Electronic structure and adhesion on metal-aluminum-oxide interfaces

This paper reports on the results of the systematic analysis of the atomic and electronic structure of the Me/α-Al₂O₃(0001) interfaces for two series of isoelectronic metals (Me = Cu, Ag, Au and Ni, Pd, Pt), depending on the termination of the oxide substrate and the configuration of oxide films. The calculations have been performed by the pseudopotential method in the plane-wave basis set. The adhesion energy of metal films has been calculated depending on the cleavage plane. It has been shown that the adhesion energy is maximum at the oxygen interface, which is caused by the ion component in chemical bonding at this interface. The aluminum and aluminum-enriched interfaces are characterized by the metallic type of bonding. The local densities of states and the charge distribution near the interface have been analyzed. It has been demonstrated that oxygen vacancies at the interface substantially weaken the adhesion due to the partial breaking of Me-O bonds.     

Permittivity and conductivity of triglycine sulfate films on Al/SiO2 and α-Al2O3 substrates

Triglycine sulfate (TGS) films have been prepared by evaporation from a saturated aqueous solution on substrates of fused quartz coated by a layer of thermally deposited aluminum (Al/SiO₂) and white sapphire (α-Al₂O₃) on whose surface interdigital electrodes have been deposited by photolithography. The TGS films have a polycrystalline structure made up of blocks measuring 0.1–0.3 mm (Al/SiO₂) and 0.1 × 1.0 mm (α-Al₂O₃). The polar axis in the blocks is mostly confined to the substrate plane. The temperature dependences of the capacitance and dielectric losses normal to and in the film plane have maxima at the temperature coinciding with that of the ferroelectric phase transition in a bulk crystal, T _c . The low-frequency conductivity G in TGS/Al/SiO₂ structures displays a frequency dispersion described by the relation G ∼ ω ^s (s ≈ 0.82). The conduction can be tentatively ascribed to the hopping mechanism involving localized carriers with a ground state energy of 0.8–0.9 eV. At temperatures above and below T _c , the low-frequency conductivity in TGS/α-Al₂O₃ films operates through a thermally-activated mechanism with an activation energy of 0.9–1.0 eV. At the phase transition, an additional contribution to conductivity appears in TGS/α-Al₂O₃ films with a dispersion G ∼ ω^0.5, which can be associated with domain-wall relaxation.     

Blue upconversion emission from Tm<Superscript>3+</Superscript> sensitized by Nd<Superscript>3+</Superscript> in aluminum oxide crystalline ceramic powders

Upconversion (UC) emission in thulium (Tm³⁺) and neodymium (Nd³⁺) co-doped aluminum oxide ceramic powders prepared by combustion synthesis was investigated at room temperature using a continuous wave laser operating at 800 nm. Our sample containing Tm³⁺ (1 wt.%) did not show any UC emission but our sample co-doped with Tm³⁺ and Nd³⁺ in 1:2 wt.% proportion presented blue (∼480 nm) UC intensity more than one order of magnitude larger than our sample co-doped with Tm³⁺ and Nd³⁺ in 1:1 wt.% proportion. X-ray diffraction data showed the presence of α-Al₂O₃ and REAlO₃ (RE=Tm or Nd) crystalline phases in co-doped powders, while the singly doped powder has only α-Al₂O₃ phase. Our results show that the UC emission efficiency of Tm³⁺ and the host crystalline structure can be tailored by manipulating the Nd³⁺ doping concentration.     

Adhesion at the interfaces between BCC metals and α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Ab initio calculations of the atomic and electronic structures of Me(111)/α-Al₂O₃(0001) interfaces (Me = V, Cr, Nb, Mo, Ta, W) in the framework of density functional theory are reported. The energies of separation of metal films from oxide surfaces have been calculated. The structural and electronic factors responsible for the strong adhesion of bcc metal films on the oxygen termination of the surface of aluminum oxide have been analyzed.     

Preparation of alumina nanowires, nanorods, and nanowalls by chemical etching

Alumina (Al₂O₃) nanowires, nanorods, and nanowalls have been prepared from anodic aluminum oxide (AAO) templates by chemical etching in NaOH solution. Heating the template prior to etching is crucial to the morphology of subsequent prepared alumina nanostructures, which greatly depend on the phases of the AAO templates. It has been found that the templates with amorphous Al₂O₃, γ-Al₂O₃, and α+γ-Al₂O₃ phases will grow nanowires, nanorods, and nanowalls, respectively. A possible mechanism for forming different alumina nanostructures is proposed.     

Thermal- and photo-induced transformations of luminescence centers in αd-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> anion-defective crystals

The thermal- and photo-induced transformations of luminescence centers in anion-defective crystals of α-Al₂O₃ have been investigated. It has been found that the exposure of crystals to ultraviolet light at temperatures in the range 50–900°C leads to substantial changes in their thermoluminescence and radioluminescence spectra. According to the optical absorption and photoluminescence data, the detected F-type centers have been identified and the temperature ranges of the F → F ⁺ → F ₂ transformations and their possible mechanisms have been determined. The special attention has been drawn to the detailed similarity in the formation of complex F ₂-type centers in the initially perfect α-Al₂O₃ crystals irradiated with fast neutrons and in the studied anion-defective crystals.     

The production of nickel–alumina composite coating via electroplating

A series of electroplating works have been conducted to investigate the best condition for the coelectrodeposition of nickel–alumina (Ni/α–Al₂O₃) composite coating. Co-electrodeposition was done onto mild steel as cathode at ambient temperature (27°C) with current density of 30 mA/cm² under α-Al₂O₃ concentration of 2 g/l and various agitation speeds of 50, 100, 150, 200, and 250 rpms. The cross-section of the composite coatings portrayed α-Al₂O₃ particles was co-deposited. Under field emission scanning electron microscopy analysis, the coating shows a coarse surface morphology, while cross-sectional microstructures shows a compact embedding of α-Al₂O₃ particle in the Ni matrix. Elemental analysis by EDX detected the presence of Ni and α-Al₂O₃. Vickers microhardness testing shows that the coating hardness increases almost 60% at the highest agitation speed, i.e., 250 rpm.     

Specific features in the kinetics of thermally stimulated luminescence of α-Al2O3 crystals containing defects

A study of specific features in the kinetics of thermoluminescence (TL) of defective α-Al₂O₃ crystals is reported. The TL properties are experimentally shown to be related to the presence of oxygen vacancies of thermochemical or radiation origin. It is established that the differences in the TL kinetics in α-Al₂O₃ samples grown under different conditions can be accounted for by the hypothesis that the energy spectra of the trapping levels have different widths. As is demonstrated with a titanium impurity, this broadening of the energy spectrum can originate from the presence of traces of native impurities in the α-Al₂O₃ lattice. Fiz. Tverd. Tela (St. Petersburg) 39, 1538–1543 (September 1997)     

K X-ray emission spectra from ν-Al2O3

Summary η-Al₂O₃ sample was bombarded with 12.5 keV electron.K X-ray spectra of this sample were compared with those of pure Al and α-Al₂O₃.     

Adhesion of niobium films to differently oriented α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> surfaces

The atomic and electronic structures of the Nb/α-Al₂O₃ interface are studied by the electron density functional method. The structural and electronic properties of three corundum surfaces, as well as chemical bonds produced by metallic niobium films at variously oriented interfaces, are discussed. Relations between the electronic structure, geometry, and mechanical properties of the interfaces are analyzed. It is shown that the adhesion of niobium films to a great extent depends on the type of oxide surface.     

Effect of temperature on the conductivity, structural, and morphology of PVA-based alkaline solid polymer electrolyte

Alkaline polymer electrolytes (ASPE) have been prepared by using poly(vinyl alcohol) (PVA) polymer and which different weight percentages of potassium hydroxide (KOH), ceramic filler (α-Al₂O₃), and propylene carbonate (PC) have been added. The pure PVA/H₂O weight ratio (1.00:1.49), the PVA/KOH/H₂O (1.00:0.67:2.22), the PVA/KOH/α-Al₂O₃/H₂O (1.00:0.67:0.09:7.56), and PVA/KOH/α-Al₂O₃/PC/H₂O (1.00:0.67:0.09:2.64:1.32) were studied. The hysteresis phenomena in the conductivity temperature of ASPE were investigated. The polymer electrolytes prepared were characterized using X-ray diffraction and scanning electron microscopy.     

Theoretical studies of the g factors and local structure for Pt3+ in α-Al2O3

The anisotropic g factors and local structure for the trigonal Pt³⁺ centre in α-Al₂O₃ are theoretically investigated from the perturbation formulas of the g factors for a 5d ⁷ ion in trigonal symmetry. The Pt³⁺ impurity is found to experience an outward displacement by about 0.18 ? away from the centre of the oxygen octahedron along the C ₃-axis. The calculated g factors based on the above axial displacement show good agreement with the observed values. Importantly, the pending problem of +3 valence state of the doped Pt in α-Al₂O₃ is theoretically clarified, and the possibility of Pt⁺ (5d ⁹) is thus excluded in this work.     

Transition metal oxide perovskites by photoelectron and x-ray absorption spectroscopy

X-ray and ultraviolet photoelectron spectroscopy as well as x-ray absorption spectroscopy have been employed to investigate transition metal oxide perovskites of the general formula ABO₃ (A = La or rare-earth ion, B=trivalent transition metal ion). Systematics in the core levels and in the valence bands in the series of LaBO₃ compounds have been discussed. Lanthanum chemical shifts in the x-ray absorption spectra in this series show interesting trends. Photoelectron spectra of the solid solutions, LaNi_1−x Co _x O₃, LaNi_1−x Fe _x O₃ and LaFe_1−x Co _x O₃ show that the rigid band model is applicable to these systems. It is shown that x-ray photoelectron spectroscopy can be employed to identify multiple oxidation states of transition metal ions in oxide perovskites. Communication No. 30 from the Solid State and Structural Chemistry Unit. An erratum to this article is available at .     

Electronic excitations of Sc3+ impurity in α-Al2O3 crystals

Optical properties, including luminescence, of scandium-doped α-Al₂O₃ crystals have been studied in the VUV range. An absorption band associated with the scandium impurity was observed at the fundamental-absorption edge of crystalline corundum. A strong luminescence band peaking at 5.6 eV, which is most effectively excited within the 7.7–8.8-eV interval, was found. The kinetic and polarization characteristics of this luminescence were studied within the temperature range 6–500 K. An excitation model of the impurity complex and the mechanism of its relaxation are discussed. Fiz. Tverd. Tela (St. Petersburg) 40, 653–654 (April 1998)     

Quantitative EPR spectroscopy: Comparison between primary standards and application to MgO-MnO and α-Al2O3-Cr2O3 solid solutions

To study their reliability as primary standards in the quantitative EPR spectroscopy, a large series of pure paramagnetic compounds with known spin concentrations, whose spectra vary considerably in intensity, shape, structure and overall width are compared. The paramagnetic species examined as pure solid compounds and solutions, were free radicals (DPPH and TEMPO), vanadyl and Cu²⁺ ions (S = 1/2), Cr³⁺ (S = 3/2) and Mn²⁺ (5 = 5/2) ions. The quantitative EPR findings suggest that all theS = 1/2 paramagnetic compounds investigated and MnSO₄ · H₂O (S = 5/2) are reliable primary standards. By contrast, none of the pure Cr³⁺ compounds proved useful as primary standards because of their large fine-structure terms or high Néel temperature that invalidated the simple Curie law. Application of quantitative EPR in the study of dilute MgO-MnO and α-Al₂O₃-Cr₂O₃ solid solutions, focussing on the circumstances making paramagnetic species undetectable, is reported. In MgO-MnO solid solutions of high surface area, detection problems arising from the variation of local site symmetry can be circumvented and almost all Mn²⁺ are detected only by reducing the surface area. In concentrated α-Al₂O₃-Cr₂O₃ solid solutions, magnetic interactions lead to paramagnetic species being undetectable.     

Structural and phase transition of α-Al2O3 powders obtained by co-precipitation method

Aluminium oxide has been synthesized by co-precipitation technique at different annealing temperature. Powder XRD confirms the formation of α-Al₂O₃ with rhombohedral crystal structure having lattice constant a = 4.76 Å and b = 12.99 Å by the Scherer formula, the average crystallite size is estimated to be 66 nm. The scanning electron microscope results expose the fact that the α-Al₂O₃ nanomaterials are seemingly porous in nature and highly agglomerated. Chemical composition of aluminium oxide is confirmed by energy dispersive spectroscopy. The molecular functional group is confirmed by FTIR. Optical absorption of α-Al₂O₃ has been studied in the UV–vis region and its direct band gap is estimated to be 5.97 eV. This study involves the structural and phase transition of Al₂O₃ and also indicates that α-Al₂O₃ has considerable properties, deserving further investigation for the energetic materials with excellent properties for the possibility of using thin-layer α-Al₂O₃ as a thermo luminescence material.     

Optical spectra of triply-charged rare-earth ions in polycrystalline corundum

Solid samples of polycrystalline corundum α-Al₂O₃ activated by triply-charged rare-earth ions RE³⁺ (R=Eu³⁺, Er³⁺, Pr³⁺) were synthesized by the sol-gel technology. Characteristic narrow-line optical absorption and luminescence spectra produced by intraconfigurational 4f-4f transitions in RE³⁺ ions have been measured. RE³⁺ ions have been established to form one dominant type of optical centers in the corundum matrix, and the energy diagram of Eu³⁺ and Er³⁺ Stark levels in corundum has been determined. Fiz. Tverd. Tela (St. Petersburg) 40, 1442–1449 (August 1998)     

Electronic structure of an oxygen vacancy in Al<Subscript>2</Subscript>O<Subscript>3</Subscript> from the results of Ab Initio quantum-chemical calculations and photoluminescence experiments

The electronic structure of an oxygen vacancy in α-Al₂O₃ and γ-Al₂O₃ is calculated. The calculation predicts an absorption peak at an energy of 6.4 and 6.3 eV in α-Al₂O₃ and γ-Al₂O₃, respectively. The luminescence and luminescence excitation spectra of amorphous Al₂O₃ are measured using synchrotron radiation. The presence of a luminescence band at 2.9 eV and a peak at 6.2 eV in the luminescence excitation spectrum indicates the presence of oxygen vacancies in amorphous Al₂O₃.     

Combined SIMS,AES, and XPS investigations of tantalum oxide layers

Thick layers of tantalum oxide prepared by thermal and anodic oxidation have been studied by combined SIMS, AES, and XPS during depth profiling by 3keV Ar⁺ ion sputtering. The chemical composition of these films is revealed by the OKLL and O 1s signals and by the “lattice valence” parameter determined from the TaO _n ^± intensities. Thus the anodic film consists of a contamination layer, an oxygen-rich reactive interface and a thick homogeneous oxide layer followed by an interface to the Ta metal. The thermal oxide shows an oxygen concentration decreasing with depth and a broad oxide-metal interface. In both cases, carbon contamination (carbide) prevents the application of the valence model to the clean Ta substrate. The sputtering yield of the oxides was found to be 0.6 Ta₂O₅/ion.     

Characteristics of γ-Al2O3 nanoparticles generated by continuous-wave laser ablation in liquid

Laser ablation in liquid is one of the most widely investigated methods for generating various nanoparticles (NPs) that are difficult to produce using other means. In this paper, we report the generation of Al-oxide NPs by continuous-wave (CW) fibre laser ablation of corundum (α-Al₂O₃) target submerged in deionised water. The effects of CW fibre laser power and radiation time have been investigated. Characterisation of the NPs generated, in terms of size, size distribution, shape, chemical composition, and phase structure, was carried out by means of high-resolution transmission electron microscopy (HR-TEM), high angle annular dark field (HAADF) in scanning-transmission (STEM) mode, energy-dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD). The results show that the average size of Al-oxide NPs, in the range of 17 to 29 nm, increased with increasing the laser power and laser exposure time, and the NPs are dominated by stoichiometric γ-Al₂O₃ with a minor phase of α-Al₂O₃. The mechanism involved in the CWLAL is also discussed.