Molecular Order Induced Charge Transfer in a C-Topological Insulator Moiré Heterostructure.

We synthesized and spectroscopically investigated monolayer (ML) C on the topological insulator (TI) BiTe. This C/BiTe heterostructure is characterized by an excellent translational order in a novel (4 × 4) C superstructure on a (9 × 9) cell of BiTe. Angle-resolved photoemission spectroscopy (ARPES) of C/BiTe reveals that ML C accepts electrons from the TI at room temperature, but no charge transfer occurs at low temperatures.

Engineering 2D Materials from Single-Layer NbS.

Starting from a single layer of NbS grown on graphene by molecular beam epitaxy, the single unit cell thick 2D materials NbS-2D and NbS-2D are created using two different pathways. Either annealing under sulfur-deficient conditions at progressively higher temperatures or deposition of increasing amounts of Nb at elevated temperature result in phase-pure NbS-2D followed by NbS-2D. The materials are characterized by scanning tunneling microscopy, scanning tunneling spectroscopy, and X-ray photoemission spectroscopy.

Spin-Dependent ππ^{*} Gap in Graphene on a Magnetic Substrate.

We present a detailed analysis of the electronic properties of graphene/Eu/Ni(111). By using angle- and spin-resolved photoemission spectroscopy and ab initio calculations, we show that the intercalation of Eu in the graphene/Ni(111) interface gives rise to a gapped freestanding dispersion of the ππ^{*} Dirac cones at the K[over ¯] point with an additional lifting of the spin degeneracy due to the mixing of graphene and Eu states. The interaction with the magnetic substrate results in a large spin-dependent gap in the Dirac cones with a topological nature characterized by a large Berry curvature and a spin-polarized Van Hove singularity, whose closeness to the Fermi level gives rise to a polaronic band.

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

Two ultimately thin vanadium-rich 2D materials based on VS 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 VS 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 VS islands without S pressure, S-vacancies spontaneously order in 1D arrays, giving rise to patterned adsorption.

Enantioselective Adsorption on Magnetic Surfaces.

From the beginning of molecular theory, the interplay of chirality and magnetism has intrigued scientists. There is still the question if enantiospecific adsorption of chiral molecules occurs on magnetic surfaces. Enantiomer discrimination was conjectured to arise from chirality-induced spin separation within the molecules and exchange interaction with the substrate's magnetization.

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

The organometallic on-surface synthesis of the eight-membered sp carbon-based ring cyclooctatetraene (CH, 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.

Tailoring magnetic anisotropy by graphene-induced selective skyhook effect on 4f-metals.

From macroscopic heavy-duty permanent magnets to nanodevices, the precise control of the magnetic properties in rare-earth metals is crucial for many applications used in our daily life. Therefore, a detailed understanding and manipulation of the 4f-metals' magnetic properties are key to further boosting the functionalization and efficiency of future applications. We present a proof-of-concept approach consisting of a dysprosium-iridium surface alloy in which graphene adsorption allows us to tailor its magnetic properties.

A Monolayer of Hexagonal Boron Nitride on Ir(111) as a Template for Cluster Superlattices.

The moiré of a monolayer of hexagonal boron nitride on Ir(111) is found to be a template for Ir, C, and Au cluster superlattices. Using scanning tunneling microscopy, the cluster structure and epitaxial relation to the substrate, the cluster binding site, the role of defects, as well as the thermal stability of the cluster lattice are investigated. The Ir and C cluster superlattices display a high thermal stability, before they decay by intercalation and Smoluchowski ripening.

Guided Molecular Assembly on a Locally Reactive 2D Material.

Atomically precise engineering of the position of molecular adsorbates on surfaces of 2D materials is key to their development in applications ranging from catalysis to single-molecule spintronics. Here, stable room-temperature templating of individual molecules with localized electronic states on the surface of a locally reactive 2D material, silicene grown on ZrB , is demonstrated. Using a combination of scanning tunneling microscopy and density functional theory, it is shown that the binding of iron phthalocyanine (FePc) molecules is mediated via the strong chemisorption of the central Fe atom to the sp -like dangling bond of Si atoms in the linear silicene domain boundaries.

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.

Interface-driven formation of a two-dimensional dodecagonal fullerene quasicrystal.

Since their discovery, quasicrystals have attracted continuous research interest due to their unique structural and physical properties. Recently, it was demonstrated that dodecagonal quasicrystals could be used as bandgap materials in next-generation photonic devices. However, a full understanding of the formation mechanism of quasicrystals is necessary to control their physical properties.

Structure and Growth of Hexagonal Boron Nitride on Ir(111).

Using the X-ray standing wave method, scanning tunneling microscopy, low energy electron diffraction, and density functional theory, we precisely determine the lateral and vertical structure of hexagonal boron nitride on Ir(111). The moiré superstructure leads to a periodic arrangement of strongly chemisorbed valleys in an otherwise rather flat, weakly physisorbed plane. The best commensurate approximation of the moiré unit cell is (12 × 12) boron nitride cells resting on (11 × 11) substrate cells, which is at variance with several earlier studies.

Sub-molecular modulation of a 4f driven Kondo resonance by surface-induced asymmetry.

Coupling between a magnetic impurity and an external bath can give rise to many-body quantum phenomena, including Kondo and Hund's impurity states in metals, and Yu-Shiba-Rusinov states in superconductors. While advances have been made in probing the magnetic properties of d-shell impurities on surfaces, the confinement of f orbitals makes them difficult to access directly. Here we show that a 4f driven Kondo resonance can be modulated spatially by asymmetric coupling between a metallic surface and a molecule containing a 4f-like moment.

Tuning the surface electronic structure of a Pt3Ti(111) electro catalyst.

Increasing the efficiency and stability of bimetallic electro catalysts is particularly important for future clean energy technologies. However, the relationship between the surface termination of these alloys and their catalytic activity is poorly understood. Therefore, we report on fundamental UHV-SPM, LEED, and DFT calculations of the Pt3Ti(111) single crystal surface.

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.

Oxygen orders differently under graphene: new superstructures on Ir(111).

Using scanning tunneling microscopy, the oxygen adsorbate superstructures on bare Ir(111) are identified and compared to the ones formed by intercalation in between graphene and the Ir(111) substrate. For bare Ir(111) we observe O-(2 × 2) and O-(2 × 1) structures, thereby clarifying a persistent uncertainty about the existence of these structures and the role of defects for their stability. For the case of graphene-covered Ir(111), oxygen intercalation superstructures can be imaged through the graphene monolayer by choosing proper tunneling conditions.

Structure and dynamics in liquid bismuth and Bi(n) clusters: a density functional study.

Density functional/molecular dynamics simulations with more than 500 atoms have been performed on liquid bismuth at 573, 773, 923, and 1023 K and on neutral Bi clusters with up to 14 atoms. There are similar structural patterns (coordination numbers, bond angles, and ring patterns) in the liquid and the clusters, with significant differences from the rhombohedral crystalline form. We study the details of the structure (structure factor, pair, and cavity distribution functions) and dynamical properties (vibration frequencies, diffusion constants, power spectra), and compare with experimental results where available.

Long-range magnetic coupling between nanoscale organic-metal hybrids mediated by a nanoskyrmion lattice.

The design of nanoscale organic-metal hybrids with tunable magnetic properties as well as the realization of controlled magnetic coupling between them open gateways for novel molecular spintronic devices. Progress in this direction requires a combination of a clever choice of organic and thin-film materials, advanced magnetic characterization techniques with a spatial resolution down to the atomic length scale, and a thorough understanding of magnetic properties based on first-principles calculations. Here, we make use of carbon-based systems of various nanoscale size, such as single coronene molecules and islands of graphene, deposited on a skyrmion lattice of a single atomic layer of iron on an iridium substrate, in order to tune the magnetic characteristics (for example, magnetic moments, magnetic anisotropies and coercive field strengths) of the organic-metal hybrids.

Local tunnel magnetoresistance of an iron intercalated graphene-based heterostructure.

The lateral variation of the tunnel magnetoresistance (TMR) of a graphene-based vertical heterostructure is studied by spin-polarized scanning tunneling microscopy (SP-STM) using an Fe-coated probe tip. The well-defined heterostructure is obtained by the intercalation of a magnetic Fe monolayer at the graphene/Ir(1 1 1) interface. Its structure is characterized by a moiré pattern with a high corrugation.

Magnetic hardening induced by nonmagnetic organic molecules.

We reveal for the first time through a theoretical first-principles study that the adsorption of a nonmagnetic π-conjugated organic molecule on a ferromagnetic surface locally increases the strength of the magnetic exchange interaction between the magnetic atoms binding directly to the molecule. This magnetic hardening effect leads to the creation of a local molecular mediated magnetic unit with a stable magnetization direction and an enhanced barrier for the magnetization switching as compared to the clean surface. Remarkably, such a hybrid organic-ferromagnetic system exhibits also a spin-filter functionality with sharp spin-split molecularlike electronic features at the molecular site.

First-principles insights into the electronic and magnetic structure of hybrid organic-metal interfaces.

In this review we summarize our experience gained from several recent ab initio studies aimed to investigate how the competition between short-ranged chemical and long-ranged dispersion interactions determines the bonding mechanism of a specific set of chemically functionalized π-conjugated organic molecules on non-magnetic and magnetic metal surfaces. A key point of this review is to provide a detailed analysis on the issue of how to tune the strength of the organic molecule-surface interaction, such that the nature of the molecular bonding exhibits the specific electronic features of the physisorption or chemisorption bonding mechanisms. In particular, we discuss in detail how the precise control of these bonding mechanisms can be used to design specific electronic and magnetic properties of hybrid organic-metallic interfaces.

Spin polarization of Co(0001)/graphene junctions from first principles.

Junctions comprised of ferromagnets and nonmagnetic materials are one of the key building blocks in spintronics. With the recent breakthroughs of spin injection in ferromagnet/graphene junctions it is possible to consider spin-based applications that are not limited to magnetoresistive effects. However, for critical studies of such structures it is crucial to establish accurate predictive methods that would yield atomically resolved information on interfacial properties.

The mechanism of caesium intercalation of graphene.

Properties of many layered materials, including copper- and iron-based superconductors, topological insulators, graphite and epitaxial graphene, can be manipulated by the inclusion of different atomic and molecular species between the layers via a process known as intercalation. For example, intercalation in graphite can lead to superconductivity and is crucial in the working cycle of modern batteries and supercapacitors. Intercalation involves complex diffusion processes along and across the layers; however, the microscopic mechanisms and dynamics of these processes are not well understood.

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.