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. Here we report the formation of a two-dimensional dodecagonal fullerene quasicrystal on a Pt3Ti(111) surface, which can be described in terms of a square-triangle tiling. Employing density functional theory calculations, we identify the complex adsorption energy landscape of the Pt-terminated Pt3Ti surface that is responsible for the quasicrystal formation. We demonstrate the presence of quasicrystal-specific phason strain, which provides the degree of freedom required to accommodate the quasicrystalline structure on the periodic substrate. Our results reveal detailed insight into an interface-driven formation mechanism and open the way to the creation of tailored fullerene quasicrystals with specific physical properties.

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. Using voltage dependent imaging the surface termination of Pt3Ti(111) was studied with atomic resolution. Combining these images with simulated STM maps based on ab initio DFT calculations allowed us to identify the three upper layers of the Pt3Ti(111) single crystal and their influence upon the surface electronic structure. Our results show that small changes in the composition of the second and third atomic layer are of significant influence upon the surface electronic structure of the Pt3Ti electro catalyst. Furthermore, we provide relevant insights into the dependence of the surface termination on the preparation conditions.

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. Depending on the pressure, temperature and duration of O2 exposure as well as on the graphene morphology, O-(2 × 2), O-(√3×√3)-R30°, O-(2 × 1) and O-(2√3 × 2√3)-R30° superstructures with respect to Ir(111) are observed under the graphene cover. Two of these structures, the O-(√3 × âˆš3)-R30° and the (2√3 × 2√3)-R30° structure are only observed when the graphene layer is on top. Phase coexistence and formation conditions of the intercalation structures between graphene and Ir(111) are analyzed. The experimental results are compared to density functional theory calculations including dispersive forces. The existence of these phases under graphene and their absence on bare Ir(111) are discussed in terms of possible changes in the adsorbate-substrate interaction due to the presence of the graphene cover.

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. In contrast to the Fe / Ir(1 1 1) surface, graphene/Fe / Ir(1 1 1) exhibits ferromagnetic order with an out-of-plane easy magnetization axis. At the nanometer scale, our experiments reveal that the moiré pattern induces a lateral variation of the TMR, which reaches 80%. The measured TMR at valleys of the moiré pattern is higher than at hills. We interpret this modulation in terms of a different hybridization between graphene and Fe at valleys and hills due to a different graphene-Fe distance at these sites, which leads to a different transmission of spin-polarized states.

Rationale for switching to nonlocal functionals in density functional theory.

Density functional theory (DFT) has been steadily improving over the past few decades, becoming the standard tool for electronic structure calculations. The early local functionals (LDA) were eventually replaced by more accurate semilocal functionals (GGA) which are in use today. A major persisting drawback is the lack of the nonlocal correlation which is at the core of dispersive (van der Waals) forces, so that a large and important class of systems remains outside the scope of DFT. The vdW-DF correlation functional of Langreth and Lundqvist, published in 2004, was the first nonlocal functional which could be easily implemented. Beyond expectations, the nonlocal functional has brought significant improvement to systems that were believed not to be sensitive to nonlocal correlations. In this paper, we use the example of graphene nanodomes growing on the Ir(111) surface, where with an increase of the size of the graphene islands the character of the bonding changes from strong chemisorption towards almost pure physisorption. We demonstrate how the seamless character of the vdW-DF functionals makes it possible to treat all regimes self-consistently, proving to be a systematic and consistent improvement of DFT regardless of the nature of bonding. We also discuss the typical surface science example of CO adsorption on (111) surfaces of metals, which shows that the nonlocal correlation may also be crucial for strongly chemisorbed systems. We briefly discuss open questions, in particular the choice of the most appropriate exchange part of the functional. As the vdW-DF begins to appear implemented self-consistently in a number of popular DFT codes, with numerical costs close to the GGA calculations, we draw the attention of the DFT community to the advantages and benefits of the adoption of this new class of functionals.

Fine tuning of the electronic structure of π-conjugated molecules for molecular electronics.

Molecular components with their inherent scalability are expected to be promising supplements for nanoscale electronic devices. Here we report on how to specifically tune the electronic structure of chemisorbed molecules and thus to gain control of molecular transport properties. The electronic structure of our prototype π-conjugated carboxylic acid anchored on the Cu(110) surface is modified systematically by inserting nitrogen atoms in a six-membered aromatic ring, a carboxylic functional group at the aromatic ring or both. Depending on the specific nature of the substituent, the relative position of the occupied or unoccupied electronic states with respect to the Fermi level can be specifically controlled and thus the transport properties of the studied molecular systems are modified intentionally, as proven by our scanning tunneling spectroscopy measurements. On the basis of the insight gained by our systematic experiment and first-principles calculations we are also able to predict the specific molecular character (σ or π) of the orbitals involved in the transport process of a carboxylate-Cu(110) system, depending on the functionalization pattern employed.

Electronic mapping of molecular orbitals at the molecule-metal interface.

The molecule-metal interface formed by pyridine-2,5-dicarboxylic acid chemically bonded to the Cu(110) surface is investigated by scanning tunneling microscopy and first-principles calculations. Our current-voltage spectroscopy studies reveal an electronic mapping of molecular orbitals as a function of tip position. By combining experimental and theoretical investigations, individual molecular orbitals are characterized by their energy and spatial distribution. The importance of adsorption geometries and conformational changes on the electron transport properties is highlighted.

Ab initio simulation of atomic-scale imaging in noncontact atomic force microscopy.

In this paper, we summarize some results of our ab initio simulations aimed at investigating the mechanism of the NC-AFM image contrast on semiconductor and metallic surfaces. We start with an introduction into the basic ideas behind the ab initio simulation process of the NC-AFM experimental results. Our simulations reveal that the interaction of a clean silicon tip with a semiconductor surface like InAs(110) might lead to bond-formation and bond-breaking processes during the approach and retraction of the tip. This imaging mechanism is very similar to that observed on a metallic surface like Ag(110). Interestingly, a clean silicon tip can become contaminated with Ag surface atoms. On both types of surface we observe a significant energy dissipation which is caused by a hysteresis in the tip-sample force curves calculated on the approach and retraction path.

Chemical versus van der Waals Interaction: the role of the heteroatom in the flat absorption of aromatic molecules C6H6, C5NH5, and C4N2H4 on the Cu(110) surface.

We perform first-principles calculations aimed at investigating the role of a heteroatom such as N in the chemical and long-range van der Waals (vdW) interactions for a flat adsorption of several pi-conjugated molecules on the Cu(110) surface. Our study reveals that the alignment of the molecular orbitals at the adsorbate-substrate interface depends on the number of heteroatoms. As a direct consequence, the molecule-surface vdW interactions involve not only pi-like orbitals which are perpendicular to the molecular plane but also sigma-like orbitals delocalized in the molecular plane.

Probing the magnetic exchange forces of iron on the atomic scale.

Applying magnetic exchange force microscopy with an Fe-coated tip, we experimentally resolve the atomic-scale antiferromagnetic structure of the Fe monolayer on W(001). On the basis of first-principles calculations, using an Fe nanocluster as a tip, we determine the distance dependence of the magnetic exchange forces. Significant relaxation of tip and sample atoms occurs, which depend sensitively on the local magnetic configuration. This shifts the onset of magnetic interactions toward larger separations and facilitates their observation. Implementing a multiatom tip in the calculations and accounting for relaxation effects are crucial to obtain the correct sign and distance dependence of the magnetic exchange interaction. By comparison with our calculations, we show that the experimentally observed contrast is due to a competition between chemical and magnetic forces.

Atomic-scale sharpening of silicon tips in noncontact atomic force microscopy.

The atomic-scale stability of clean silicon tips used in noncontact atomic force microscopy (NC-AFM) is simulated by ab initio calculations based on density functional theory. The tip structures are modeled by silicon clusters with and termination. For the often assumed Si(111)-type tip we observe the sharpening of the initially blunt tip via short-range chemical forces during the first approach and retraction cycle. The structural changes corresponding to this intrinsic process are irreversible and lead to stable NC-AFM imaging conditions. In opposition to the picture used in literature, the Si(001)-type tip does not exhibit the so-called "two-dangling bond" feature as a bulklike termination suggests.