Hydroxylation-induced modifications of the Al2O3/NiAl(0 0 1) surface at low water vapour pressure

STM, STS, LEED and XPS data for crystalline θ-Al₂O₃ and non-crystalline Al₂O₃ ultra-thin films grown on NiAl(0 0 1) at 1025 K and exposed to water vapour at low pressure (1 × 10⁻⁷-1 × 10⁻⁵ mbar) and room temperature are reported. Water dissociation is observed at low pressure. This reactivity is assigned to the presence of a high density of coordinatively unsaturated cationic sites at the surface of the oxide film. The hydroxyl/hydroxide groups cannot be directly identify by their XPS binding energy, which is interpreted as resulting from the high BE positions of the oxide anions (O_1s signal at 532.5-532.8 eV). However the XPS intensities give evidence of an uptake of oxygen accompanied by an increase of the surface coverage by Al³⁺ cations, and a decrease of the concentration in metallic Al at the alloy interface. A value of ∼2 for the oxygen to aluminium ions surface concentration ratio indicates the formation of an oxy-hydroxide (AlO_xOH_y with x + y ∼ 2) hydroxylation product. STM and LEED show the amorphisation and roughening of the oxide film. At P(H₂O) = 1 × 10⁻⁷ mbar, only the surface of the oxide film is modified, with formation of nodules of ∼2 nm lateral size covering homogeneously the surface. STS shows that essentially the valence band is modified with an increase of the density of states at the band edge. With increasing pressure, hydroxylation is amplified, leading to an increased coverage of the alloy by oxy-hydroxide products and to the formation of larger nodules (∼7 nm) of amorphous oxy-hydroxide. Roughening and loss of the nanostructure indicate a propagation of the reaction that modifies the bulk structure of the oxide film. Amorphisation can be reverted to crystallization by annealing under UHV at 1025 K when the surface of the oxide film has been modified, but not when the bulk structure has been modified.     

Luminescence properties of anodic aluminum oxide films with organic luminophores embedded into pores

Luminescence properties of porous anodic aluminum oxide films formed in a 0.6 M solution of citric acid and luminescence of paraterphenyl, perylene, coumarin 7, and rhodamine 6G dyes adsorbed by the films are investigated. The nature of emitting centers in anodic aluminum oxide is revealed. Intense photoluminescence of all tested dyes embedded into pores of anodic aluminum oxide has been found. A redshift of fluorescence spectra of dyes adsorbed by the matrix and emergence of an additional longwave band have been detected. Data obtained can be used in developing new thin-film luminescent coatings for future applications in optoelectronics and molecular electronics. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No 4, pp. 483–488, July–August, 1997.     

The 2D Rancieite-type manganic acid and its alkali-exchanged derivatives: Part I — Chemical characterization and thermal behavior

The 2D Rancieite type manganic acid was prepared by reduction of KMnO₄ in acidic medium. Its ion exchange behavior allows to prepare alkali derivatives. All compounds were characterized with use of a combination of X-ray diffraction, chemical analyses, TGA, magnetic measurements and spectroscopic techniques. The evolution of their chemical composition versus temperature was studied between 180 and 400 °C. It shows that the dehydration process is partly reversible in these compounds whereas the weak reduction is irreversible. The 2D Rancieite-type manganic acid is readily different from a Birnessite-type phyllomanganate, as shown by several features: the interlayer distance, the ion exchange capacity, the thermal behavior, the interlayer cation content, the manganese average oxidation state, the magnetic behavior and the IR spectrum.     

Heat-treatment studies of molybdenum oxide-monohydrate

The dehydration of molybdic acid, MoO₃---H₂O, was studied by thermal analysis, X-ray diffractometry and FTIR spectroscopy. The results show that an intermediate phase, MoO₃-2/3H₂O is formed at 216 °C and the monoclinic form of MoO₃ is grown above 350 °C. The mechanism of dehydration and structural rearrangement were confirmed by the features of the infrared spectra showing formation of corner-shared MoO₆ octahedra.     

Phase transfer of highly monodisperse iron oxide nanocrystals with Pluronic F127 for biomedical applications

Iron oxide nanoparticles made from the thermal decomposition method are highly uniform in all respects (size, shape, composition and crystallography), making them ideal candidates for many bioapplications. The surfactant coating on the as-synthesized nanoparticles renders the nanoparticles insoluble in aqueous solutions. For biological applications nanoparticles must be water soluble. Here we demonstrate the phase transfer of our nanoparticles with the biocompatible copolymer Pluronic F127. Transmission electron microscopy, Fourier transform infrared spectroscopy and dynamic light scattering indicate that the nanoparticles are coated discretely. Magnetic measurements show that the nanoparticles remain superparamagnetic with saturation magnetization ∼96% of the maximum theoretical value.     

Dextran-modified iron oxide nanoparticles

Dextran-modified iron oxide nanoparticles were prepared by precipitation of Fe（Ⅱ） and Fe（Ⅲ） salts with ammonium hydroxide by two methods. Iron oxide was precipitated either in the presence of dextran solution, or the dextran solution was added after precipitation. In the second method, the iron oxide particle size and size distribution could be controlled depending on the concentration of dextran in the solution. The nanoparticles were characterized by size-exclusion chromatography, transmission electron microscopy and dynamic light scattering. Optimal conditions for preparation of stable iron oxide colloid particles were determined, The dextran/iron oxide ratio 0-0,16 used in precipitation of iron salts can be recommended for synthesis of nanoparticles suitable for biomedical applications, as the colloid does not contain excess dextran and does not coagulate.     

High-density plasma etching of indium-zinc oxide films in Ar/Cl2 and Ar/CH4/H2 chemistries

The dry etching characteristics of transparent and conductive indium-zinc oxide (IZO) films have been investigated using an inductively coupled high-density plasma. While the Cl₂-based plasma mixture showed little enhancement over physical sputtering in a pure argon atmosphere, the CH₄/H₂/Ar chemistry produced an increase of the IZO etch rate. On the other hand, the surface morphology of IZO films after etching in Ar and Ar/Cl₂ discharges is smooth, whereas that after etching in CH₄/H₂/Ar presents particle-like features resulting from the preferential desorption of In- and O-containing products. Etching in CH₄/H₂/Ar also produces formation of a Zn-rich surface layer, whose thickness (∼40 nm) is well-above the expected range of incident ions in the material (∼1 nm). Such alteration of the IZO layer after etching in CH₄/H₂/Ar plasmas is expected to have a significant impact on the transparent electrode properties in optoelectronic device fabrication.     

Different effects of cerium ions doping on properties of anatase and rutile TiO2

Pure and Ce⁴⁺ doped anatase and rutile TiO₂ were prepared by hydrothermal methods and characterized by XRD, TEM, UV-vis diffusion spectroscopy, and XPS measurements. The photocatalytic reactivity of the catalysts was evaluated by the photodegradation of Rhodamine B (RB) under ultraviolet irradiation. The photocatalytic efficiency of the rutile sample doped with an appropriate amount of Ce⁴⁺ was enhanced while all Ce⁴⁺ doped anatase samples showed a much lower activity than pure anatase. The reasons were discussed     

Nanostructure characterization of high k materials by spectroscopic ellipsometry

In this work, the optical and structural properties of high k materials such as tantalum oxide and titanium oxide were studied by spectroscopic ellipsometry, where a Tauc-Lorentz dispersion model based in one (amorphous films) or two oscillators (microcrystalline films) was used. The samples were deposited at room temperature by radio frequency magnetron sputtering and then annealed at temperatures from 100 to 500 °C. Concerning the tantalum oxide films, the increase of the annealing temperature, up to 500 °C does not change the amorphous nature of the films, increasing, however, their density. The same does not happen with the titanium oxide films that are microcrystalline, even when deposited at room temperature. Data concerning the use of a four-layer model based on one and two Tauc-Lorentz dispersions is also discussed, emphasizing its use for the detection of an amorphous incubation layer, normally present on microcrystalline films grown by sputtering.