The preparation of thin ordered transition metal oxide films on metal single crystals for surface science studies

In this paper the preparation, characterization and properties of metal oxide overlayers on dissimilar metal substrates is reviewed. It is shown that using a general recipe metal oxide surfaces can be produced, which are easily accessible with modern surface science techniques. Many different stoichiometries and structures of the oxides can be prepared by variation of the preparation conditions, that do or do not have a counterpart in bulk oxide surfaces. In addition information about the metal oxide surfaces is obtained without experimental problems such as sample mounting, sample heating and sample purity.     

Wrapping and inclusion of organic molecules with ultrathin,amorphous metal oxide films

In this review, we overview metal oxide nanostructures in which organic molecules play important roles as templates, as structural units, and, in some cases, as hosts. Their structural precision and diversity are discussed from the viewpoint of the topology of a metal-oxygen network. Supramolecular capsules of metal oxides are prepared by the self-assembly of polyoxometalates. Zeolites and mesoporous materials are synthesized by using organic molecules with their assemblies acting as templates. The topological networking of silsesquioxanes makes it possible to produce novel nanocomposites and microporous materials. In the final section, we demonstrate our recent studies into molecular imprinting, the encapsulation of a fluorescent dye, and the wrapping of individual polymer chains. Ultrathin, amorphous metal oxide films can retain the shape of organic molecules and can be used to create molecular composites by precisely wrapping individual molecules. These films are also effective in insulating molecular functions from external environments. The advantages of amorphous metal oxides are discussed in relation to the properties of the corresponding crystalline metal oxides and their potential prospects in nanotechnology.     

Magnetism and surface structure of atomically controlled ultrathin metal films

We review the correlation of magnetism and surface structure in ultrathin metal films, including the tailoring of novel magnetic properties using atomic scale control of the nanostructure. We provide an overview of modern fabrication and characterization techniques used to create and explore these fascinating materials, and highlight important phenomena of interest. We also discuss techniques that control and characterize both the magnetic and structural properties on an atomic scale. Recent advances in the development and applications of these techniques allow nanomagnetism to be investigated in an unprecedented manner.A system cannot necessarily retain a two-dimensional structure as it enters the ultrathin region, but it can transform into a three-dimensional, discontinuous structure due to the Volmer–Weber growth mechanism. This structural transformation can give rise to superparamagnetism. During this evolution, competing factors such as interparticle interactions and the effective magnetic anisotropy govern the magnetic state. These magnetic parameters are influenced by the nanostructure of the film. In particular, controlling the magnetic anisotropy is critical for determining the magnetic properties. Surface effects play especially important roles in influencing both the magnitude and direction of the magnetic anisotropy in ultrathin films. By properly altering the surface structure, the strength and direction of the magnetic anisotropy are controlled via spin–orbit and/or dipole interactions.     

Direct formation of form I poly(1‐butene) single crystals from melt crystallization in ultrathin films

The morphologies and crystalline structures of melt‐crystallized ultrathin isotactic poly(1‐butene) films have been studied with transmission electron microscopy and electron diffraction. It is demonstrated that a bypass of form II crystallization can be achieved with an increase in its crystallization temperature. Electron microscopy observations show that melt‐grown isotactic poly(1‐butene) single crystals have a well‐shaped hexagonal form, whereas form I crystals converted from form II display the morphologies of their tetragonal precursors. Electron diffraction results indicate that, instead of the twinned hexagonal pattern of the converted form I crystal, the directly formed form I single crystals exhibit an untwinned hexagonal pattern. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2641–2645, 2002     

Considerations on ultra-high frequency electric field effects on oxygen vacancy concentration in oxide thin films

Atomistic simulations employing dynamic charge transfer between atoms are used to investigate ultra-thin oxide growth on Al(100) metal substrates in the presence of an ac electric field. In the range of 1-10 GHz frequencies, the enhancement in oxidation kinetics by ～12% over natural oxidation can be explained by the Cabrera-Mott mechanism. At field frequencies approaching 0.1-1 THz, however, we observe a dramatic lowering of the kinetics of oxygen incorporation by ～35% compared to the maximum oxidation achieved, which results in oxygen non-stoichiometry near the oxide-gas interface (O/Al ≈ 1.0). This is attributed to oxygen desorption from the oxide surface. These results suggest a general strategy to tune oxygen concentration at oxide surfaces using ac electric fields that could be of interest in diverse fields related to surface chemistry and applications such as tunnel barriers, thin dielectrics and oxide interfaces.     

Thin films of nematic liquid crystal on liquid substrate. Bulk and surface structures,surface and line tensions

Summary The structure of a liquid crystal (L.C) thin film on water has been studied optically and the molecular orientation at its interfaces has been deduced. The surface tension shift corresponding to the orientations of the molecules either normal or parallel to the free surface has been deduced. From the study of the formation and of the stability of holes in the thin film we deduce the order of magnitude of the line tensionx. This tension originates in the elastic deformation of LC in the neighbourhood of the hole.     

Calculated bulk vacancy formation energy (Ev) for a Schottky defect in Al single crystals

In this paper the bulk vacancy formation energies (E_v) of Al single crystals (with different surface orientations (111), (100) and (110)) were calculated with the embedded atom method using the empirical many‐body potential of Sutton and Chen. These calculations indicate that there is a significant difference in the bulk vacancy formation energy underneath different surface orientations. The crystal with the (111) surface had the highest bulk vacancy formation energy and the crystal with the (110) surface had the lowest bulk vacancy formation energy. Copyright © 2003 John Wiley & Sons, Ltd.     

Formation and dissolution of phase-separated structures in ultrathin blend films

The phase separation of ultrathin polymer blend films of deuterated poly(styrene)/poly(vinylmethylether) leads to a variety of film morphologies, depending on polymer composition. Phase-separation measurements are made at a constant temperature difference from the critical temperature, leading to a bicontinuous spinodal decomposition pattern for near-critical blend compositions and to “mounds” and “holes” for PVME-rich and dPS-rich off-critical mixtures, respectively. Reverse temperature jumps of the phase-separated blend films into the one-phase region result in dissolution of the undulating surface patterns, confirming the phase-separation origin of the film patterns. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 191–200, 1998     

Comparing the activation energy of diffusion in bulk and ultrathin fluid films

We have measured the activation energy (E act) of translational diffusion for a dissolved fluorescent dye in bulk and within an ultrathin liquid film formed on a solid substrate. The experiments were performed using the single-molecule sensitive technique of fluorescence correlation spectroscopy. From the temperature-dependent measurements, we have determined that the activation energy for a few nanometer thick fluid film increases by a factor of approximately 3-4 compared to bulk liquid. The results are confirmed for two distinctly different systems in regard to molecular shape, tetrakis (2-ethylhexoxy) silane and hexadecane.     

Molecular surface chemistry by metal single crystals and nanoparticles from vacuum to high pressure

Model systems for studying molecular surface chemistry have evolved from single crystal surfaces at low pressure to colloidal nanoparticles at high pressure. Low pressure surface structure studies of platinum single crystals using molecular beam surface scattering and low energy electron diffraction techniques probe the unique activity of defects, steps and kinks at the surface for dissociation reactions (H-H, C-H, C-C, O=O bonds). High-pressure investigations of platinum single crystals using sum frequency generation vibrational spectroscopy have revealed the presence and the nature of reaction intermediates. High pressure scanning tunneling microscopy of platinum single crystal surfaces showed adsorbate mobility during a catalytic reaction. Nanoparticle systems are used to determine the role of metal-oxide interfaces, site blocking and the role of surface structures in reactive surface chemistry. The size, shape and composition of nanoparticles play important roles in determining reaction activity and selectivity and is covered in this tutorial review.     

Photoelectron studies of adsorption and catalysis on the surface of metal single crystals and polycrystals

The potential of photoelectron spectroscopy (XPS) and its use in studies of the state of the surface and adsorption processes on bulk metal samples (disk single crystals, polycrystalline foil and plates) are discussed. Methods for determining the electronic state of the surface layer and geometrical localization of adsorbed atoms on the metal surface using angle-resolved photoelectron spectroscopy are described. The spectrokinetic use of the dynamic mode of XPS with high accuracy and time resolution for kinetic studies of fast processes on the surface (adsorption-desorption, reconstruction, reaction, diffusion-segregation) is considered in detail.     

Molecular probe techniques for studying diffusion and relaxation in thin and ultrathin polymer films

Two optically based, molecular probe techniques are employed to study relaxation and small-molecule translational diffusion in thin and ultrathin (thicknesses < ∼200 nm) polymer films. Second harmonic generation (SHG) is used to study the reorientational dynamics of a nonlinear optical chromophore, Disperse Red 1 (DR1) (previously shown to be an effective probe of α-relaxation dynamics) either covalently attached or freely doped in polymer films. Our studies on films ranging in thickness from 7 nm to 1 μm show little change in T_g with film thickness; however, a substantial broadening of the relaxation distribution is observed as film thickness decreases below approximately 150 nm. Experimental guidelines are given for using fluorescence nonradiative energy transfer (NRET) to study translational diffusion in ultrathin polymer films. Appropriate choice of a fluorescence donor species is important along with ensuring that diffusion is slow enough to be measured appropriately. Initial results on the diffusion of a small-molecule probe, lophine, in poly(isobutyl methacrylate) indicates that there is little change in probe diffusion coefficients in films as thin as 90 nm as compared to bulk films. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2795–2802, 1997     

Oxygen vacancy formation for transient structures on the CeO2(110) surface at 300 and 750 K

Ab initio embedded-cluster calculations have been performed for the CeO2(110) surface using temperature induced structures from molecular dynamics (MD) snapshots. As a first step towards understanding how temperature induced distortions of the surface structure influence the surface oxygen reactivity, the energy cost of removing an O atom from the surface was calculated for 41 snapshots from the MD simulation at 300 K. The quantum mechanical embedded-cluster calculations show that already at 300 K the dynamics causes significant fluctuations (root mean square of 0.37 eV) in the O vacancy formation energy (Evac) while the distribution of the two excess electrons associated with the vacancy is virtually unaffected by the surface dynamics and remains localized on the two Ce ions close to the vacancy. It is also found that the quantum mechanical Evac fluctuations can be reproduced by oxygen vacancy calculations using only the relaxed shell-model force field (FF) itself and the MD geometries. Using the FF as the interaction model, the effect of raising the temperature to 750 K and the effect of doping with Ca were investigated for the oxygen vacancy formation.     

Zinc oxide nanoparticles incorporated in ultrathin layer silicate films and their photocatalytic properties

This study has been conducted to determine whether the nanosized semiconductor crystals qualify as photocatalysts also in that case when they are self-assembled to form ultrathin films in the thickness range of 10–500 nm. For this purpose, multilayer films of Zn(OH)₂ and ZnO nanoparticles were prepared by the layer-by-layer self-assembly method on glass surface. A transparent layer silicate, synthetic hectorite was used as sticking material. The quality of multilayer formation has been investigated in detail by absorption spectrophotometry, XRD and atomic force microscopy (AFM). Evidence was found for the uniform deposition of the different components. The increment of nanofilm thickness was constant and independent from the number of layers deposited previously. Photocatalytic measurements were made with model organic materials β-naphtol and industrial kerosene in a home-made loop-type batch reactor. Decomposition has been continously monitored by UV spectrometry. Significant photodegradation of the organic molecules were only found in the presence of the nanofilms.     

New rare-earth metal acyl pyrazolonates: Synthesis,crystals structures,and luminescence properties

Ligand 3-methyl-1-phenyl-4-stearoylpyrazol-5-one (HQ) is synthesized and used to obtain new complexes of rare-earth metals (Eu, Gd, and Tb) of the composition [Ln(Q)₃(H₂O)(EtOH)]. The crystal structure of the terbium complex is determined by X-ray diffraction analysis (CIF file CCDC 975286). In a molecule of the complex, three aliphatic fragments n-C₁₇H₃₅ are codirected, which results in the formation of layers bound according to the fastener-sticker principle. The molecules of the complex are joined by a hydrogen bond network involving the pyrazolone rings and oxygen atoms of the inner-sphere solvent molecules (H₂O and EtOH). The terbium complex is luminescent at room temperature, whereas the luminescence of the europium complex is very weak at room temperature and increases by 60 times at lowered temperatures. This makes it possible to consider these compounds as a new class of “luminescent thermometers.”     

Conduction and tritium diffusion studies in single crystals of potassium hydrogen sulfate

Direct-current electrical conductivity of single crystals of KHSO₄ doped with 5, 11, 30, and 437 ppm of cobalt-II is studied in the temperature range 25 to 165°C. The point defect parameters are calculated by graphical analysis of the conductivity data. Various parameters are obtained: enthalpy for the migration of proton (referred to as the enthalpy for the rotation of HSO₄ ion), H_M = 0.55 ± 0.01 eV; the enthalpy for the formation of the intrinsic defects (referred to as the enthalpy for the breaking of the HSO₄ dimers), H_F = 1.30 ± 0.01 eV; and the enthalpy for the impurity-vacancy association H_a = ?0.14 ± 0.01 eV. The tritium diffusion studies in the pure KHSO₄ single crystals give 0.22 ± 0.01 eV and ?1.09 × 10^?3 eV K^?1 as the activation enthalpy and entropy for the process, respectively. The Nernst-Einstein relation is not obeyed. The mechanisms for the conduction and diffusion preocesses in this crystal are discussed.     

Surface diffusion of nickel in metal oxide superconductors and external effects

The effects of crystallite size, oxygen disordering, and adsorption of water vapors on Ni diffusion in YBa₂Cu₃O_7–x were investigated. The transformation of single to double component diffusion was found. The surface character of both components was proved.     

Magnesium-stabilised transition metal formyl complexes: structures,bonding, and ethenediolate formation

Herein we report the first comprehensive series of crystallographically characterised transition metal formyl complexes. In these complexes, the formyl ligand is trapped as part of a chelating structure between a transition metal (Cr, Mn, Fe, Co, Rh, W, and Ir) and a magnesium (Mg) cation. Calculations suggest that this bonding mode results in significant oxycarbene-character of the formyl ligand. Further reaction of a heterometallic Cr–Mg formyl complex results in a rare example of C–C coupling and formation of an ethenediolate complex. DFT calculations support a key role for the formyl-intermediate in ethenediolate formation. These results show that well-defined transition metal formyl complexes are potential intermediates in the homologation of carbon monoxide.

Herein we report a comprehensive series of crystallographically characterised transition metal formyl complexes.