High-temperature electrical transport in Al-doped calcium and strontium titanates

The electrical conductivity of perovskite-related oxides CaTi_1−xAl_xO_3−δ and SrTi_1−xAl_xO_3−δ (x=0−0.4) were investigated within the temperature range 900 to 1000 °C and the oxygen partial pressure range between 10⁻²⁰ and 0.21 atm using a dc four-point technique. The materials investigated show predominantly p-type electronic conductivity at high, n-type electronic conductivity at low, and ionic conductivity at intermediate oxygen partial pressures. The values of ionic conductivity in CaTi_1−xAl_xO_3−δ were found to be lower than those in CaTi_1−xFe_xO_3−δ. The effect of aluminium concentration on the high-temperature transport properties was examined. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Preparation and electrochemical properties of nano Al<Subscript>0.2</Subscript>V<Subscript>2</Subscript>O<Subscript>5.3−<Emphasis Type="BoldItalic">δ</Emphasis></Subscript> cathode materials for rechargeable lithium batteries

Nano-sized Al³⁺-doped V₂O₅ cathode materials, Al_0.2V₂O_5.3−δ , were prepared by an oxalic acid assisted sol–gel method at 350 °C (sample A) and 400 °C (sample B). X-ray diffraction confirmed that samples A and B were pure phase Al_0.2V₂O_5.3−δ with an orthorhombic structure close to that of V₂O₅. Scanning electron microscopy showed that sample A was in nanoscale with a mean particle size about 50 nm. Cyclic voltammetry showed the good electrochemical and structural reversibility of the Al_0.2V₂O_5.3−δ nanoparticles during the Li⁺ insertion/extraction process. The Al_0.2V₂O_5.3−δ nanoparticles exhibited excellent charge–discharge cycling performance and rate capability compared to that of bulky V₂O₅ electrodes. For instance, the materials delivered a reversible specific capacity about 180 mAh g⁻¹ (sample A) and 150 mAh g⁻¹ (sample B), in the potential window of 4.0–2.0 V at the current density of 150 mA g⁻¹. The Al_0.2V₂O_5.3−δ nanoparticles in particular showed almost no capacity fading for at least 50 cycles.     

The metal-semiconductor transition monitored by excited state lifetimes of Al4O m − clusters

The lifetimes of electronically excited states of Al₄O _m ⁻ clusters are measured for m=1,3,4,5, and 6 using time-resolved photoelectron spectroscopy. With increasing number of oxygen atoms the lifetimes increase. This can be explained qualitatively by a metal-semiconductor transition occurring between the metal-like Al₄ ⁻ cluster and the fully oxidized semiconductor-like Al₄O₆ ⁻ cluster. Long lifetimes of electron-hole excitations are characteristic for semiconductors, while in metals the strong interaction between the delocalized electrons causes short lifetimes.     

Novel trivalent cation conducting solids and their application

Among the trivalent ion conductors reported, the highest ion conductivity was realized with the trivalent Al³⁺ ion conducting (Al_xZr_1−x)_4/(4−x)Nb(PO₄)₃ solid electrolyte and the value enters into the region between yttria stabilized zirconia (YSZ) and calcia stabilized zirconia (CSZ) that are well known to be high oxide anion conductors commercialized. The improvement of the ion conductivity and the mechanical strength was simultaneously achieved by adding B₂O₃ during the sintering procedure. The Al³⁺ ion conducting (Al_xZr_1−x)_4/(4−x)Nb(PO₄)₃ solid electrolyte with B₂O₃ treatment was combined with YSZ, and the 0.7La₂O₂SO₄-0.3Li₂SO₄ solid was attached on the (Al_xZr_1−x)_4/(4−x)Nb(PO₄)₃ solid surface as the auxiliary electrode for sulfur dioxide (SO₂) gas sensing. The sensor response was rapid, reproducible and continuous with obeying the Nernst theoretical relationship. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

O<Subscript>2</Subscript> photodesorption from AuO<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> and Au<Subscript>2</Subscript>O<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack>

Using time-resolved photoelectron spectroscopy, the decay channels of AuO₂⁻ and Au₂O₂⁻ following photoexcitation with 3.1-eV photons have been studied. For AuO₂⁻, a state with a rather long lifetime of 30 ps has been identified. Its decay path could not be determined but photodesorption can be excluded. For Au₂O₂⁻, the spectra indicate O₂ desorption after 3.1-eV photoexcitation on a time scale of 1 ps. While comparing these results on Au _n O₂⁻ with analogous data on Ag _n O₂⁻ clusters, a discernible pattern emerges: for dissociatively bound O₂(AuO₂⁻, Ag₃O₂⁻), there are long-living excited states which do not decay by oxygen desorption, while for molecular chemisorption (Au₂O₂⁻, Ag₂O₂⁻, Ag₄O₂⁻, Ag₈O₂⁻), the 3.1-eV photoexcitation triggers fast O₂ desorption with a high quantum yield.     

μ− SR studies of oxide-superconductorsSR studies of oxide-superconductors

The negative muon spin rotation method (μ⁻ SR) has been applied to studies of electronic states at oxygen sites of oxide superconductors YBa₂Cu₃O₇, Nd_2−x Ce _x CuO_4−δ (x=0.15, oxygen reduced), LiTi₂O₄ and related oxide-insulators La₂CuO_4−δ, CuO, Cu₂O. The paramagnetic shifts of μ⁻ trapped at oxygen nuclei in these polycrystalline powder samples have been measured at 300 K. All the measured shifts are positive. In copper-oxides the paramagnetic shifts are of the order 10⁻³, while in LiTi₂O₄ is very small (8.4±3.34×10⁻⁵). In YBa₂Cu₃O₇, a fast μ⁻ spin relaxation timeT ₂ ^* (∼ 200 ns) has been observed; the reason for this is unknown and further studies are now in progress.     

Structure, morphology and electrochemistry of doped lithium cobalt oxides

The structure, morphology and electrochemical performance of LiCoO₂ powders doped with various trivalent cations such as M³⁺=Ni³⁺, Al³⁺, and B³⁺ have been investigated. X-ray diffraction patterns and FTIR data show that LiCo_1−yNi_yO₂ oxides display a solid solution in the whole range 0≤y≤1, while the solubility limit of LiCo_1−yAl_yO₂ and LiCo_1−yB_yO₂ materials is about y=0.35. Electrochemical features of LiCo_1−yNi_yO₂ cathode materials show remarkable stability in their charge-discharge profiles. Aluminum substitution also stabilizes the two-dimensional framework and induces an increasing average cell potential than for LiCoO₂. The overall capacity of the LiCo_1−yB_yO₂ oxides has been reduced due to the sp metal substitution, however, a more stable charge-discharge cycling characteristic has been observed when electrodes are charged up to 4.4 V as compared to the performances of the native oxides. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Photoluminescence of zinc oxide modified by nanopowders

The modifying effect of Al₂O₃, Al₂O₃ · CeO₂, ZrO₂, ZrO₂ · Y₂O₃ nanopowders on the photoluminescence spectra of ZnO powder in the 360–660 nm range is investigated. It is found that the introduction of nanoparticles causes a decrease in the ultraviolet band intensity and an increase in the visual spectral band intensity. The change in the intensity of elementary components of the visible range band during modification seems to be explained by the emergence of oxygen and zinc vacancies (V _O⁺ and V _Zn⁻) and interstitial oxygen ions (O _i ⁻).     

Surface Plasmon Resonance of Au Nanoparticles Fabricated by Negative Ion Implantation and Grid Structure toward Plasmonic Applications

Optical properties of Au nanoparticle composites and a grid structure of Cu nanoparticle composite were studied. Negative ion implantation was applied to synthesize Au and Cu nanoparticles in amorphous SiO₂ and Al₂O₃. Au nanoparticles were embedded within a depth of 30 nm by 60keV Au⁻ implantation. The surface plasmon resonance (SPR) of Au:SiO₂ and Au: Al₂O₃ composites shifted to red and to blue, respectively, compared to calculated ones by the Mie theory. Optical nonlinearity was measured with pump-probe femtosecond spectroscopy and the transient spectrum of Au: Al₂O₃ composite presented a large red shift from the SPR peak. Image mapping of far-field transmitted intensity of Cu-implanted SiO₂ with a fine grid structure drawn by laser-lithography was observed by a scanning near-field optical microscopy (SNOM) system.     

Theoretical analysis of the thermal conductivity of high-temperature superconductors

Summary The thermal conductivity of YBa₂Cu₃O_7−δ high-T _c superconductor is analysed self-consistently on both normal and superconducting states on the base of the Bardeen-Rickayzen-Tewordt extended theory to take into account the effects of magnetic field and superconducting fluctuations. It is shown that experimental data are in a quantitative agreement with theory even if the number and variation intervals of adjustable parameters are substantially reduced in comparison with previous works. Phonon relaxation rates due to different mechanisms of phonon scattering as well as the parameters of electron-phonon interaction are estimated. It is shown that thermal conductivity in YBa₂Cu₃O_7−δ is consistent with the BCS model with intermediate electron-phonon coupling λ=1–3 the phonon-electron and electron-phonon relaxation times near critical temperature are evaluated to be 10⁻¹⁰s and 10⁻¹²s, respectively.     

Hf-sputtered indium oxide films doped with tin

Indium oxide films doped with tin (ITO-films) have been hf-sputtered from an 80 at-%In₂O₃/20 at-%SnO₂ target onto glass substrates. The sputter atmosphere contained mainly argon (10⁻²Torr) with addition of oxygen (0≦p _{O 2}≦2·10⁻²Torr). The sputtered films aren-conductors. The conductivity and density of charge carriers depend on the oxygen content of the sputter gas. They could be varied by two orders of magnitude. In air or in oxygen atmosphere the films oxidize at the surface and for a certain depth beneath the surface, thus decreasing the conductivity. The Hall mobility of the sputtered films is smaller (≈10 cm²V⁻¹ s⁻¹) than one observes at ITO films produced by CVD sparaying or other methods. The conductivity of as sputtered films approached maximum values of about 1000Ώ⁻¹cm⁻¹.     

Electrical and magnetic properties of [(CoFeZr)x(Al2O3)1 ? x/(α-SiH)]n multilayer structures

The concentration dependences of the electrical resistivity and complex permeability of [“(Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} ”/“α-Si: H”] _n multilayer structures and (Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} composites have been studied. It has been established that introduction of a semiconductor interlayer into the (Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} composites substantially decreases the electrical resistivity of [“(Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} ”/“α-Si: H”] _n multilayer structures. The concentration dependences of the real and imaginary parts of the complex permeability of the [“(Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} ”/“α-Si: H”] _n nanomultilayer structures substantially differ from those of the (Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} composites. The real part of the complex permeability of the [“(Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} ”/“α-Si: H”] _n nanomultilayer structures follows the curve with a minimum near the percolation threshold of the composite, and the imaginary part smoothly decreases as the ferromagnetic phase concentration increases. The results obtained are explained by the increase in the bifurcation temperature due to the conduction electrons of the semiconductor interlayer, which favor magnetic ordering of ferromagnetic grains.     

The effects of ceramic fillers on the PMMA-based polymer electrolyte systems

The effects of ceramics fillers on the polymethylmethacrylate (PMMA)-based solid polymer electrolytes have been studied using ac impedance spectroscopy and infrared spectroscopy. The polymer film samples were prepared using solution cast technique, tetrahydrofuran (THF) used as a solvent, and ethylene carbonate (EC) has been used as plasticizer. Lithium triflate salt (LiCF₃SO₃) has been incorporated into the polymer electrolyte systems. Two types of ceramic fillers, i.e., SiO₂ and Al₂O₃, were then implemented into the polymer electrolyte systems. The solutions were stirred for several hours before it is poured into petri dishes for drying under ambient air. After the film has formed, it was transferred into desiccator for further drying before the test. From the observation done by impedance spectroscopy, the room temperature conductivity for the highest conducting film from the (PMMA–EC–LiCF₃SO₃) system is 1.36 × 10⁻⁵ S cm⁻¹. On addition of the SiO₂ filler and Al₂O₃ filler, the conductivity are expected to increase in the order of ∼10⁻⁴ S cm⁻¹. Infrared spectroscopy indicates complexation between the polymer and the plasticizer, the polymer and the salts, the plasticizer and the salts, and the polymer and the fillers. The interactions have been observed in the C=O band, C–O–C band, and the O–CH₃ band. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7-9, 2006.     

Factors determining the energy yield of luminophors based on single-crystal films of Al2−Y2O3−R2O3 oxides

We consider the factors determining the energy yield of crystallophosphors based on single-crystal films of oxides of the system Al₂−Y₂O₃−R₂O₃ (R is the rare-earth ions) that are used as different types of luminescent converters. Special features of producing the films by the method of liquid-phase epitaxy from Pb−B₂O₃ and Bi₂O₃-based fluxes are analyzed, and the advantages of this method for production of efficient luminophors, which are based on high-melting oxides doped with mercury-like impurities, are shown. It is established that the main factor that bounds the crystallophosphor luminous yield is the presence of donor-acceptor complexes of the Pb²⁺−Pb⁴⁺ and Fe³⁺−Fe²⁺-type that form different channels of dissipation of excitation energy. The means of minimizing the contribution of these ions to the processes of excitation-energy relaxation are discussed. Institute of Applied Physics, I. Franko L'vov State University, 49 General Chuprynka Str., L'vov, 290044, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 6, pp. 819–823, November–December, 1999.     

Optical and thermal properties of metals,ceramics, and CVD diamond films upon high-temperature laser heating

A complex optical method for simultaneous determination of optical and thermal properties of solids (true temperature, reflectance, transmittance, absorbance, extinction, specific heat capacity, thermal conductivity, and diffusivity) in a wide temperature range (800–2700°C) was proposed and experimentally demonstrated. The developed setup is characterized by a high processing rate (the time taken for measuring all parameters is from milliseconds to tens of seconds). It allows the study of rather small samples (about several milligrams), which is a significant advantage as applied to new or expensive materials. New and widely used materials (AlN, Al₂O₃, Si₃N₄, SiC, and Al₂O₃/SiC ceramics; C45, 16MnCrS5, 115CrV3, X5NiCr18 9, X12CrNi17 7, Sd, and Satellite 6 steels; E-Cu, CuSn, AlMgSi1, and AlCuMgPb copper and aluminum alloys; as well as chemical vapor deposition (CVD) diamond films) were studied at heating rates of 10³−10⁴K·s⁻¹ in various atmospheres (air and argon at pressures of 1 and 10⁻³ atm). This study demonstrated high efficiency and informativity of the proposed method. The data obtained can be used to develop theoretical models describing the solid structure and properties at high temperatures in oxidizing, neutral, or regenerative atmospheres.     

Polaron and ion diffusion in a poly(3-hexylthiophene) thin-film transistor gated with polymer electrolyte dielectric

Electrolytes are finding applications as dielectric materials in low-voltage organic thin-film transistors (OTFT). The presence of mobile ions in these materials (polymer electrolytes or ion gels) gives rise to very high capacitance (>10 μF/cm²) and thus low transistor turn-on voltage. In order to establish fundamental limits in switching speeds of electrolyte gated OFETs, we carry out in situ optical spectroscopy measurement of a poly(3-hexylthiophene) (P3HT) OTFT gated with a LiClO₄:poly(ethyleneoxide) (PEO) dielectric. Based on spectroscopic signatures of molecular vibrations and polaron transitions, we quantitatively determine charge carrier concentration and diffusion constants. We find two distinctively different regions: at V _G≥−1.5 V, drift-diffusion (parallel to the semiconductor/dielectric interface) of hole-polarons in P3HT controls charging of the device; at V _G<−1.5 V, electrochemical doping of the entire P3HT film occurs and charging is controlled by drift/diffusion (perpendicular to the interface) of ClO₄ ⁻ counter ions into the polymer semiconductor.     

Band alignment and interfacial properties of atomic layer deposited (TiO2)x(Al2O3)1?x gate dielectrics on Ge

(TiO₂) _x (Al₂O₃)_1−x (x=0.7,0.8,0.9) gate dielectrics were deposited on Ge by atomic layer deposition using trimethylaluminium and Ti isopropoxide. The interfacial properties and band alignment were investigated by means of transmission electron microscopy (TEM) and X-ray photoemission spectroscopy. High-resolution TEM results show that the (TiO₂)_0.8(Al₂O₃)_0.2 film annealed at 500°C is amorphous with sharp interface between (TiO₂)_0.8(Al₂O₃)_0.2 and Ge. The conduction-band offsets are enhanced from 1.04 to 1.40 eV with increasing Al content. Capacitance equivalent thickness of 15.8 ? for (TiO₂)_0.9(Al₂O₃)_0.1 gate dielectrics is achieved with a gate leakage current of 2.70×10⁻⁵ A/cm² at V _g=+1 V.     

Theoretical study of ZnO adsorption and bonding on Al<Subscript>2</Subscript>O<Subscript>3</Subscript> (0001) surface

ZnO adsorption on sapphire (0001) surface is theoretically calculated by using a plane wave ultrasoft pseudo-potential method based onab initio molecular dynamics. The results reveal that the surface relaxation in the first layer Al-O is reduced, even eliminated after the surface adsorption of ZnO, and the chemical bonding energy is 434.3(±38.6) kJ · mol⁻¹. The chemical bond of ZnO (0.185 ± 0.01 nm) has a 30° angle away from the adjacent, Al-O bond, and the stable chemical adsorption position of the Zn is deflected from the surface O-hexagonal symmetry with an angle of about 30°. The analysis of the atomic populations, density of state and bonding electronic density before and after the adsorption indicates that the chemical bond formed by the O²⁻ of the ZnO and the surface Al³⁺ has a strong ionic bonding characteristic, while the chemical bond formed by the Zn²⁺ and the surface O²⁻ has an obvious covalent characteristic, which comes mainly from the hybridization of the Zn 4s and the O 2p and partially from that of the Zn 3d and the O 2p.     

Interaction of muonium with oxygen on silica powder surfaces

Results of the first μSR studies using Merck FO Optipur silica powder, which contains paramagnetic impurities at the ppb level and has a surface area of 610±20 m²/g. are reported. Above 20 K, the transverse field muonium relaxation rate is roughly constant at 0.5 μs⁻¹. Upon the addition of oxygen at ppm levels, the relaxation rate increases linearly with O₂ concentration in the temperature range from 40–100 K yielding two-dimensional depolarization rate constants on the order of 10⁻⁴ cm² molecule⁻¹ s⁻¹. As the temperature is increased further, both oxygen and muonium desorb from the surface yielding a three-dimensional rate constants at 300 K of 3.1(3)×10–10⁻¹⁰ cm³ molecule⁻¹ s⁻¹, in agreement with the gas phase value. Longitudinal field measurements suggest that MuO₂ is formed and is able to spin exchange with other oxygen molecules.     

Electrochemical promotion of Pd for the hydrogenation of C2H2

The effect of Non-Faradaic Electrochemical Modification of Catalytic Activity, orin-situ controlled promotion, was investigated during Acetylene selective hydrogenation on Pd films deposited on β″ - Al₂O₃, a Na⁺ conductor, at temperatures from 60 to 100 °C and GHSVs from 10³ to 10⁴ h-⁻¹, i.e., under conditions similar to those used in industrial processes. It was found that both acetylene conversion and hydrogenation selectivity can be affected by means of externally applied potentials, i.e., by supplying or removing sodium ions to or from the catalyst surface. Electrochemical sodium supply to the Pd catalyst surfaċe was found to supress both the rate of acetylene hydrogenation and, to a larger extent the rate of ethylene hydrogenation to ethane. Consequently electrochemical sodium supply was found to enhance the selectivity to ethylene. Thus, β″ - Al₂O₃ can act as an active catalyst support causing enhanced performance of the Pd catalyst. Acetylene conversion and hydrogenation selectivity values up to 90 % and 95 %, respectively, were obtained. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.