Mesoscopic Structures and Coexisting Phases in Silica Films.

Silica films represent a unique two-dimensional film system, exhibiting both crystalline and vitreous forms. While much scientific work has focused on the atomic-scale features of this film system, mesoscale structures can play an important role for understanding confined space reactions and other applications of silica films. Here, we report on mesoscale structures in silica films grown under ultrahigh vacuum and examined with scanning tunneling microscopy (STM). Silica films can exhibit coexisting phases of monolayer, zigzag, and bilayer structures. Both holes in the film structure and atomic-scale substrate steps are observed to influence these coexisting phases. In particular, film regions bordering holes in silica bilayer films exhibit vitreous character, even in regions where the majority film structure is crystalline. At high coverages mixed zigzag and bilayer phases are observed at step edges, while at lower coverages silica phases with lower silicon densities are observed more prevalently near step edges. The STM images reveal that silica films exhibit rich structural diversity at the mesoscale.

Growth and Atomic-Scale Characterization of Ultrathin Silica and Germania Films: The Crucial Role of the Metal Support.

The present review reports on the preparation and atomic-scale characterization of the thinnest possible films of the glass-forming materials silica and germania. To this end state-of-the-art surface science techniques, in particular scanning probe microscopy, and density functional theory calculations have been employed. The investigated films range from monolayer to bilayer coverage where both, the crystalline and the amorphous films, contain characteristic XO4 (X=Si,Ge) building blocks. A side-by-side comparison of silica and germania monolayer, zigzag phase and bilayer films supported on Mo(112), Ru(0001), Pt(111), and Au(111) leads to a more general comprehension of the network structure of glass former materials. This allows us to understand the crucial role of the metal support for the pathway from crystalline to amorphous ultrathin film growth.

Sensing the Spin of an Individual Ce Adatom.

The magnetic moment of rare earth elements originates from electrons in the partially filled 4f orbitals. Accessing this moment electrically by scanning tunneling spectroscopy is hampered by shielding of outerlying orbitals. Here, we show that we can detect the magnetic moment of an individual Ce atom adsorbed on a Cu_{2}N ultrathin film on Cu(100) by using a sensor tip that has its apex functionalized with a Kondo screened spin system. We calibrate the sensor tip by deliberately coupling it to a well characterized Fe atom. Subsequently, we use the splitting of the tip's Kondo resonance when approaching a spectroscopically dark Ce atom to sense its magnetic moment.

From Crystalline to Amorphous Germania Bilayer Films at the Atomic Scale: Preparation and Characterization.

A new two-dimensional (2D) germanium dioxide film has been prepared. The film consists of interconnected germania tetrahedral units forming a bilayer structure, weakly coupled to the supporting Pt(111) metal-substrate. Density functional theory calculations predict a stable structure of 558-membered rings for germania films, while for silica films 6-membered rings are preferred. By varying the preparation conditions the degree of order in the germania films is tuned. Crystalline, intermediate ordered and purely amorphous film structures are resolved by analysing scanning tunnelling microscopy images.

Charge Control in Model Catalysis: The Decisive Role of the Oxide-Nanoparticle Interface.

In chemistry and physics the electronic charge on a species or material is one important determinant of its properties. In the present Minireview, the essential requirements for a model catalyst system suitable to study charge control are discussed. The ideal model catalyst for this purpose consists of a material system, which comprises a single crystal metal support, covered by an epitaxially grown ultrathin oxide film, and flat, two-dimensional nanoparticles residing on this film. Several examples from the literature are selected and presented, which illustrate various aspects of electron transport from the support to the nanoparticle and vice versa. Key experiments demonstrate charge control within such model catalysts and give direct evidence for a chemical reaction at the perimeter of Au nanoparticles. The concepts derived from these studies are then taken a step further to see how they may be applied for bulk powder oxide supported nanoparticles as they are frequently found in catalytically active materials.

Molecular Adsorption Changes the Quantum Structure of Oxide-Supported Gold Nanoparticles: Chemisorption versus Physisorption.

STM conductance spectroscopy and mapping has been used to analyze the impact of molecular adsorption on the quantized electronic structure of individual metal nanoparticles. For this purpose, isophorone and CO2, as prototype molecules for physisorptive and chemisorptive binding, were dosed onto monolayer Au islands grown on MgO thin films. The molecules attach exclusively to the metal-oxide boundary, while the interior of the islands remains pristine. The Au quantum well states are perturbed due to the adsorption process and increase their mutual energy spacing in the CO2 case but move together in isophorone-covered islands. The shifts disclose the nature of the molecule-Au interaction, which relies on electron exchange for the CO2 ligands but on dispersive forces for the organic species. Our experiments reveal how molecular adsorption affects individual quantum systems, a topic of utmost relevance for heterogeneous catalysis.

Phonon-mediated electron transport through CaO thin films.

Scanning tunneling microscopy has developed into a powerful tool for the characterization of conductive surfaces, for which the overlap of tip and sample wave functions determines the image contrast. On insulating layers, as the CaO thin film grown on Mo(001) investigated here, direct overlap between initial and final states is not enabled anymore and electrons are transported via hopping through the conduction-band states of the oxide. Carrier transport is accompanied by strong phonon excitations in this case, imprinting an oscillatory signature on the differential conductance spectra of the system. The phonons show a characteristic spatial dependence and become softer around lattice irregularities in the oxide film, such as dislocation lines.

Dynamical Coulomb blockade observed in nanosized electrical contacts.

Electrical contacts between nanoengineered systems are expected to constitute the basic building blocks of future nanoscale electronics. However, the accurate characterization and understanding of electrical contacts at the nanoscale is an experimentally challenging task. Here, we employ low-temperature scanning tunneling spectroscopy to investigate the conductance of individual nanocontacts formed between flat Pb islands and their supporting substrates. We observe a suppression of the differential tunnel conductance at small bias voltages due to dynamical Coulomb blockade effects. The differential conductance spectra allow us to determine the capacitances and resistances of the electrical contacts which depend systematically on the island-substrate contact area. Calculations based on the theory of environmentally assisted tunneling agree well with the measurements.

Scanning tunneling microscopy and spectroscopy of supported nanostructures.

Recent advances in low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS) have provided new opportunities for the investigation of the local geometric, electronic, magnetic, and optical properties of nanostructures. This review focuses on the presentation and discussion of single molecules, supramolecular assemblies, and other nanostructures; all research results obtained in our laboratory. The emphasis is directed to the observation of new effects, where the properties of matter at the nanoscale differ from those at the mesoscopic or macroscopic scale: small is different. This fact is illustrated for the conservation of chirality in a hierarchical supramolecular assembly of organic molecules and for local light emission from supported molecules. The latter indicates a possible route towards an optical spectroscopic analysis on the scale of single molecules.

Supramolecular self-assembly driven by electrostatic repulsion: The 1D aggregation of rubrene pentagons on Au111.

At present, organic molecules are among the best candidate "building blocks" for the construction of self-assembling nanoscale devices based on metal substrates. Control of the formation of specific patterns in the submonolayer regime is usually achieved by appropriate choice and/or functionalization of the adsorbates. The effect of this intervention, though, is limited by the typically short-range character of the bonding. We present here a theoretical study on the system rubrene/gold to show that substrate-induced molecular charging can instead determine the assembly on larger scales. DFT calculations and electrostatic considerations are used to discuss the charge transfer at the metal/organic interface. This allows rationalization of previous puzzling experimental results and, in particular, of the unusual molecular gap broadening upon adsorption observed in STS spectra. The self-assembly process is further studied by means of classical molecular dynamics simulations. The charged adsorbates are modeled as mutually repulsive standing dipoles, with van der Waals interactions intervening at short distances. The striking resemblance between the experimental STM images and the results of our MD simulations shows that this simple model is able to capture the key effects driving the assembly in this system. The competition between long-range repulsive interactions and short-range attractive forces leads to characteristic and easily recognizable 1D patterns. We suggest that experimental evidence of the presence of similar patterns in other metal/organic systems can provide crucial information on the electronic level alignment at the interface, that is, on the occurrence of charge-transfer processes between metal and organic adsorbates.

Coverage-dependent self-assembly of rubrene molecules on noble metal surfaces observed by scanning tunneling microscopy.

Coverage-dependent self-assembly of rubrene molecules on different noble metal surfaces, Au(111) and Au(100), Ag(111) and Ag(100), is presented. On Au(111), the homochiral supramolecular assemblies evolve with increasing rubrene coverage from very small structures composed of a few molecules, to honeycomb islets, and to one-dimensional chains of supramolecular pentamers. At higher coverage, the racemic mixture of molecules forms close-packed islands. On Au(100), chains of pentamers and two different types of densely packed islands are formed. On the Ag surfaces, exclusively close-packed islands are created, independently of the rubrene coverage. Moreover, the role of the chiral nature of the molecules in the self-assembly process is discussed, as well as the existence of different molecular conformers depending on the supramolecular assembled phase. The observed differences and similarities reflect the influence of the electronic properties and the geometric structure of the various substrates on molecular self-assembly.

Reduction of the superconducting gap of ultrathin Pb islands grown on Si(111).

The energy gap Delta of superconducting Pb islands grown on Si(111) was probed in situ between 5 and 60 monolayers by low-temperature scanning tunneling spectroscopy. Delta was found to decrease from its bulk value as a function of inverse island thickness. Corresponding T_{c} values, estimated using bulk gap-to-T_{c} ratio, are in quantitative agreement with ex situ magnetic susceptibility measurements, however, in strong contrast to previous scanning probe results. Layer-dependent ab initio density functional calculations for freestanding Pb films show that the electron-phonon coupling constant, determining T_{c}, decreases with diminishing film thickness.

Three-dimensional chirality transfer in rubrene multilayer islands on Au(111).

The growth of rubrene (C(42)H(28), 5,6,11,12-tetraphenylnaphthacene) multilayer islands up to a thickness of six layers on a Au(111) surface has been investigated by scanning tunneling microscopy. The molecules self-organize in parallel twin rows, forming mirror domains of defined local structural chirality. Each layer is composed of twin-row domains of the same structural handedness rotated by 120 degrees with respect to each other. Moreover, this structural chirality is transferred to all successive layers in the island, resulting in the formation of three-dimensional objects having a defined structural chirality. The centered rectangular surface unit cell differs from the one characteristic for the single-crystal orthorhombic phase.

Plasmon enhanced luminescence from fullerene molecules excited by local electron tunneling.

Tunneling electrons from a scanning tunneling microscope (STM) induce luminescence from C(60) and C(70) molecules forming fullerene nanocrystals grown on ultrathin NaCl films on Au(111). Intramolecular fluorescence and phosphorescence associated with the transitions between the lowest electronic excited state and ground state of C(70) molecules are identified, leading to unambiguous chemical recognition on the nanoscale. Moreover we demonstrate that the molecular luminescence is selectively enhanced by localized surface plasmons in the STM tip-sample gap.

Spectroscopic manifestations of the Kondo effect on single adatoms.

The present topical review focuses on recent advances concerning an intriguing phenomenon in condensed matter physics, the scattering of conduction electrons at the localized spin of a magnetic impurity: the Kondo effect. Spectroscopic signatures of this effect have been observed in the past by high-resolution photoemission which, however, has the drawback of averaging over a typical surface area of 1 mm(2). By combining the atomic-scale spatial resolution of the scanning tunneling microscope (STM) with an energy resolution of a few tens of µeV achievable nowadays in scanning tunneling spectroscopy (STS), and by exposing the magnetic adatom to external magnetic fields, our understanding of the interaction of a single magnetic impurity with the conduction electrons of the nonmagnetic host has been considerably deepened. New insight has emerged by taking advantage of quantum size effects in the metallic support and by decoupling the magnetic adatom from the supporting host metal, for instance by embedding it inside a molecule or by separating it by an ultrathin insulating film from the metal surface. In this way, Kondo resonances and Kondo temperatures can be tailored and manipulated by changing the local density of states of the environment. In the weak coupling limit between a Kondo impurity and a superconductor only a convolution of tip and sample DOS is observed while for strongly coupled systems midgap states appear, indicating superconducting pair breaking. Magnetic impurities with co-adsorbed hydrogen on metallic surfaces show pseudo-Kondo resonances owing to very low-energy vibrational excitations detected by inelastic tunneling spectroscopy. One of the most recent achievements in the field has been the clarification of the role of magnetic anisotropy in the Kondo effect for localized spin systems with a spin larger than S = 1/2.

Diatomic molecular switches to enable the observation of very-low-energy vibrations.

Using low-temperature scanning tunneling microscopy and spectroscopy, we found that the coadsorption of atomic hydrogen to single transition-metal and rare-earth-metal atoms on a Ag(100) surface gives rise to surprising phenomena, a bias dependent switching from a large to a small apparent size of the diatomic molecules and a concomitant appearance of very low-energy vibrational features of 3 to 7 meV in the differential conductance spectra. These phenomena, which have until now escaped observation, may be of general relevance for low-temperature adsorption.

Fluorescence and phosphorescence from individual molecules excited by local electron tunneling.

Using the highly localized current of electrons tunneling through a double barrier scanning tunneling microscope junction, we excite luminescence from a selected C60 molecule in the surface layer of fullerene nanocrystals grown on an ultrathin NaCl film on Au(111). In the observed fluorescence and phosphorescence spectra, pure electronic as well as vibronically induced transitions of an individual C60 molecule are identified, leading to unambiguous chemical recognition on the single-molecular scale.

Scanning-tunneling spectroscopy of surface-state electrons scattered by a slightly disordered two-dimensional dilute "solid": Ce on Ag(111).

Low temperature (3.9 K) scanning-tunneling spectroscopy on a hexagonal superlattice of Ce adatoms on Ag(111) reveals site-dependent characteristic features in differential conductance spectra and in spectroscopic images at atomic-scale spatial resolution. Using a tight-binding model, we relate the overall spectral structures to the scattering of Ag(111) surface-state electrons by the Ce adatoms, the site dependence to the disorder induced by imperfections of the superlattice, and the opening of a gap in the local density of states to the observed stabilization of superlattices with adatom distances in the range of 2.3-3.5 nm.