Renald Schaub

Enhanced Bonding of Gold Nanoparticles on Oxidized TiO2(110)

We studied the nucleation of gold clusters on TiO2(110) surfaces in three different oxidation states by high-resolution scanning tunneling microscopy. The three TiO2(110) supports chosen were (i) reduced (having bridging oxygen vacancies), (ii) hydrated (having bridging hydroxyl groups), and (iii) oxidized (having oxygen adatoms). At room temperature, gold nanoclusters nucleate homogeneously on the terraces of the reduced and oxidized supports, whereas on the hydrated TiO2(110) surface, clusters form preferentially at the step edges. From interplay with density functional theory calculations, we identified two different gold-TiO2(110) adhesion mechanisms for the reduced and oxidized supports. The adhesion of gold clusters is strongest on the oxidized support, and the implications of this finding for catalytic applications are discussed.

Size-Selective Carbon Nanoclusters as Precursors to the Growth of Epitaxial Graphene

The nucleation and growth mechanisms of graphene on Rh(111) via temperature-programmed growth of C(2)H(4) are studied by scanning tunneling microscopy and spectroscopy, and by density functional theory calculations. By combining our experimental and first-principles approaches, we show that carbon nanoislands form in the initial stages of graphene growth, possessing an exclusive size of seven honeycomb carbon units (hereafter labeled as 7C(6)). These clusters adopt a domelike hexagonal shape indicating that bonding to the substrate is localized on the peripheral C atoms. Smoluchowski ripening is identified as the dominant mechanism leading to the formation of graphene, with the size-selective carbon islands as precursors. Control experiments and calculations, whereby coronene molecules, the hydrogenated analogues of 7C(6), are deposited on Rh(111), provide an unambiguous structural and chemical identification of the 7C(6) building blocks.

Coupling Epitaxy, Chemical Bonding, and Work Function at the Local Scale in Transition Metal-Supported Graphene

Resonance tunneling spectroscopy and density functional theory calculations are employed to explore local variations in the electronic surface potential of a single graphene layer grown on Rh(111). A work function modulation of 220 meV is experimentally measured, indicating that the chemical bonding strength varies significantly across the supercell of the Moiré pattern formed when graphene is bonded to Rh(111). In combination with high-resolution images, which provide precise knowledge of the local atomic registry at the carbon-metal interface, we identify experimentally, and confirm theoretically, the atomic configuration of maximum chemical bonding to the substrate. Our observations are at odds with reported trends for other transition metal substrates. We explain why this is the case by considering the various factors that contribute to the bonding at the graphene/metal interface.

Strong Electron Correlations in the Normal State of the Iron-Based FeSe0.42Te0.58 Superconductor Observed by Angle-Resolved Photoemission Spectroscopy

A. Tamai, A.Y. Ganin, E. Rozbicki, J. Bacsa, W. Meevasana, P.D.C. King, M. Caffio, R. Schaub, S. Margadonna, K. Prassides, M.J. Rosseinsky, and F. Baumberger School of Physics and Astronomy, University of St. Andrews, St. Andrews, Fife KY16 9SS, United Kingdom Department of Chemistry, University of Liverpool, Liverpool L69 7ZD, United Kingdom School of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 9ST, United Kingdom School of Chemistry, University of Edinburgh, Edinburgh EH9 3JJ, United Kingdom Department of Chemistry, Durham University, Durham DH1 3LE, United Kingdom (Dated: February 10, 2010)

Observation of all the intermediate steps of a chemical reaction on an oxide surface by scanning tunneling microscopy.

By means of high-resolution scanning tunneling microscopy (STM), we have revealed unprecedented details about the intermediate steps for a surface-catalyzed reaction. Specifically, we studied the oxidation of H adatoms by O(2) molecules on the rutile TiO(2)(110) surface. O(2) adsorbs and successively reacts with the H adatoms, resulting in the formation of water species. Using time-lapsed STM imaging, we have unraveled the individual reaction intermediates of HO(2), H(2)O(2), and H(3)O(2) stoichiometry and the final reaction product-pairs of water molecules, [H(2)O](2). Because of their different appearance and mobility, these four species are discernible in the time-lapsed STM images. The interpretation of the STM results is corroborated by density functional theory calculations. The presented experimental and theoretical results are discussed with respect to previous reports where other reaction mechanisms have been put forward.

Weak mismatch epitaxy and structural feedback in graphene growth on copper foil

AbstractGraphene growth by low-pressure chemical vapor deposition on low cost copper foils shows great promise for large scale applications. It is known that the local crystallography of the foil influences the graphene growth rate. Here we find an epitaxial relationship between graphene and copper foil. Interfacial restructuring between graphene and copper drives the formation of (n10) facets on what is otherwise a mostly Cu(100) surface, and the facets in turn influence the graphene orientations from the onset of growth. Angle resolved photoemission shows that the electronic structure of the graphene is decoupled from the copper indicating a weak interaction between them. Despite this, two preferred orientations of graphene are found, ±8° from the Cu[010] direction, creating a non-uniform distribution of graphene grain boundary misorientation angles. Comparison with the model system of graphene growth on single crystal Cu(110) indicates that this orientational alignment is due to mismatch epitaxy. Despite the differences in symmetry the orientation of the graphene is defined by that of the copper. We expect these observations to not only have importance for controlling and understanding the growth process for graphene on copper, but also to have wider implications for the growth of two-dimensional materials on low cost metal substrates.

Construction of an internally B3N3-doped nanographene molecule

The synthesis of a hexa-peri-hexabenzocoronene (HBC) with a central borazine core is described. The solid-state structure of this BN-doped HBC (BN-HBC) is isotypic with that of the parent HBC. Scanning tunneling microscopy shows that BN-HBC lies flat on Au(111) in a two-dimensional pattern.

Electrodeposition of Palladium onto a Pyridine-Terminated Self-Assembled Monolayer

The electrodeposition of Pd onto self-assembled monolayers (SAMs) of 3-(4-pyridine-4-ylphenyl)propane-1-thiol on Au(111) has been investigated by scanning tunneling microscopy. Two schemes are compared: One involves an established two-step procedure where Pd(2+) ions are first coordinated to the pyridine moieties and subsequently reduced in Pd(2+)-free electrolyte. The second deposition routine involves electroreduction in an electrolyte containing low concentration of Pd(2+) which merges both steps and, thus, significantly simplifies metal deposition onto pyridine-terminated SAMs. Both strategies produce identical Pd nanoparticles (NPs) which exhibit a narrow size distribution and an apparent STM height of ∼2.4 nm. The observation of a Coulomb blockade and easy displacement of the nanoparticles in STM experiments evidence deposition on top of the SAM. The NPs are concluded to be essentially spherical. Growth of the NPs is found to be self-limiting since repeating the complexation-deposition cycle increases the density of the nanoparticles rather than their size but only close to full coverage. At high concentration of the Pd(2+) electrolyte, deposition on top of the SAM is impeded by a competitive mushroom-type growth.

Deposition of mass-selected clusters studied by thermal energy atom scattering and low-temperature scanning tunneling microscopy: An experimental setup

We present an experimental setup for the investigation of the processes occurring during the deposition of mass-selected clusters on a well-defined surface. The sample is analyzed in situ by two complementary methods: thermal energy atom scattering (TEAS) and scanning tunneling microscopy (STM). TEAS is used to study the dynamical processes during the deposition and to gather statistical information about the resulting structures on the surface. Subsequent STM measurements allow us to investigate the collision outcome on an atomic scale. The setup is highly versatile and guarantees ultra-high-vacuum conditions and cryogenic temperatures (≈30 K) of the sample at all times even during sample transfer. Clusters are produced in a CORDIS-type cluster source. A new compact multichannel effusive He source in combination with a new Wien-filter-based He detector are used for TEAS measurements. The new low-temperature STM allows measurements in a temperature range between 8 and 450 K. Atomic resolution on the Pt(11...

New class of metal bound molecular switches involving H-tautomerism.

A potential end-point in the miniaturization of electronic devices lies in the field of molecular electronics, where molecules perform the function of single components. To date, hydrogen tautomerism in unimolecular switches has been restricted to the central macrocycle of porphyrin-type molecules. The present work reveals how H-tautomerism is the mechanism for switching in substituted quinone derivatives, a novel class of molecules with a different chemical structure. We hence reveal that the previous restrictions applying to tautomeric molecular switches bound to a surface are not valid in general. The activation energy of switching in a prototypical quinone derivative is determined using inelastic electron tunneling. Through computational modeling, we show that the mechanism underlying this process is tautomerization of protons belonging to two amino groups. This switching property is retained upon functionalization by the addition of side groups, meaning that the switch can be chemically modified to fit specific applications.