Electrical conductivity,diffusion of iron and the defect structure of α-Al2O3: Fe

A detailed defect model is developed for α-Al₂O₃:Fe accounting for conduction and diffusion at high temperatures as a function of iron concentration, oxygen pressure and temperature. This model involves single native and iron defects as well as triplets of (Fe_AlAl_iFe_Al), the latter dominating the defect structure at high Fe concentrations. Diffusion of Fe in A1₂O₃ is attributed to Fe_i^3.. The position of the Fe_Al' level is estimated.     

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.     

Nature of the anomalies of the thermolumenescence properties of dosimetric α-Al2O3 crystals

The results of investigations into the anomalies of the thermoluminescence properties of dosimetric corundum crystals are presented. The decisive role of deep-lying traps in the quenching of luminescence in anion-defect Al₂O₃ monocrystals is shown. The existence of deep-lying traps is demonstrated by the method of direct observations of thermoluminescence (TL) peaks associated with them. Experimental evidence for the influence of the degree of occupation of deep-lying traps on the main features of the TL dosimetric peak at 450 K is given. The results obtained are interpreted for a model of the interactive system of traps, which differs radically from the models described in the literature by a consideration of the temperature dependence of the probability of trapping of charge carriers on deep-lying traps. We believe that the heat quenching of luminescence is due to the thermal ionization of excited F-center states. Ural State Technical University. Translated from Izvestiya Vysshikh Uchebhykh Zavedenii, Fizika, No. 3, pp. 55–65, March, 2000.     

The fluorescence and thermoluminescence characteristics of α-Al2O3:C ceramics

This paper reports that polycrystalline α-Al₂O₃:C ceramics are fabricated by conventional ceramics process. The excitation, emission spectra, thermoluminescence (TL) and optical stimulated luminescence (OSL) of α-Al₂O₃:C polycrystalline ceramics are investigated. There exists 410nm maximum emission peak which is caused by recombination of an electron with F⁺ centre to produce an excited F centre. The samples show three clear TL glow peaks at 405, 493 and 610K. The attenuation constant of exponentially decaying fast component (τ₁) and slow component(τ₂) of OSL curve are 8.43s and 41.73s, respectively. Those fluorescence and thermoluminescence characteristics are similar with α-Al₂O₃:C crystal.     

Ionoluminescence and formation of color centers in α-Al2O3 single crystals under proton irradiation

This paper describes results of experimental studies on radiation defects in nominally pure single crystals of corundum in two initial states: α-Al₂O₃ with an unperturbed lattice and α-Al₂O₃:C with a high concentration of anion vacancies. Defects were identified from optical absorption spectra, ionoluminescence, pulsed cathodoluminescence and photoluminescence spectra. It is shown that mostly color centers of the F- and F⁺-types are formed in the α-Al₂O₃ lattice under irradiation with 5,7 MeV protons.     

The effect of gamma-ray irradiation on the electrical conductivity of CuO–PbO glasses

The effect of gamma-ray irradiation on the dc electrical conductivity of CuO–PbO glasses has been studied as a function of temperature. A 33% CuO–67% PbO glass composition has been prepared, using the melt-quenching technique. The samples have been irradiated to a dose of 0.5 MGy using a ⁶⁰Co γ-source. The electrical conductivity of this glass composition was investigated before and after gamma-ray irradiation. The values of the dc electrical conductivity have been measured from 303 to 373 K, and the activation energy of samples before and after gamma irradiation has been calculated. The observed data show that the electrical conductivity increases with temperature and following gamma irradiation. The electrical conductivity of CuO–PbO can be interpreted in terms of mixed ionic–electronic conduction.     

Structure determination of MnO2 films grown on single crystal α-Al2O3 substrates

Manganese oxide films have been grown by atomic layer deposition and investigated using electron diffraction and high-resolution electron microscopy (HREM). The films were deposited on the (001) surface of monocrystalline α-Al₂O₃. The films were found to consist of an ordered version of the hexagonal ε-MnO₂ (Akhtenskite) type. Using X-ray diffraction, the cell parameters were determined to be a?=?2.75(2)?Å and c?=?4.302(5)?Å. The films are epitaxial with a specific orientation relative to the Al₂O₃ substrate. The [210] and [001] axes of ε-MnO₂ are parallel to the [110] and [001] axes of α-Al₂O₃, respectively. Evidence of cation ordering was found by parallel beam electron diffraction. The ordered domains are needle shaped with widths of 2–10?nm. The unit cell of the ordered structure was found to be orthorhombic with cell dimensions a?=?2.75, b?=?4.76, c?=?4.302?Å and space group Pmnn (No. 58).     

DFT study of carbon monoxide adsorption on α-Al2O3(0001)

The adsorption of CO on α-Al₂O₃(0001) was studied using the DFT-GGA computational method and on α-Al₂O₃ powder experimentally by Infra red spectroscopy. The core and valence level regions of α-Al₂O₃(0001) single crystal surface were also studied experimentally. Ar ions sputtering of the surface results in a slight but reproducible decrease in the XPS O2p lines in the valence band regions due to preferential removal of surface (and near surface) O atoms. Core level XPS O1s and Al2p further confirmed oxygen depletion with an associated surface stoichiometry close to Al₂O_2.9. The adsorption energy of CO was computed and found equal to 0.52 eV for θ = 0.25, it decreased to 0.42 eV at θ = 1. The IR frequency of νCO was also computed and in all cases it was blue shifted with respect to gas phase CO. The shift, Δν, decreased with increasing coverage where it was found equal to 56 cm^? 1 for θ = 0.25 and decreased to 30 cm^? 1 for θ = 1. Structural analyses indicated that the change in the adsorption energy and the associated frequency shift is due to surface relaxation upon adsorption. Experimentally the adsorption of CO gave rise to one main IR peak at 2154 cm^? 1 at 0.3 Torr and above. Two far smaller peaks are also seen at lower pressures of 0.03–0.2 Torr at 2189 and 2178 cm^? 1. The isosteric heat of adsorption was computed for the IR band at 2154 cm^? 1 and was found equal to 0.2 eV which did not change with coverage in the investigated range up to θ = 0.6.     

The role of deep traps in luminescence of anion-defective α-Al2O3: C crystals

This paper presents the results of a study of deep traps responsible for thermally stimulated luminescence in single crystals of the anion-defective corundum α-Al₂O₃: C observed at temperatures of about 703, 778, 830, and 903 K. The effect of the filling of these traps by carriers of both signs on the sensitivity to radiation of the main thermoluminescence peak at 450 K, optically stimulated luminescence, and phototransferred thermoluminescence has been investigated. The results obtained are treated in terms of a model involving interactive competition of traps of different depth.     

Pulsed laser deposition of Eu:Y2O3 thin films on (0001) α-Al2O3

This paper focuses on the preparation and characterization of crystalline thin films of rare-earth-doped sesquioxides (Y₂O₃, Lu₂O₃) grown by pulsed laser deposition on single-crystal (0001) sapphire substrates. X-ray diffraction measurements show that the films with thicknesses between 1 nm and 500 nm were highly textured along the 111 direction. Using Rutherford backscattering analysis, the correct stoichiometric composition of the films was established. The emission and excitation spectra of europium-doped films with a thickness 100 nm look similar to those of the corresponding crystalline bulk material, whereas films with a thickness 20 nm show a completely different emission behavior. PACS 68.55.Jk; 78.66.Nk; 81.15.F     

Study of the Defect Structure and Crystal-Field Parameters of α-Al2O3:Yb3+

The methods currently used for studying the defect structure of laser host crystals doped with transition metal or rare-earth ions have several drawbacks or limitations. This study proposes an alternative approach for obtaining optimized impurity structures using molecular dynamics calculation in conjunction with the superposition model. This new approach is specifically applied to a system named α-Al₂O₃:Yb³⁺, in which the simulated defect structure is used to fit the superposition model parameters directly onto the observed energy levels. Such an approach provides predicted values of crystal-field parameters, Zeeman splitting g-factor, and hyperfine structure constants. Moreover, the C_3v site symmetry is found to be a good approximation for the actual C₃ site of Yb³⁺, as doped in an α-Al₂O₃ crystal.     

The effect of humidity on the ionic conductivity of Mg2+-stabilized K+-β-ferrite

The ionic conductivity of Mg²⁺-stabilized potassium β-ferrites was studied in wet and dry air atmosphere and in the temperature range between room temperature and 500 °C. Several conductivity processes were determined. The impedance spectroscopic measurements were combined with thermogravimetric analysis data, and a microscopic interpretation for the effect of humidity on the conductivity of K⁺-β-ferrite is proposed. Between 400 and 500 °C, a change in the conductivity behavior is observed which is associated with the magnetic ordering temperature and a structural ordering in the conductivity planes of the materials. The activation energy values of the different conduction processes have been calculated.     

The effect of oxygen and water vapor partial pressures on the total conductivity of BaCe0.7Zr0.1Y0.2O3–δ

Ionics - The effect of oxygen and water vapor partial pressure on the total conductivity of the proton-conducting BaCe0.7Zr0.1Y0.2O3–δ material is investigated in the present work....     

Possible cage motion of interstitial Fe in α-Al 2 O 3

In addition to spectral components due to Fe^2?+? and Fe^3?+?, a single line is observed in emission Mössbauer spectra following low fluence (<10¹⁵ cm^???2) implantation of ⁵⁷Fe*, ⁵⁷Mn and ⁵⁷Co in α-Al₂O₃. For the ⁵⁷Co and ⁵⁷Mn implantations, the intensity of the single line is found to depend on the emission angle relative to the crystal symmetry axis. This angular dependence can be explained by a non-isotropic f-factor and/or motion of the Fe ion between sites in an interstitial cage. It is argued that interstitial cage motion is a more likely explanation, as this can account for the lack of quadrupole splitting of the line.     

Adsorption and dehydrogenation of 2-propanol on the surface of γ-Al2O3-supported gold

The adsorption and reactions of 2-propanol on γ-Al₂O₃ and γ-Al₂O₃-supported gold samples were investigated by infrared (IR) spectroscopy, modulated differential scanning calorimetry (MDSC) and mass spectrometry. Adsorption of the alcohol on the samples at room temperature led to formation of molecularly adsorbed 2-propanol and 2-propoxide species bonded to Al³⁺ sites. Treatment of γ-Al₂O₃ after alcohol adsorption in flowing He from 25 to 300 °C led to 2-propanol desorption, without evidence of surface reactions. In contrast, when supported gold samples were exposed to the same thermal treatment, formation of acetone and H₂ was observed by mass spectra of the effluent gases from the flow reactor. Concomitantly, IR spectra of the samples showed the appearance of a band at 1698 cm^? 1, assigned to ν_CO vibrations of adsorbed acetone. The formation of acetone occurred by the dehydrogenation of 2-propoxide species bonded to Al³⁺ sites, as evidenced by (a) the decrease in the intensities of their IR bands and (b) the presence of a MDSC peak at approximately the same temperature as that at which acetone was formed and the 2-propoxide species were consumed. It is proposed that gold particles on the γ-Al₂O₃ surface facilitate breaking of the β-CH bond of neighboring surface 2-propoxide species to give acetone. Our results emphasize the bifunctional character of supported gold catalysts for the dehydrogenation of alcohols.     

The effect of vacuum annealing on the remediation abilities of iron and iron−nickel nanoparticles

Zero-valent iron nanoparticles are effective remediators of uranium from solution. It is postulated that the improved core crystallinity and the migration of impurity phases to the nanoparticle surfaces induced by annealing may improve their corrosion resistance and reactive lifespan. The ability of annealed and non-annealed Fe and FeNi nanoparticles to remediate a U-contaminated effluent from AWE, Aldermaston was investigated. Nanoparticles (of diameter typically between 0 and 100 nm) were introduced to the effluent and allowed to react for 7 days during which the liquid and nanoparticulate solids were periodically sampled. In all the systems, the maximum U-uptake occurred within 1 h of introduction, with variable efficiency. The Fe nanoparticles removed 98% of the total U from solution, resulting in a final U-concentration of <4 μg/L. A rapid release of Fe into solution was recorded early in the reaction period: attributed to limited partial dissolution of the nanoparticles. Annealing the Fe nanoparticles did not affect their efficiency but the dissolution of Fe was significantly reduced and X-ray Photoelectron Spectroscopy indicated slower progressive oxidation. The performance of the FeNi nanoparticles was significantly improved by annealing, with U-uptake increasing from 50 to 94%. Although the dissolution of Ni was completely inhibited by annealing, the Fe dissolution increased compared to that observed for the non-annealed FeNi nanoparticles, in contrast to behaviour exhibited by Fe-annealed nanoparticles. In all the systems, U was reduced to U(IV) and retained on the surfaces of the nanoparticulate solids for up to 48 h; the U-stability was not affected by annealing the Fe or the FeNi nanoparticles before use.     

Structure of the (0001) surface of α-Al2O3 from first principles calculations

Fully self-consistent ab initio calculations based on pseudopotentials are used to study the structure and energetics of the basal-plane surface of α-Al₂O₃. The calculated forces on the atoms are used to relax the atomic positions to equilibrium. It is shown that surface relaxations are very large and lead to a reduction of the surface energy by over a factor of two. The results support the validity of earlier work based on pair-interaction models.     

The effect of the irradiation of germanium with α-particles on the recombination of current carriers

A study was made of the effect of irradiation with -particles on surface recombination on germanium. An approximative evaluation of the results showed that the position of the energy level of the recombination centre produced by irradiation lies near to the upper edge of the valence band or the lower edge of the conduction band. A value of roughly 3. 10^–12 cm² was obtained for the effective recombination surface produced by the absorption of one -particle.