Tungsten and molybdenum oxide nanostructures: two-dimensional layers and nanoclusters.

W- and Mo-oxides form an interesting class of materials, featuring structural complexities, stoichiometric flexibility, and versatile physical and chemical properties that render them attractive for many applications in diverse fields of nanotechnologies. In nanostructured form, novel properties and functionalities emerge as a result of quantum size and confinement effects. In this topical review, W- and Mo-oxide nanosystems are examined with particular emphasis on two-dimensional (2D) layers and small molecular-type clusters.

Formation of Supported Graphene Oxide: Evidence for Enolate Species.

Graphene oxides are promising materials for novel electronic devices or anchoring of the active sites for catalytic applications. Here we focus on understanding the atomic oxygen (AO) binding and mobility on different regions of graphene (Gr) on Ru(0001). Differences in the Gr/Ru lattices result in the superstructure, which offers an array of distinct adsorption sites.

Growth and Stability of Titanium Dioxide Nanoclusters on Graphene/Ru(0001).

Titanium dioxide/graphene composites have recently been demonstrated to improve the photocatalytic activity of TiO in visible light. To better understand the interactions of TiO with graphene we have investigated the growth of TiO nanoclusters on single-layer graphene/Ru(0001) using scanning tunneling microscopy (STM) and Auger electron spectroscopy (AES). Deposition of Ti in the O background at 300 K resulted in the formation of nanoclusters nucleating on intrinsic defects in the graphene (Gr) layer.

Lattice Strain Defects in a Ceria Nanolayer.

An ultrathin two-dimensional CeO2 (ceria) phase on a Cu(110) surface has been fabricated and fully characterized by high-resolution scanning tunneling microscopy, photoelectron spectroscopy, and density functional theory. The atomic lattice structure of the ceria/Cu(110) system is revealed as a hexagonal CeO2(111)-type monolayer separated from the Cu(110) surface by a partly disordered Cu-O intercalated buffer layer. The epitaxial coupling of the two-dimensional ceria overlayer to the Cu(110)-O surface leads to a nanoscopic stripe pattern, which creates defect regions of quasi-periodic lattice distortions.

Revealing the Buried Metal-Organic Interface: Restructuring of the First Layer by van der Waals Forces.

With the use of molecular manipulation in a cryogenic scanning tunneling microscope, the structure and rearrangement of sexiphenyl molecules at the buried interface of the organic film with the Cu(110) substrate surface have been revealed. It is shown that a reconstruction of the first monolayer of flat lying molecules occurs due to the van der Waals pressure from subsequent layers. In this rearrangement, additional sexiphenyl molecules are forced into the established complete monolayer and adopt an edge-on configuration.

Growth of Ceria Nano-Islands on a Stepped Au(788) Surface.

The growth morphology and structure of ceria nano-islands on a stepped Au(788) surface has been investigated by scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED). Within the concept of physical vapor deposition, different kinetic routes have been employed to design ceria-Au inverse model catalysts with different ceria nanoparticle shapes and arrangements. A two-dimensional superlattice of ceria nano-islands with a relatively narrow size distribution (5 ± 2 nm²) has been generated on the Au(788) surface by the postoxidation method.

Cerium Oxide Nanoclusters on Graphene/Ru(0001): Intercalation of Oxygen via Spillover.

Cerium oxide is an important catalytic material known for its ability to store and release oxygen, and as such, it has been used in a range of applications, both as an active catalyst and as a catalyst support. Using scanning tunneling microscopy and Auger electron spectroscopy, we investigated oxygen interactions with CeOx nanoclusters on a complete graphene monolayer-covered Ru(0001) surface at elevated temperatures (600-725 K). Under oxidizing conditions (PO2 = 1 × 10(-7) Torr), oxygen intercalation under the graphene layer is observed.

Redox processes at a nanostructured interface under strong electric fields.

Manipulation of chemistry and film growth via external electric fields is a longstanding goal in surface science. Numerous systems have been predicted to show such effects but experimental evidence is sparse. Here we demonstrate in a custom-designed UHV apparatus that the application of spatially extended, homogeneous, very high (>1 V nm(-1)) DC-fields not only changes the system energetics but triggers dynamic processes which become important much before static contributions appreciably modify the potential energy landscape.

Metal tungstates at the ultimate two-dimensional limit: fabrication of a CuWO₄ nanophase.

Metal tungstates (with general formula MWO4) are functional materials with a high potential for a diverse set of applications ranging from low-dimensional magnetism to chemical sensing and photoelectrocatalytic water oxidation. For high level applications, nanoscale control of film growth is necessary, as well as a deeper understanding and characterization of materials properties at reduced dimensionality. We succeeded in fabricating and characterizing a two-dimensional (2-D) copper tungstate (CuWO4).

Alternating chirality in the monolayer H2TPP on Cu(110)-(2 × 1)O.

In this work, the structure of the tetraphenylporphyrin (H2TPP) monolayer grown on the oxygen passivated Cu(110)-(2 × 1)O surface has been investigated with LT-STM and elucidated by DFT-calculations. The monolayer is commensurate with all molecules occupying the same adsorption site, but there are two molecules per unit cell. The STM images suggest alternating chirality for the molecules within one unit cell which is supported by DFT total energy calculations for monolayers on the Cu-O substrate.

Ordered arrays of size-selected oxide nanoparticles.

A bottom-up approach to produce a long-range ordered superlattice of monodisperse and isomorphic metal-oxide nanoparticles (NP) supported onto an oxide substrate is demonstrated. The synthetic strategy consists of self-assembling metallic NP on an ultrathin nanopatterned aluminum oxide template followed by a morphology-conserving oxidation process, and is exemplified in the case of Ni, but is generally applicable to a wide range of metallic systems. Both fully oxidized and core-shell metal-metal-oxide particles are synthesized, up to 3-4 nm in diameter, and characterized via spectroscopic and theoretical tools.

Layer resolved evolution of the optical properties of α-sexithiophene thin films.

We report a combined reflectance difference spectroscopy and scanning tunneling microscopy study of ultrathin α-sexithiophene (6T) films deposited on the Cu(110)-(2×1)O surface. The correlation between the layer resolved crystalline structure and the corresponding optical spectra data reveals a highly sensitive dependence of the excitonic optical properties on the layer thickness and crystalline structure of the 6T film.

Work Function of Oxide Ultrathin Films on the Ag(100) Surface.

Theoretical calculations of the work function of monolayer (ML) and bilayer (BL) oxide films on the Ag(100) surface are reported and analyzed as a function of the nature of the oxide for first-row transition metals. The contributions due to charge compression, charge transfer and rumpling are singled out. It is found that the presence of empty d-orbitals in the oxide metal can entail a charge flow from the Ag(100) surface to the oxide film which counteracts the decrease in the work function due to charge compression.

Synchrotron x-ray photoemission study of soft x-ray processed ultrathin glycine-water ice films.

Ultrathin glycine-water ice films have been prepared in ultrahigh vacuum by condensation of H(2)O and glycine at 90 K on single crystalline alumina surfaces and processed by soft x-ray (610 eV) exposure for up to 60 min. The physicochemical changes in the films were monitored using synchrotron x-ray photoemission spectroscopy. Two films with different amounts of H(2)O have been considered in order to evaluate the influence of the water ice content on the radiation-induced effects.

Kondo versus magnetic coupling of cobalt dimers in a Cu-O (2 × 1) reconstruction.

Co atoms and dimers embedded in a Cu(110)(2 × 1)-O surface oxide are investigated via low-temperature STM/STS experiments and first-principles simulations. It is found that Co dimers incorporated into adjacent rows of the Cu(110)(2 × 1)-O reconstruction show Kondo resonances decoupled from each other, whereas they are antiferromagnetically coupled (and do not exhibit a Kondo effect) when they are aligned on the same row. This shows that it is possible to decouple single carriers of the Kondo effect via a proper choice of the adsorption and host geometry.

A momentum space view of the surface chemical bond.

Well-ordered and oriented monolayers of conjugated organic molecules can offer new perspectives on surface bonding. We will demonstrate the importance of the momentum distribution, or symmetry, of the adsorbate molecules' π orbitals in relation to the states available for hybridization at the metal surface. Here, the electronic band structure of the first monolayer of sexiphenyl on Cu(110) has been examined in detail with angle-resolved ultraviolet photoemission spectroscopy over a large momentum range and will be compared to measurements of a multilayer thin film and to density functional calculations.

Oxide-metal nanowires by oxidation of a one-dimensional Mn-Pd alloy: stability and reactivity.

Distinct one-dimensional (1D) oxide nanowires decorating the step edges of a stepped Pd(1 1 9) surface are formed by partial and complete oxidation of a 1D Mn-Pd alloy. Under full postoxidation treatment at 470-570 K, 1D MnO(2) nanowires coupled pseudomorphically to the Pd steps are obtained. Oxidized nanowires, which maintain the basic structural pattern of the 1D Mn-Pd alloy, are instead prepared by exposure of the Mn-Pd alloy to O(2) at 90 K and subsequent short heating to 400 K.

Revealing the buried interface: para-sexiphenyl thin films grown on TiO2(110).

The thickness dependent optical and electronic structure of para-sexiphenyl thin films grown on TiO(2)(110) at around 400 K reveals that the substrate is first wet by one monolayer of molecules lying with their long axis parallel to the [001] direction of the substrate, while the molecules in subsequent layers are almost standing upright. Whilst ultraviolet photoemission spectroscopy (UPS) is sensitive to the molecules in the outermost layer, reflection difference spectroscopy (RDS) shows that the molecules at the buried interface do not dewet and maintain the orientation of the original wetting monolayer.

Reconstruction of molecular orbital densities from photoemission data.

Photoemission spectroscopy is commonly applied to study the band structure of solids by measuring the kinetic energy versus angular distribution of the photoemitted electrons. Here, we apply this experimental technique to characterize discrete orbitals of large pi-conjugated molecules. By measuring the photoemission intensity from a constant initial-state energy over a hemispherical region, we generate reciprocal space maps of the emitting orbital density.

The molecular orientation of para-sexiphenyl on Cu(110) and Cu(110) p(2x1)O.

Controlling the molecular growth of organic semiconductors is an important issue to optimize the performance of organic devices. Conjugated molecules, used as building blocks, have an anisotropic shape and also anisotropic physical properties like charge transport or luminescence. The main challenge is to grow highly crystalline layers with molecules of defined orientation.

Fluctuations and phase separation in a quasi-one-dimensional system.

Phase transitions in a quasi-one-dimensional surface system on a metal substrate are investigated as a function of temperature. Upon cooling the system shows a loss of long-range order, fluctuations, and a transition into an inhomogeneous ground state due to competition of local adsorbate-adsorbate interactions with an incommensurate charge density wave. This agrees with a general phase diagram for correlated systems and high-temperature superconductors.

Surface chemistry of ultrathin films of histidine on gold as probed by high-resolution synchrotron photoemission.

Procedures for the vacuum deposition of thin histidine films on polycrystalline Au(111) and their characterization with high-resolution synchrotron-radiation-based photoelectron spectroscopy are reported. The chemical form of histidine (anionic vs zwitterionic) and the nature of its interactions with the substrate (strong ionic-covalent vs weak van der Waals bonding) in mono- and multilayer films are analyzed. It is shown that water adsorption on a pre-prepared histidine film at 100 K results in protonation of histidine molecules and partial formation of hydroxyl anions.

Heteroepitaxy of organic-organic nanostructures.

Highly crystalline organic heteroepitaxial layers with controlled molecular orientations and morphologies are one of the keys for optimum organic device performance. With studies of molecular orientation, structure, and morphology, we have investigated the ability of oriented organic films to act as substrate templates for the growth of a second organic layer. Depending on the molecular orientation in the sexiphenyl substrate, crystalline sexithiophene nanostructures of either pyramidal or needlelike morphology, with either near vertical or parallel molecular orientations, respectively, grow.