Spray pyrolysis deposition of undoped SnO2 and In2O3 films and their structural properties

In this paper the results of structural analysis of the SnO₂ and In₂O₃ films deposited by spray pyrolysis are presented. The main goals of this analysis are summarizing the results obtained in this field, highlighting a correlation between parameters of film deposition and the material structure and formulating some general regularities, typical for metal oxides. Peculiarities and mechanisms of pyrosol deposition as well as advantages and disadvantages of this technology for deposition of the films with required parameters were also discussed. It is shown that this technology has great potential for controlling structural parameters of metal oxides such as thickness, the grain size, texturing, roughness, the grain faceting and the porosity.     

Lengthscale-dependent,elastically anisotropic,physically-based hcp crystal plasticity: Application to cold-dwell fatigue in Ti alloys

A crystal plasticity model for hcp materials is presented which is based on dislocation glide and pinning. Slip is assumed to occur on basal and prismatic systems, and dislocation pinning through the generation of geometrically necessary dislocations (GNDs). Elastic anisotropy and, through the coupling of GNDs with slip rate, physically-based lengthscale effects are included.     

Atomic structure and tip-induced reconstruction of bromide covered Cu(1 1 0) electrodes

The behavior of specifically adsorbed bromide on Cu(1 1 0) in 10 mM HBr has been studied using cyclic voltammetry in combination with high resolution in situ electrochemical scanning tunneling microscopy (EC-STM).At cathodic potentials near the onset of the hydrogen evolution reaction the structure of the bare copper surface was observed by EC-STM. A variation of the electrode potential in positive direction causes a specific anion adsorption leading to the formation of a highly ordered superstructure with a quasi-hexagonal symmetry. The two-dimensional lattice of this adlayer can be described by a c(3 × 2) unit cell. The bromide anions are arranged parallel to the close packed copper rows and are located in three different types of adsorption sites. These inequivalently bound bromide species are imaged with different brightness in the STM-pictures. As a result the bromide adlayer exhibits a long-ranged wavy superstructure superimposed on the atomic corrugation.Tip induced copper corrosion is used to obtain highly ordered nanostructures due to a locally confined electrochemical annealing process proceeding along the [0 0 1]-direction of the substrate. This annealing process results in the formation of Cu(1 0 0)-facets.     

Low-temperature and ambient-pressure synthesis and shape evolution of nanocrystalline pure, La-doped and Gd-doped CeO2

Nanocrystalline cuboidal ceria has been synthesized by low-temperature hydrothermal reaction of cerium nitrate hexahydrate with hexamethylene tetramine. The particles have been doped with La and Gd by adding aqueous solution of the nitrate salts of the metals to the reaction mixture. The pure and doped particles are cubic in crystal structure and 10-25 nm in size. The pure and La-doped ceria are cuboidal in morphology, whereas the Gd-doped particles are irregular in shape. High-resolution TEM imaging and image simulation indicates that atomic level steps are present on the particle surfaces. The particles are faceted parallel to the {1 1 1} and {1 0 0} crystallographic planes and a continuous switching takes place between the two possible surface facets. It appears that the surface energies of the {1 1 1} and {1 0 0} facets are quite similar in magnitude and the interplay of surface energy determines the particle shape. Chemically sensitive imaging and spectroscopy shows that the dopants are homogeneously distributed within the particles and that the oxidation state of Ce is a mixture of +3 and +4. No preferential segregation either of the dopant or the oxidation state was observed. However, since the facet switching does depend on the chemistry of the dopant, there must be an affect on the atomic scale.     

Adsorption and decomposition of NO on O-covered planar and faceted Ir(2 1 0)

We report on the adsorption and decomposition of NO on O-covered planar Ir(2 1 0) and nanofaceted Ir(2 1 0) with variable facet sizes investigated using temperature programmed desorption (TPD), high-resolution electron energy loss spectroscopy (HREELS), and density functional theory (DFT). When pre-covered with up to 0.5 ML O, both planar and faceted Ir(2 1 0) exhibit unexpectedly high reactivity for NO decomposition. Upon increasing the oxygen coverage to 0.7 ML O, planar Ir(2 1 0) has little activity while faceted Ir(2 1 0) still remains active toward NO decomposition, although NO decomposition is completely inhibited when both surfaces are pre-covered by 1 ML O. NO molecularly adsorbs on O-covered Ir at 300 K. At low NO and oxygen coverage, NO adsorbs on the atop sites of planar Ir(2 1 0) while on the bridge and atop sites of faceted Ir(2 1 0) composed of (1 1 0) and {3 1 1} faces. No evidence for size effects in the decomposition of NO on O-covered faceted Ir(2 1 0) is observed for average facet size in the range 5-14 nm. Our findings should be of importance for development of Ir-based catalysts for NO decomposition under oxygen-rich conditions.     

Faceting of nanoscale fingers on the (1 1 1) surface of gold

Gold fingers, one atomic layer (0.25 nm) high, 4-5 nm wide, and several hundred nm long are formed on the (1 1 1) surface of gold at room temperature by a combination of atomic manipulation and surface self-organisation. Each finger has two parallel edges (type A and type B, respectively) running along its length. The type A step is found to have higher step energy and become nanofaceted when disturbed by either thermal energy or the electric field under the STM tip, leading to the transformation of fingers to “nano-knives”. Our findings reveal the important role of step energy in the process of nanostructure fabrication on surfaces. The gold fingers also provide an ideal system for the investigation of meta-stable nanostructures.     

Molecular dynamics study of the primary ferrofluid aggregate formation

Investigations of the phase transitions and self-organization in the magnetic aggregates are of the fundamental and applied interest. The long-range ordering structures described in the Tománek's systematization (M. Yoon, and D. Tománek, 2010 [1]) are not yet obtained in the direct molecular dynamics simulations. The resulted structures usually are the linear chains or circles, or, else, amorphous (liquid) formations. In the present work, it was shown, that the thermodynamically equilibrium primary ferrofluid aggregate has either the long-range ordered or liquid phase. Due to the unknown steric layer force and other model idealizations, the clear experimental verification of the real equilibrium phase is still required. The predicted long-range ordered (crystallized) phase produces the faceting shape of the primary ferrofluid aggregate, which can be recognized experimentally. The medical (antiviral) application of the crystallized aggregates has been suggested. Dynamic formation of all observed ferrofluid nanostructures conforms to the Tománek's systematization.     

The growth and stability of Fe layers on the Mo(1 1 1) surface

The initial growth and the stability of Fe layers on the Mo(1 1 1) surface was studied with Auger electron spectroscopy, low energy electron diffraction, scanning tunneling microscopy and thermal desorption spectroscopy. At room temperature at least the first two monolayers grow layer-by-layer. The first layer is stable up to about 1200 K. Excess Fe starts to agglomerate at about 400 K and forms with increasing temperature thick flat-top islands which start to sublime at a somewhat below 1200 K. A strong decrease of the adsorption energy with coverage was found in the first monolayer. No {2 1 1} or { 1 1 0} micro-faceting could be seen at any coverage upon annealing.     

Edge-Defined Film-Fed (EFG) Growth of Rare-Earth Orthovanadates REVO4 (RE=Y,Gd): Approaches to Attain High-Quality Shaped Growth

In spite of their superior laser and polarizer properties rare-earth orthovanadates (REVO₄) single crystals have not been adopted yet into extensive industrial applications because of crystal growth difficulties. The main problems of CZ technique are compositional change and diameter instability. This work presents the first attempt to apply the edge-defined film-fed growth (EFG) technique by which well-shaped REVO₄crystals have been grown directly. The capillary properties of YVO₄ and GdVO₄ melt have been measured. The applicability of shaped growth for rare-earth orthovanadate family was approved by successful EFG growth of transparent rod-like macro-defect-free single crystals of YVO₄ and GdVO₄. We address two main approaches to enhance the quality of EFG crystals: (i) meniscus and crystal shape stability dependence on die top shape and (ii) the strategy of effective operating control. Concave die top was found to be the best choice for high-quality EFG growth of REVO₄ along [001] direction. The spectral analysis of weight signal from growing crystal was shown to be a useful feedforward clue to prevent crystallinity degradation at a very early stage. A reasonable stability of the EFG process was achieved using [211], [101], [001] and [100] pulling directions.     

Physical and chemical properties of bimetallic surfaces

Recent studies dealing with the structural, electronic, chemical and catalytic properties of well-defined bimetallic surfaces are reviewed. LEED and STM show that two metals interacting on a surface can form compounds with structures not seen in bulk alloys. Many novel phenomena related to the kinetics of growth of metals on metals have been discovered. The knowledge gathered in this area provides a solid basis for the synthesis of new materials with applications in areas of catalysis, electro-chemistry and microelectronics. In many cases, the formation of a surface bimetallic bond induces large changes in the band structure of the metals. For surfaces that contain transition or s,p metals, the strongest metal-metal interactions occur in systems that combine a metal with a valence band almost fully occupied and a metal in which the valence band is almost empty. A very good correlation is found between the electronic perturbations in a bimetallic system and its cohesive energy. Bimetallic bonds that display a large stability usually involve a significant redistribution of charge around the metal centers. The electronic perturbations affect the reactivity of the bonded metals toward small molecules (CO, NO, H₂, O₂, S₂, C₂H₄, CH₃OH, etc.). For supported monolayers of Ni, Pd, Pt and Cu a correlation is observed between the shifts in surface core-level binding energies and changes in the desorption temperature of CO from the metal adlayers. Examples are provided which demonstrate the utility of single-crystal studies for understanding the role of “ensemble” and “ligand” effects in bimetallic catalysts.