Unconventional Charge-Density-Wave Gap in Monolayer NbS2.

Using scanning tunneling microscopy and spectroscopy, for a monolayer of transition metal dichalcogenide H-NbS2 grown by molecular beam epitaxy on graphene, we provide unambiguous evidence for a charge density wave (CDW) with a 3 × 3 superstructure, which is not present in bulk NbS2. Local spectroscopy displays a pronounced gap on the order of 20 meV at the Fermi level. Within the gap, low-energy features are present. The gap structure with its low-energy features is at variance with the expectation for a gap opening in the electronic band structure due to a CDW. Instead, comparison with ab initio calculations indicates that the observed gap structure must be attributed to combined electron-phonon quasiparticles. The phonons in question are the elusive amplitude and phase collective modes of the CDW transition. Our findings advance the understanding of CDW mechanisms in 2D materials and their spectroscopic signatures.

Selecting the Reaction Path in On-Surface Synthesis through the Electron Chemical Potential in Graphene.

The organometallic on-surface synthesis of the eight-membered sp2 carbon-based ring cyclooctatetraene (C8H8, Cot) with the neighboring rare-earth elements ytterbium and thulium yields fundamentally different products for the two lanthanides, when conducted on graphene (Gr) close to the charge neutrality point. Sandwich-molecular YbCot wires of more than 500 Å length being composed of an alternating sequence of Yb atoms and upright-standing Cot molecules result from the on-surface synthesis with Yb. In contrast, repulsively interacting TmCot dots consisting of a single Cot molecule and a single Tm atom result from the on-surface synthesis with Tm. While the YbCot wires are bound through van der Waals interactions to the substrate, the dots are chemisorbed to Gr via the Tm atoms being more electropositive compared to Yb atoms. When the electron chemical potential in Gr is substantially raised (n-doping) through backside doping from an intercalation layer, the reaction product in the synthesis with Tm can be tuned to TmCot sandwich-molecular wires rather than TmCot dots. By use of density functional theory, it is found that the reduced electronegativity of Gr upon n-doping weakens the binding as well as the charge transfer between the reaction intermediate TmCot dot and Gr. Thus, the assembly of the TmCot dots to long TmCot sandwich-molecular wires becomes energetically favorable. It is thereby demonstrated that the electron chemical potential in Gr can be used as a control parameter in an organometallic on-surface synthesis to tune the outcome of a reaction.

Temperature-Controlled Rotational Epitaxy of Graphene.

When graphene is placed on a crystalline surface, the periodic structures within the layers superimpose and moiré superlattices form. Small lattice rotations between the two materials in contact strongly modify the moiré lattice parameter, upon which many electronic, vibrational, and chemical properties depend. While precise adjustment of the relative orientation in the degree- and sub-degree-range can be achieved via careful deterministic transfer of graphene, we report on the spontaneous reorientation of graphene on a metallic substrate, Ir(111). We find that selecting a substrate temperature between 1530 and 1000 K during the growth of graphene leads to distinct relative rotational angles of 0°, ± 0.6°, ±1.1°, and ±1.7°. When modeling the moiré superlattices as two-dimensional coincidence networks, we can ascribe the observed rotations to favorable low-strain graphene structures. The dissimilar thermal expansion of the substrate and graphene is regarded as an effective compressive biaxial pressure that is more easily accommodated in graphene by small rotations rather than by compression.

Suppression of wrinkle formation in graphene on Ir(111) by high-temperature, low-energy ion irradiation.

Graphene on Ir(111) is irradiated with small fluences of 500 eV He ions at temperatures close to its chemical vapor deposition growth temperature. The ion irradiation experiments explore whether it is possible to suppress the formation of wrinkles in Gr during growth. It is found that the release of thermal mismatch strain by wrinkle formation can be entirely suppressed for an irradiation temperature of 880 °C. A model for the ion beam induced suppression of wrinkle formation in supported Gr is presented, and underpinned by experiments varying the irradiation temperature or involving intercalation subsequent to irradiation.

Resonance Raman Spectrum of Doped Epitaxial Graphene at the Lifshitz Transition.

We employ ultra-high vacuum (UHV) Raman spectroscopy in tandem with angle-resolved photoemission (ARPES) to investigate the doping-dependent Raman spectrum of epitaxial graphene on Ir(111). The evolution of Raman spectra from pristine to heavily Cs doped graphene up to a carrier concentration of 4.4 × 1014 cm-2 is investigated. At this doping, graphene is at the onset of the Lifshitz transition and renormalization effects reduce the electronic bandwidth. The optical transition at the saddle point in the Brillouin zone then becomes experimentally accessible by ultraviolet (UV) light excitation, which achieves resonance Raman conditions in close vicinity to the van Hove singularity in the joint density of states. The position of the Raman G band of fully doped graphene/Ir(111) shifts down by ∼60 cm-1. The G band asymmetry of Cs doped epitaxial graphene assumes an unusual strong Fano asymmetry opposite to that of the G band of doped graphene on insulators. Our calculations can fully explain these observations by substrate dependent quantum interference effects in the scattering pathways for vibrational and electronic Raman scattering.

Suppression of Quasiparticle Scattering Signals in Bilayer Graphene Due to Layer Polarization and Destructive Interference.

We study chemically gated bilayer graphene using scanning tunneling microscopy and spectroscopy complemented by tight-binding calculations. Gating is achieved by intercalating Cs between bilayer graphene and Ir(111), thereby shifting the conduction band minima below the chemical potential. Scattering between electronic states (both intraband and interband) is detected via quasiparticle interference. However, not all expected processes are visible in our experiment. We uncover two general effects causing this suppression: first, intercalation leads to an asymmetrical distribution of the states within the two layers, which significantly reduces the scanning tunneling spectroscopy signal of standing waves mainly present in the lower layer; second, forward scattering processes, connecting points on the constant energy contours with parallel velocities, do not produce pronounced standing waves due to destructive interference. We present a theory to describe the interference signal for a general n-band material.

From Permeation to Cluster Arrays: Graphene on Ir(111) Exposed to Carbon Vapor.

Our scanning tunneling microscopy and X-ray photoelectron spectroscopy experiments along with first-principles calculations uncover the rich phenomenology and enable a coherent understanding of carbon vapor interaction with graphene on Ir(111). At high temperatures, carbon vapor not only permeates to the metal surface but also densifies the graphene cover. Thereby, in addition to underlayer graphene growth, upon cool down also severe wrinkling of the densified graphene cover is observed. In contrast, at low temperatures the adsorbed carbon largely remains on top and self-organizes into a regular array of fullerene-like, thermally highly stable clusters that are covalently bonded to the underlying graphene sheet. Thus, a new type of predominantly sp2-hybridized nanostructured and ultrathin carbon material emerges, which may be useful to encage or stably bind metal in finely dispersed form.

On-Surface Synthesis of Sandwich Molecular Nanowires on Graphene.

We demonstrate a new synthesis route for the growth of organometallic sandwich molecular nanowires, taking the example of Eu-cyclooctatetraene (EuCot), a predicted ferromagnetic semiconductor. We employ simultaneous exposure of Cot molecules and Eu vapor in ultrahigh vacuum to an inert substrate, such as graphene. Using a Cot excess under temperature conditions of a finite residence time of the molecule, the reactand diffusion confined to two dimensions results in a clean product of ultralong wires. In situ scanning tunneling microscopy reveals not only their molecular structure but also a rich and intriguing growth morphology. The new on-surface synthesis permits experimental access to a largely unexplored class of one-dimensional organometallic systems with potential for exciting electronic and magnetic properties.

Blister-free ion beam patterning of supported graphene.

Ion irradiation of metal supported two-dimensional layers results over a broad parameter space in noble gas trapping at the interface of the two-dimensional layer and the metal substrate. Trapping may give rise to the formation of gas filled blisters which deteriorate the structural and electronic properties of graphene. Here, we investigate the dependence of noble gas trapping at a graphene/Ir(111) interface and of graphene sputtering on the angle of incidence using scanning tunneling microscopy. Our experimental results are compared to dedicated molecular dynamics simulations. We find that at large impact angles of [Formula: see text] graphene can be eroded without noble gas trapping and thereby establish conditions for nanopatterning without concomitant blister formation.

Tuning the van der Waals Interaction of Graphene with Molecules via Doping.

We use scanning tunneling microscopy to visualize and thermal desorption spectroscopy to quantitatively measure that the binding of naphthalene molecules to graphene, a case of pure van der Waals interaction, strengthens with n and weakens with p doping of graphene. Density-functional theory calculations that include the van der Waals interaction in a seamless, ab initio way accurately reproduce the observed trend in binding energies. Based on a model calculation, we propose that the van der Waals interaction is modified by changing the spatial extent of graphene's π orbitals via doping.

Spin-polarized surface state in EuO(100).

High-quality films of the ferromagnetic semiconductor EuO are grown on epitaxial graphene on Ir(111) and investigated in situ with scanning tunneling microscopy and spectroscopy. Electron scattering at defects leads to standing-wave patterns, manifesting the existence of a surface state in EuO. The surface state is analyzed at different temperatures and energies. We observe a pronounced energy shift of the surface state when cooling down below the Curie temperature TC, which indicates a spin polarization of this state at low temperatures. The experimental results are in agreement with corresponding density functional theory calculations.

Silicide induced ion beam patterning of Si(001).

Low energy ion beam pattern formation on Si with simultaneous co-deposition of Ag, Pd, Pb, Ir, Fe or C impurities was investigated by in situ scanning tunneling microscopy as well as ex situ atomic force microscopy, scanning electron microscopy, transmission electron microscopy and Rutherford backscattering spectrometry. The impurities were supplied by sputter deposition. Additional insight into the mechanism of pattern formation was obtained by more controlled supply through e-beam evaporation. For the situations investigated, the ability of the impurity to react with Si, i.e. to form a silicide, appears to be a necessary, but not a sufficient condition for pattern formation. Comparing the effects of impurities with similar mass and nuclear charge, the collision kinetics is shown to be not of primary importance for pattern formation. To understand the observed phenomena, it is necessary to assume a bi-directional coupling of composition and height fluctuations. This coupling gives rise to a sensitive dependence of the final morphology on the conditions of impurity supply. Because of this history dependence, the final morphology cannot be uniquely characterized by a steady state impurity concentration.

Ion impacts on graphene/Ir(111): interface channeling, vacancy funnels, and a nanomesh.

By combining ion beam experiments and atomistic simulations we study the production of defects in graphene on Ir(111) under grazing incidence of low energy Xe ions. We demonstrate that the ions are channeled in between graphene and the substrate, giving rise to chains of vacancy clusters with their edges bending down toward the substrate. These clusters self-organize to a graphene nanomesh via thermally activated diffusion as their formation energy varies within the graphene moiré supercell.

The backside of graphene: manipulating adsorption by intercalation.

The ease by which graphene is affected through contact with other materials is one of its unique features and defines an integral part of its potential for applications. Here, it will be demonstrated that intercalation, the insertion of atomic layers in between the backside of graphene and the supporting substrate, is an efficient tool to change its interaction with the environment on the frontside. By partial intercalation of graphene on Ir(111) with Eu or Cs we induce strongly n-doped graphene patches through the contact with these intercalants. They coexist with nonintercalated, slightly p-doped graphene patches. We employ these backside doping patterns to directly visualize doping induced binding energy differences of ionic adsorbates to graphene through low-temperature scanning tunneling microscopy. Density functional theory confirms these binding energy differences and shows that they are related to the graphene doping level.

2D Vanadium Sulfides: Synthesis, Atomic Structure Engineering, and Charge Density Waves.

Two ultimately thin vanadium-rich 2D materials based on VS2 are created via molecular beam epitaxy and investigated using scanning tunneling microscopy, X-ray photoemission spectroscopy, and density functional theory (DFT) calculations. The controlled synthesis of stoichiometric single-layer VS2 or either of the two vanadium-rich materials is achieved by varying the sample coverage and sulfur pressure during annealing. Through annealing of small stoichiometric single-layer VS2 islands without S pressure, S-vacancies spontaneously order in 1D arrays, giving rise to patterned adsorption. Via the comparison of DFT calculations with scanning tunneling microscopy data, the atomic structure of the S-depleted phase, with a stoichiometry of V4S7, is determined. By depositing larger amounts of vanadium and sulfur, which are subsequently annealed in a S-rich atmosphere, self-intercalated ultimately thin V5S8-derived layers are obtained, which host 2 × 2 V-layers between sheets of VS2. We provide atomic models for the thinnest V5S8-derived structures. Finally, we use scanning tunneling spectroscopy to investigate the charge density wave observed in the 2D V5S8-derived islands.

Strain in epitaxial graphene visualized by intercalation.

Intercalation of Eu under graphene on Ir(111) results in patterns oriented along the graphene moiré and quantized in size by its unit mesh. The patterns are formed by stripes, compact islands, and channels. Over a wide range of intercalated amounts the step concentration of the pattern has a rather constant saturation value. These findings are explained by the chemically modulated binding of graphene to the substrate and the preexisting strain in graphene due to its cooldown from the growth temperature. Local variations in the intercalation step density appear to reflect local variations in the preexisting strain.

Mapping image potential states on graphene quantum dots.

Free-electron-like image potential states are observed in scanning tunneling spectroscopy on graphene quantum dots on Ir(111) acting as potential wells. The spectrum strongly depends on the size of the nanostructure as well as on the spatial position on top, indicating lateral confinement. Analysis of the substructure of the first state by the spatial mapping of the constant energy local density of states reveals characteristic patterns of confined states. The most pronounced state is not the ground state, but an excited state with a favorable combination of the local density of states and parallel momentum transfer in the tunneling process. Chemical gating tunes the confining potential by changing the local work function. Our experimental determination of this work function allows us to deduce the associated shift of the Dirac point.

Interplay of wrinkles, strain, and lattice parameter in graphene on iridium.

Following graphene growth by thermal decomposition of ethylene on Ir(111) at high temperatures we analyzed the strain state and the wrinkle formation kinetics as function of temperature. Using the moiré spot separation in a low energy electron diffraction pattern as a magnifying mechanism for the difference in the lattice parameters between Ir and graphene, we achieved an unrivaled relative precision of ±0.1 pm for the graphene lattice parameter. Our data reveals a characteristic hysteresis of the graphene lattice parameter that is explained by the interplay of reversible wrinkle formation and film strain. We show that graphene on Ir(111) always exhibits residual compressive strain at room temperature. Our results provide important guidelines for strategies to avoid wrinkling.

Unidirectional Nano-modulated Binding and Electron Scattering in Epitaxial Borophene.

A complex interplay between the crystal structure and the electron behavior within borophene renders this material an intriguing 2D system, with many of its electronic properties still undiscovered. Experimental insight into those properties is additionally hampered by the limited capabilities of the established synthesis methods, which, in turn, inhibits the realization of potential borophene applications. In this multimethod study, photoemission spectroscopies and scanning probe techniques complemented by theoretical calculations have been used to investigate the electronic characteristics of a high-coverage, single-layer borophene on the Ir(111) substrate. Our results show that the binding of borophene to Ir(111) exhibits pronounced one-dimensional modulation and transforms borophene into a nanograting. The scattering of photoelectrons from this structural grating gives rise to the replication of the electronic bands. In addition, the binding modulation is reflected in the chemical reactivity of borophene and gives rise to its inhomogeneous aging effect. Such aging is easily reset by dissolving boron atoms in iridium at high temperature, followed by their reassembly into a fresh atomically thin borophene mesh. Besides proving electron-grating capabilities of the boron monolayer, our data provide comprehensive insight into the electronic properties of epitaxial borophene which is vital for further examination of other boron systems of reduced dimensionality.

Water Chemistry beneath Graphene: Condensation of a Dense OH-H2O Phase under Graphene.

Room temperature oxygen hydrogenation below graphene flakes supported by Ir(111) is investigated through a combination of X-ray photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory calculations using an evolutionary search algorithm. We demonstrate how the graphene cover and its doping level can be used to trap and characterize dense mixed O-OH-H2O phases that otherwise would not exist. Our study of these graphene-stabilized phases and their response to oxygen or hydrogen exposure reveals that additional oxygen can be dissolved into them at room temperature creating mixed O-OH-H2O phases with an increased areal coverage underneath graphene. In contrast, additional hydrogen exposure converts the mixed O-OH-H2O phases back to pure OH-H2O with a reduced areal coverage underneath graphene.