Testing functional anchor groups for the efficient immobilization of molecular catalysts on silver surfaces.

Modifications of complexes by attachment of anchor groups are widely used to control molecule-surface interactions. This is of importance for the fabrication of (catalytically active) hybrid systems, viz. of surface immobilized molecular catalysts. In this study, the complex fac-Re(S-Sbpy)(CO)3Cl (S-Sbpy = 3,3'-disulfide-2,2'-bipyridine), a sulfurated derivative of the prominent Re(bpy)(CO)3Cl class of CO2 reduction catalysts, was deposited onto the clean Ag(001) surface at room temperature. The complex is thermostable upon sublimation as supported by infrared absorption and nuclear magnetic resonance spectroscopy. Its anchoring process has been analyzed using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The growth behavior was directly contrasted to the one of the parent complex fac-Re(bpy)(CO)3Cl (bpy = 2,2'-bipyridine). The sulfurated complex nucleates as single molecule at different surface sites and at molecule clusters. In contrast, for the parent complex nucleation only occurs in clusters of several molecules at specifically oriented surface steps. While this shows that surface immobilization of the sulfurated complex is more efficient as compared to the parent, symmetry analysis of the STM topographic data supported by DFT calculations indicates that more than 90% of the complexes adsorb in a geometric configuration very similar to the one of the parent complex.

Combining grating-coupled illumination and image recognition for stable and localized optical scanning tunneling microscopy.

Combining scanning tunneling microscopy (STM) and optical excitation has been a major objective in STM for the last 30 years to study light-matter interactions on the atomic scale. The combination with modern pulsed laser systems even made it possible to achieve a temporal resolution down to the femtosecond regime. A promising approach toward a truly localized optical excitation is featured by nanofocusing via an optical antenna spatially separated from the tunnel junction. Until now, these experiments have been limited by thermal instabilities introduced by the laser. This paper presents a versatile solution to this problem by actively coupling the laser and STM, bypassing the vibration-isolation without compromising it. We utilize optical image recognition to monitor the position of the tunneling junction and compensate for any movement of the microscope relative to the laser setup with up to 10 Hz by adjusting the beamline. Our setup stabilizes the focus position with high precision (<1 µm) on long timescales (>1 h) and allows for high resolution STM under intense optical excitation with femtosecond pulses.

Making and breaking of chemical bonds in single nanoconfined molecules.

Nanoconfinement of catalytically active molecules is a powerful strategy to control their chemical activity; however, the atomic-scale mechanisms are challenging to identify. In the present study, the site-specific reactivity of a model rhenium catalyst is studied on the subnanometer scale for complexes confined within quasi-one-dimensional molecular chains on the Ag(001) surface by scanning tunneling microscopy. Injection of tunneling electrons causes ligand dissociation in single molecules. Unexpectedly, while half of the complexes show only the dissociation, the confined molecules show also the reverse reaction. On the basis of density functional theory calculations, this drastic difference can be attributed to the limited space in confinement. That is, the split-off ligand adsorbs closer to the molecule and the dissociation causes less structural disruption. Both of these facilitate the reverse reaction. We demonstrate formation and disruption of single chemical bonds of nanoconfined molecules with potential application in molecular data storage.

Anomalies at the Dirac Point in Graphene and Its Hole-Doped Compositions.

We study the properties of the Dirac states in SiC-graphene and its hole-doped compositions employing angle-resolved photoemission spectroscopy and density functional theory. The symmetry-selective measurements for the Dirac bands reveal their linearly dispersive behavior across the Dirac point which was termed as the anomalous region in earlier studies. No gap is observed even after boron substitution that reduced the carrier concentration significantly from 3.7×10^{13} cm^{-2} in SiC-graphene to 0.8×10^{13} cm^{-2} (5% doping). The anomalies at the Dirac point are attributed to the spectral width arising from the lifetime and momentum broadening in the experiments. The substitution of boron at the graphitic sites leads to a band renormalization and a shift of the Dirac point towards the Fermi level. The internal symmetries appear to be preserved in SiC-graphene even after significant boron substitutions. These results suggest that SiC-graphene is a good platform to realize exotic science as well as advanced technology where the carrier properties like concentration, mobility, etc., can be tuned keeping the Dirac fermionic properties protected.

Ordering a rhenium catalyst on Ag(001) through molecule-surface step interaction.

Atomic scale studies of the anchoring of catalytically active complexes to surfaces may provide valuable insights for the design of new catalytically active hybrid systems. In this work, the self-assembly of 1D, 2D and 3D structures of the complex fac-Re(bpy)(CO)3Cl (bpy = 2,2'-bipyridine), a CO2 reduction catalyst, on the Ag(001) surface are studied by a combination of low-temperature scanning tunneling microscopy and density functional theory calculations. Infrared and sum frequency generation spectroscopy confirm that the complex remains chemically intact under sublimation. Deposition of the complexes onto the silver surface at 300 K leads to strong local variations in the resulting surface coverage on the nanometer scale, indicating that in the initial phase of deposition a large fraction of the molecules is desorbing from the surface. Low coverage regions show a decoration of step edges aligned along the crystal's symmetry axes <110>. These crystallographic directions are found to be of major importance to the binding of the complexes to the surface. Moreover, the interaction between the molecules and the substrate promotes the restructuring of surface steps along these directions. Well-aligned and decorated steps are found to act as nucleation point for monolayer growth (2D) before 3D growth starts.

Substrate induced nanoscale resistance variation in epitaxial graphene.

Graphene, the first true two-dimensional material, still reveals the most remarkable transport properties among the growing class of two-dimensional materials. Although many studies have investigated fundamental scattering processes, the surprisingly large variation in the experimentally determined resistances is still an open issue. Here, we quantitatively investigate local transport properties of graphene prepared by polymer assisted sublimation growth using scanning tunneling potentiometry. These samples exhibit a spatially homogeneous current density, which allows to analyze variations in the local electrochemical potential with high precision. We utilize this possibility by examining the local sheet resistance finding a significant variation of up to 270% at low temperatures. We identify a correlation of the sheet resistance with the stacking sequence of the 6H silicon carbide substrate and with the distance between the graphene and the substrate. Our results experimentally quantify the impact of the graphene-substrate interaction on the local transport properties of graphene.

Magnetotransport on the nano scale.

Transport experiments in strong magnetic fields show a variety of fascinating phenomena like the quantum Hall effect, weak localization or the giant magnetoresistance. Often they originate from the atomic-scale structure inaccessible to macroscopic magnetotransport experiments. To connect spatial information with transport properties, various advanced scanning probe methods have been developed. Capable of ultimate spatial resolution, scanning tunnelling potentiometry has been used to determine the resistance of atomic-scale defects such as steps and interfaces. Here we combine this technique with magnetic fields and thus transfer magnetotransport experiments to the atomic scale. Monitoring the local voltage drop in epitaxial graphene, we show how the magnetic field controls the electric field components. We find that scattering processes at localized defects are independent of the strong magnetic field while monolayer and bilayer graphene sheets show a locally varying conductivity and charge carrier concentration differing from the macroscopic average.

From time-resolved atomic-scale imaging of individual donors to their cooperative dynamics.

The key elements in the steady miniaturization process of cutting-edge semiconductor devices are the understanding and controlling of charge dynamics on the atomic scale. In detail, we address the study of charging processes of individual doping atoms and, especially, the interaction of those atoms with their surroundings. We use pulsed optical excitation in combination with scanning tunneling microscopy at the n-doped gallium arsenide [GaAs(110)] surface to investigate single donor dynamics within a nanoscaled, localized space charge region. Tuning the tunnel rate can drive the system into nonequilibrium conditions, allowing distinction between the decay of optically induced free charge carriers and the decay of donor charge states. The latter process is atomically resolved and discussed with respect to donor-level binding energies and local donor configurations.

Controlling the screening process of a nanoscaled space charge region by minority carriers.

The miniaturization of future electronic devices is intimately connected to the ability to control electric fields on the atomic scale. In a nanoscopic system defined by a limited number of charges, the combined dynamics of bound and free charges become important. Here we present a model system based on the electrostatic interaction between a metallic tip of a scanning tunnelling microscope and a GaAs(110) semiconductor surface. The system is driven out of equilibrium by optical excitation, which provides ambipolar free charge carriers, and by an optically induced unipolar tunnel current. This combination enables the active control of the density and spatial distribution of free and bound charge in the space-charge region, that is, modifying the screening processes. Temporal fluctuations of single dopants are modified, meaning we are able to control the noise of the system. It is found that free charge carriers suppress the noise level in field-controlled, nanoscopic systems.

Doping of Graphene by Low-Energy Ion Beam Implantation: Structural, Electronic, and Transport Properties.

We investigate the structural, electronic, and transport properties of substitutional defects in SiC-graphene by means of scanning tunneling microscopy and magnetotransport experiments. Using ion incorporation via ultralow energy ion implantation, the influence of different ion species (boron, nitrogen, and carbon) can directly be compared. While boron and nitrogen atoms lead to an effective doping of the graphene sheet and can reduce or raise the position of the Fermi level, respectively, (12)C(+) carbon ions are used to study possible defect creation by the bombardment. For low-temperature transport, the implantation leads to an increase in resistance and a decrease in mobility in contrast to undoped samples. For undoped samples, we observe in high magnetic fields a positive magnetoresistance that changes to negative for the doped samples, especially for (11)B(+)- and (12)C(+)-ions. We conclude that the conductivity of the graphene sheet is lowered by impurity atoms and especially by lattice defects, because they result in weak localization effects at low temperatures.

Spatial extent of a Landauer residual-resistivity dipole in graphene quantified by scanning tunnelling potentiometry.

Electronic transport on a macroscopic scale is described by spatially averaged electric fields and scattering processes summarized in a reduced electron mobility. That this does not capture electronic transport on the atomic scale was realized by Landauer long ago. Local and non-local scattering processes need to be considered separately, the former leading to a voltage drop localized at a defect, the so-called Landauer residual-resistivity dipole. Lacking precise experimental data on the atomic scale, the spatial extent of the voltage drop remained an open question. Here, we provide an experimental study showing that the voltage drop at a monolayer-bilayer boundary in graphene clearly extends spatially up to a few nanometres into the bilayer and hence is not located strictly at the structural defect. Moreover, different scattering mechanisms can be disentangled. The matching of wave functions at either side of the junction is identified as the dominant process, a situation similar to that encountered when a molecule bridges two contacts.

Interplay between the Kondo effect and the Ruderman-Kittel-Kasuya-Yosida interaction.

The interplay between the Ruderman-Kittel-Kasuya-Yosida interaction and the Kondo effect is expected to provide the driving force for the emergence of many phenomena in strongly correlated electron materials. Two magnetic impurities in a metal are the smallest possible system containing all these ingredients and define a bottom-up approach towards a long-term understanding of concentrated/dense systems. Here we report on the experimental and theoretical investigation of iron dimers buried below a Cu(100) surface by means of low-temperature scanning tunnelling spectroscopy combined with density functional theory and numerical renormalization group calculations. The Kondo effect, in particular the width of the Abrikosov-Suhl resonance, is strongly altered or even suppressed due to magnetic coupling between the impurities. It oscillates as a function of dimer separation revealing that it is related to indirect exchange interactions mediated by the conduction electrons.

Fixing the energy scale in scanning tunneling microscopy on semiconductor surfaces.

In scanning tunneling experiments on semiconductor surfaces, the energy scale within the tunneling junction is usually unknown due to tip-induced band bending. Here, we experimentally recover the zero point of the energy scale by combining scanning tunneling microscopy with Kelvin probe force spectroscopy. With this technique, we revisit shallow acceptors buried in GaAs. Enhanced acceptor-related conductance is observed in negative, zero, and positive band-bending regimes. An Anderson-Hubbard model is used to rationalize our findings, capturing the crossover between the acceptor state being part of an impurity band for zero band bending and the acceptor state being split off and localized for strong negative or positive band bending, respectively.

Harmonic oscillator wave functions of a self-assembled InAs quantum dot measured by scanning tunneling microscopy.

InAs quantum dots embedded in an AlAs matrix inside a double barrier resonant tunneling diode are investigated by cross-sectional scanning tunneling spectroscopy. The wave functions of the bound quantum dot states are spatially and energetically resolved. These bound states are known to be responsible for resonant tunneling phenomena in such quantum dot diodes. The wave functions reveal a textbook-like one-dimensional harmonic oscillator behavior showing up to five equidistant energy levels of 80 meV spacing. The derived effective oscillator mass of m* = 0.24m0 is 1 order of magnitude higher than the effective electron mass of bulk InAs that we attribute to the influence of the surrounding AlAs matrix. This underlines the importance of the matrix material for tailored QD devices with well-defined properties.

Seeing the Fermi surface in real space by nanoscale electron focusing.

The Fermi surface that characterizes the electronic band structure of crystalline solids can be difficult to image experimentally in a way that reveals local variations. We show that Fermi surfaces can be imaged in real space with a low-temperature scanning tunneling microscope when subsurface point scatterers are present: in this case, cobalt impurities under a copper surface. Even the very simple Fermi surface of copper causes strongly anisotropic propagation characteristics of bulk electrons that are confined in beamlike paths on the nanoscale. The induced charge density oscillations on the nearby surface can be used for mapping buried defects and interfaces and some of their properties.