Shaping Graphene Superconductivity with Nanometer Precision.

Graphene holds great potential for superconductivity due to its pure 2D nature, the ability to tune its carrier density through electrostatic gating, and its unique, relativistic-like electronic properties. At present, still far from controlling and understanding graphene superconductivity, mainly because the selective introduction of superconducting properties to graphene is experimentally very challenging. Here, a method is developed that enables shaping at will graphene superconductivity through a precise control of graphene-superconductor junctions. The method combines the proximity effect with scanning tunnelling microscope (STM) manipulation capabilities. Pb nano-islands are first grown that locally induce superconductivity in graphene. Using a STM, Pb nano-islands can be selectively displaced, over different types of graphene surfaces, with nanometre scale precision, in any direction, over distances of hundreds of nanometres. This opens an exciting playground where a large number of predefined graphene-superconductor hybrid structures can be investigated with atomic scale precision. To illustrate the potential, a series of experiments are performed, rationalized by the quasi-classical theory of superconductivity, going from the fundamental understanding of superconductor-graphene-superconductor heterostructures to the construction of superconductor nanocorrals, further used as "portable" experimental probes of local magnetic moments in graphene.

Bound Hole States Associated to Individual Vanadium Atoms Incorporated into Monolayer WSe_{2}.

Doping a two-dimensional semiconductor with magnetic atoms is a possible route to induce magnetism in the material. We report on the atomic structure and electronic properties of monolayer WSe_{2} intentionally doped with vanadium atoms by means of scanning transmission electron microscopy and scanning tunneling microscopy and spectroscopy. Most of the V atoms incorporate at W sites. These V_{W} dopants are negatively charged, which induces a localized bound state located 140 meV above the valence band maximum. The overlap of the electronic potential of two charged V_{W} dopants generates additional in-gap states. Eventually, the negative charge may suppress the magnetic moment on the V_{W} dopants.

Atomic-Layer Controlled Transition from Inverse Rashba-Edelstein Effect to Inverse Spin Hall Effect in 2D PtSe2 Probed by THz Spintronic Emission.

2D materials, such as transition metal dichalcogenides, are ideal platforms for spin-to-charge conversion (SCC) as they possess strong spin-orbit coupling (SOC), reduced dimensionality and crystal symmetries as well as tuneable band structure, compared to metallic structures. Moreover, SCC can be tuned with the number of layers, electric field, or strain. Here, SCC in epitaxially grown 2D PtSe2 by THz spintronic emission is studied since its 1T crystal symmetry and strong SOC favor SCC. High quality of as-grown PtSe2 layers is demonstrated, followed by in situ ferromagnet deposition by sputtering that leaves the PtSe2 unaffected, resulting in well-defined clean interfaces as evidenced with extensive characterization. Through this atomic growth control and using THz spintronic emission, the unique thickness-dependent electronic structure of PtSe2 allows the control of SCC. Indeed, the transition from the inverse Rashba-Edelstein effect (IREE) in 1-3 monolayers (ML) to the inverse spin Hall effect (ISHE) in multilayers (>3 ML) of PtSe2 enabling the extraction of the perpendicular spin diffusion length and relative strength of IREE and ISHE is demonstrated. This band structure flexibility makes PtSe2 an ideal candidate to explore the underlying mechanisms and engineering of the SCC as well as for the development of tuneable THz spintronic emitters.

Observation of Yu-Shiba-Rusinov States in Superconducting Graphene.

When magnetic atoms are inserted inside a superconductor, the superconducting order is locally depleted as a result of the antagonistic nature of magnetism and superconductivity. Thereby, distinctive spectral features, known as Yu-Shiba-Rusinov states, appear inside the superconducting gap. The search for Yu-Shiba-Rusinov states in different materials is intense, as they can be used as building blocks to promote Majorana modes suitable for topological quantum computing. Here, the first observation of Yu-Shiba-Rusinov states in graphene, a non-superconducting 2D material, and without the participation of magnetic atoms, is reported. Superconductivity in graphene is induced by proximity effect brought by adsorbing nanometer-scale superconducting Pb islands. Using scanning tunneling microscopy and spectroscopy the superconducting proximity gap is measured in graphene, and Yu-Shiba-Rusinov states are visualized in graphene grain boundaries. The results reveal the very special nature of those Yu-Shiba-Rusinov states, which extends more than 20 nm away from the grain boundaries. These observations provide the long-sought experimental confirmation that graphene grain boundaries host local magnetic moments and constitute the first observation of Yu-Shiba-Rusinov states in a chemically pure system.

Quantum Confinement of Dirac Quasiparticles in Graphene Patterned with Sub-Nanometer Precision.

Quantum confinement of graphene Dirac-like electrons in artificially crafted nanometer structures is a long sought goal that would provide a strategy to selectively tune the electronic properties of graphene, including bandgap opening or quantization of energy levels. However, creating confining structures with nanometer precision in shape, size, and location remains an experimental challenge, both for top-down and bottom-up approaches. Moreover, Klein tunneling, offering an escape route to graphene electrons, limits the efficiency of electrostatic confinement. Here, a scanning tunneling microscope (STM) is used to create graphene nanopatterns, with sub-nanometer precision, by the collective manipulation of a large number of H atoms. Individual graphene nanostructures are built at selected locations, with predetermined orientations and shapes, and with dimensions going all the way from 2 nm up to 1 µm. The method permits the patterns to be erased and rebuilt at will, and it can be implemented on different graphene substrates. STM experiments demonstrate that such graphene nanostructures confine very efficiently graphene Dirac quasiparticles, both in 0D and 1D structures. In graphene quantum dots, perfectly defined energy bandgaps up to 0.8 eV are found that scale as the inverse of the dot's linear dimension, as expected for massless Dirac fermions.

Beyond van der Waals Interaction: The Case of MoSe2 Epitaxially Grown on Few-Layer Graphene.

Van der Waals heterojunctions composed of graphene and transition metal dichalcogenides have gain much attention because of the possibility to control and tailor band structure, promising applications in two-dimensional optoelectronics and electronics. In this report, we characterized the van der Waals heterojunction MoSe2/few-layer graphene with a high-quality interface using cutting-edge surface techniques scaling from atomic to microscopic range. These surface analyses gave us a complete picture of the atomic structure and electronic properties of the heterojunction. In particular, we found two important results: the commensurability between the MoSe2 and few-layer graphene lattices and a band-gap opening in the few-layer graphene. The band gap is as large as 250 meV, and we ascribed it to an interface charge transfer that results in an electronic depletion in the few-layer graphene. This conclusion is well supported by electron spectroscopy data and density functional theory calculations. The commensurability between the MoSe2 and graphene lattices as well as the band-gap opening clearly show that the interlayer interaction goes beyond the simple van der Waals interaction. Hence, stacking two-dimensional materials in van der Waals heterojunctions enables us to tailor the atomic and electronic properties of individual layers. It also permits the introduction of a band gap in few-layer graphene by interface charge transfer.

Weakly Trapped, Charged, and Free Excitons in Single-Layer MoS2 in the Presence of Defects, Strain, and Charged Impurities.

Few- and single-layer MoS2 host substantial densities of defects. They are thought to influence the doping level, the crystal structure, and the binding of electron-hole pairs. We disentangle the concomitant spectroscopic expression of all three effects and identify to what extent they are intrinsic to the material or extrinsic to it, i.e., related to its local environment. We do so by using different sources of MoS2-a natural one and one prepared at high pressure and high temperature-and different substrates bringing varying amounts of charged impurities and by separating the contributions of internal strain and doping in Raman spectra. Photoluminescence unveils various optically active excitonic complexes. We discover a defect-bound state having a low binding energy of 20 meV that does not appear sensitive to strain and doping, unlike charged excitons. Conversely, the defect does not significantly dope or strain MoS2. Scanning tunneling microscopy and density functional theory simulations point to substitutional atoms, presumably individual nitrogen atoms at the sulfur site. Our work shows the way to a systematic understanding of the effect of external and internal fields on the optical properties of two-dimensional materials.

Atomic-scale control of graphene magnetism by using hydrogen atoms.

Isolated hydrogen atoms absorbed on graphene are predicted to induce magnetic moments. Here we demonstrate that the adsorption of a single hydrogen atom on graphene induces a magnetic moment characterized by a ~20-millielectron volt spin-split state at the Fermi energy. Our scanning tunneling microscopy (STM) experiments, complemented by first-principles calculations, show that such a spin-polarized state is essentially localized on the carbon sublattice opposite to the one where the hydrogen atom is chemisorbed. This atomically modulated spin texture, which extends several nanometers away from the hydrogen atom, drives the direct coupling between the magnetic moments at unusually long distances. By using the STM tip to manipulate hydrogen atoms with atomic precision, it is possible to tailor the magnetism of selected graphene regions.

Multiscale investigation of graphene layers on 6H-SiC(000-1).

In this article, a multiscale investigation of few graphene layers grown on 6H-SiC(000-1) under ultrahigh vacuum (UHV) conditions is presented. At 100-µm scale, the authors show that the UHV growth yields few layer graphene (FLG) with an average thickness given by Auger spectroscopy between 1 and 2 graphene planes. At the same scale, electron diffraction reveals a significant rotational disorder between the first graphene layer and the SiC surface, although well-defined preferred orientations exist. This is confirmed at the nanometer scale by scanning tunneling microscopy (STM). Finally, STM (at the nm scale) and Raman spectroscopy (at the µm scale) show that the FLG stacking is turbostratic, and that the domain size of the crystallites ranges from 10 to 100 nm. The most striking result is that the FLGs experience a strong compressive stress that is seldom observed for graphene grown on the C face of SiC substrates.