subsequent ZnS shell growth), XPS analysis reveals a graded core/shell interface. We demonstrate the existence of In-S and S(x)-In-P(1-x) bonding states in both types of InP/ZnS nanocrystals, which allows a refined view on the underlying reaction mechanisms.

Structural coherency of epitaxial graphene on 3C-SiC(111) epilayers on Si(111)

Graphene has emerged as a promising nanoelectronic material in electronic devices applications and studying two-dimensional electron gases with relativistic dispersion near Dirac point. Nonetheless, the control of the preparation conditions for homogeneous large-area graphene layers is difficult. Here, we illustrate evidence for high structural and electronic quality epitaxial graphene on 3C-SiC(111). Morphology and electronic structure of the graphene layers have been analyzed with low energy electron microscopy and angle resolved photoemission spectroscopy. Using scanning tunneling microscopy and scanning transmission electron microscopy, we show that graphene exhibits remarkably continuity of step edges suggesting the possibility of growing large scale graphene layer

TEMPO: a New Insertion Device Beamline at SOLEIL for Time Resolved Photoelectron Spectroscopy Experiments on Solids and Interfaces

A new insertion device beamline is now operational on straight section 8 at the SOLEIL synchrotron radiation source in France. The beamline and the experimental station were developed to optimize the study of the dynamics of electronic and magnetic properties of materials. Here we present the main technical characteristics of the installation and the general principles behind them. The source is composed of two APPLE II type insertion devices. The monochromator with plane gratings and spherical mirrors is working in the energy range 40–1500 eV. It is equipped with VLS, VGD gratings to allow the user optimization of flux or higher harmonics rejection. The observed resonance structures measured in gas phase enable us to determine the available energy resolution: a resolving power higher than 10000 is obtained at the Ar 2p, N 1s and Ne K‐edges when using all the optical elements at full aperture. The total flux as a function of the measured photon energy and the characterization of the focal spot size comple...

Electronic and surface properties of PbS nanoparticles exhibiting efficient multiple exciton generation

Ultrafast transient absorption measurements have been used to study multiple exciton generation in solutions of PbS nanoparticles vigorously stirred to avoid the effects of photocharging. The threshold and slope efficiency of multiple exciton generation are found to be 2.5 ± 0.2 ×E(g) and 0.34 ± 0.08, respectively. Photoemission measurements as a function of nanoparticle size and ageing show that the position of the valence band maximum is pinned by surface effects, and that a thick layer of surface oxide is rapidly formed at the nanoparticle surfaces on exposure to air.

Large-Area and High-Quality Epitaxial Graphene on Off-Axis SiC Wafers

The growth of large and uniform graphene layers remains very challenging to this day due to the close correlation between the electronic and transport properties and the layer morphology. Here, we report the synthesis of uniform large-scale mono- and bilayers of graphene on off-axis 6H-SiC(0001) substrates. The originality of our approach consists of the fine control of the growth mode of the graphene by precise control of the Si sublimation rate. Moreover, we take advantage of the presence of nanofacets on the off-axis substrate to grow a large and uniform graphene with good long-range order. We believe that our approach represents a significant step toward the scalable synthesis of graphene films with high structural qualities and fine thickness control, in order to develop graphene-based electronic devices.

Time‐resolved photoelectron spectroscopy using synchrotron radiation time structure

Synchrotron radiation time structure is becoming a common tool for studying dynamic properties of materials. The main limitation is often the wide time domain the user would like to access with pump-probe experiments. In order to perform photoelectron spectroscopy experiments over time scales from milliseconds to picoseconds it is mandatory to measure the time at which each measured photoelectron was created. For this reason the usual CCD camera-based two-dimensional detection of electron energy analyzers has been replaced by a new delay-line detector adapted to the time structure of the SOLEIL synchrotron radiation source. The new two-dimensional delay-line detector has a time resolution of 5 ns and was installed on a Scienta SES 2002 electron energy analyzer. The first application has been to characterize the time of flight of the photoemitted electrons as a function of their kinetic energy and the selected pass energy. By repeating the experiment as a function of the available pass energy and of the kinetic energy, a complete characterization of the analyzer behaviour in the time domain has been obtained. Even for kinetic energies as low as 10 eV at 2 eV pass energy, the time spread of the detected electrons is lower than 140 ns. These results and the time structure of the SOLEIL filling modes assure the possibility of performing pump-probe photoelectron spectroscopy experiments with the time resolution given by the SOLEIL pulse width, the best performance of the beamline and of the experimental station.

Valence Electron Photoemission Spectrum of Semiconductors: Ab Initio Description of Multiple Satellites

The experimental valence band photoemission spectrum of semiconductors exhibits multiple satellites that cannot be described by the GW approximation for the self-energy in the framework of many-body perturbation theory. Taking silicon as a prototypical example, we compare experimental high energy photoemission spectra with GW calculations and analyze the origin of the GW failure. We then propose an approximation to the functional differential equation that determines the exact one-body Greens function, whose solution has an exponential form. This yields a calculated spectrum, including cross sections, secondary electrons, and an estimate for extrinsic and interference effects, in excellent agreement with experiment. Our result can be recast as a dynamical vertex correction beyond GW, giving hints for further developments.