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.     

Synthesis and ionic conduction of apatite-type materials

Apatite is a mineral with general formula M₁₀(XO₄)₆Z₂, where M are metallic elements such as Li⁺, Na⁺, K⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ln³⁺ etc.; X=P, V, S, Si, Ge, Re, Cr etc; Z=F⁻, Cl⁻, I⁻, OH⁻, O²⁻, S²⁻ etc. Some materials with apatite structure (S.G. P6₃/m) exhibit quite high cationic (Li⁺, H⁺ etc.) and/or anionic (F⁻, Cl⁻ etc.) conduction. Recently, it was reported that some rare earth silicates, e.g., La₁₀(SiO₄)₆O₃, exhibit quite high oxide-ion conductivity. In this paper, we discuss chemical composition, structure, synthetic procedure and ionic conduction of apatite-type materials. Recent improvements are briefly reviewed. High ionic conductivity has been observed for both cation deficient, oxygen stoichiometric La_9.33(SiO₄)₆O₂ and cation stoichiometric, oxygen excess La₁₀(SiO₄)₆O₃ compositions. Grain boundary conductivity is usually low, which tends to dominate the impedance response. The resistance, particularly the grain boundary resistance is also found to depend on pO₂. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

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.     

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.     

Large optical nonlinearity in CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> thin films

CaCu₃Ti₄O₁₂ (CCTO) thin films were successfully prepared on LaAlO₃ substrates by pulsed laser deposition technique. We measured the nonlinear optical susceptibility of the thin films using Z-scan method at a wavelength of 532 nm with pulse durations of 25 ps and 7 ns. The large values of the third-order nonlinear optical susceptibility, χ ⁽³⁾, of the CCTO film were obtained to be 2.79×10⁻⁸ esu and 3.30×10⁻⁶ esu in picosecond and nanosecond time regimes, respectively, which are among the best results of some representative nonlinear optical materials. The origin of optical nonlinearity of CCTO films was discussed. The results indicate that the CCTO films on LaAlO₃ substrates are promising candidate materials for applications in nonlinear optical devices.     

The growth,thermal and nonlinear optical properties of single-crystal GdAl3(BO3)4

The nonlinear optical single-crystals GdAl₃(BO₃)₄ (GAB), space group R32, were grown by the top-seed solution growth (TSSG) method. The thermal properties and the nonlinear optical characteristics have been investigated. The two principal coefficients of thermal expansion along (100) and (001) were measured to be 5.30 × 10⁻⁶, 1.88 × 10⁻⁵ K⁻¹. The transmission spectrum was measured and the second-harmonic generation (SHG) was presented. By way of our designed cross superimposed laser crystal multiplier, the frequency doubling laser at wavelength 457.5 nm was measured to be 18.2 mW and the facular properties indicated the multiplier contributed to the improvement of the frequency doubling conversion efficiency.     

Synthesis and electrical characterisation of the perovskite niobate-titanates,Sr1−x/2Ti1−xNbxO3−δ

The synthesis and electrical characterisation over a range of oxygen partial pressures (10⁻²⁰ to 1 atm) are reported for the cubic perovskite niobate-titanates Sr_1−x/2Ti_1−xNb_xO_3−δ, which are proposed as potential anode materials for solid oxide fuel cells. Single phase samples were observed for 0≤x≤0.4, and phase purity was retained on annealing at both high and low oxygen partial pressures. Good electrical conductivity was observed on reduction in low oxygen partial pressures, with a maximum for the sample with 25% Nb (x=0.25), σ=5.6 Scm⁻¹ at 930°C (P (O₂)=10⁻¹⁸ atm). For dense samples the higher the Nb content the more resistant the reduced sample was to reoxidation as the oxygen partial pressure was increased. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Combustion synthesis and luminescent properties of green-emitting phosphor (Sr, Zn) Al2O4: Eu2+, B3+ for white light emitting diodes (WLED)

In this study, the phosphors (Sr_1−x , Zn _x )_0.9(Al_2−y , B _y )O₄ doped 10 mol % Eu²⁺, were prepared by combustion method as the fluorescent material for white light emitting diodes (WLEDs), performing as a light source. The luminescent properties were investigated by changing the combustion temperature, the boron concentration, and the ratio of Sr to Zn. The luminescence, crystallinity and particle morphology were investigated by using a luminescence spectrometer, X-ray diffractometer (XRD) and transmission electron microscopy (TEM), respectively. The highest intensity of Sr_0.9(Al_2−y , B _y )O₄: Eu_0.1²⁺ phosphor was achieved when the combustion temperature was 600° and the concentration of B³⁺ was 8 mol % of the aluminate. A new blue emission was observed when the high Zn concentration (x ⩾ 0.8), and this blue emission disappeared with the Zn concentration became lower than 0.8. The combustion method synthesized phosphor (Sr_0.6, Zn_0.4)_0.9(Al_1.92, B_0.08)O₄: Eu_0.1²⁺ showed 3.3 times improved emission intensity compared with that of the Sr_0.9(Al_1.92, B_0.08)O₄:Eu_0.1²⁺ phosphor under λ _ex = 390 nm.      

Thermomechanical and conductivity studies of doped niobium titanates as possible current collector material in the SOFC anode

In the reducing atmosphere of the SOFC anode at operating temperatures of 800 °C and above Nb₂TiO₇ is reduced to Nb_1.33Ti_0.67O₄. This material displays very high electronic conductivity of >100 Scm⁻¹, suitable for use in such applications as a current collector. It has a low thermal expansion coefficient of 3 × 10⁻⁶ K⁻¹, however, which may cause problems due to mismatch with other SOFC components, e.g. YSZ. Doping with Fe₂O₃ successfully increased the thermal expansion to a maximum of 6 × 10⁻⁶ K⁻¹. A conductivity of 140 Scm⁻¹ at 900 °C in dry 5% H₂/Ar, with an activation energy of 0.18 eV, was achieved for the Nb_1.344Ti_0.642Fe_0.014O₄, making it suitable for the use as a current collector. Conductivity runs in wet 5%H₂/Ar showed lower conductivities of 15–18 Scm⁻¹ and lower activation energies of 0.08 − 0.09 eV. Single cell tests of Nb_1.33Ti_0.67O₄ showed power outputs of 5.5 − 7.2 mW·cm⁻² at 850 °C, lower than for Ni with 150 − 200 mW·cm⁻² at 850 °C, however, this material displayed much better stability at high temperatures than Ni. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Defects and transport in SrFe1−xCoxO3−δ

The non-stoichiometry and chemical diffusion coefficient of SrFe_1−xCo_xO_3-δ have been measured by steady state and transient thermogravimetry in the temperature range 750–1200 °C at different oxygen partial pressures. At high oxygen partial pressures, the chemical diffusion coefficient was in the range 1·10⁻⁴ – 7·10⁻⁴ cm²/s. This, combined with high concentration of disordered vacancies make these materials perhaps the fastest solid oxygen ion diffusers known at high temperatures and high oxygen partial pressures. However, due to the high concentration of defects in SrFe_1−xCo_xO_3-δ the compound transforms from a cubic (disordered) perovskite to a brownmillerite type of structure under reduced oxygen partial pressures below approx. 900 °C. Due to this phase transition, the mobility of oxygen vacancies in SrFe_1−xCo_xO_3-δ decreases up to about an order of magnitude at 850 °C. We also observe an ordering effect at 1000 °C, although smaller in size, and this is suggested to be due to short range ordering of four-coordinated polyhedra of Fe. For possible use as oxygen separation membranes, phase stability against sulphur and carbon containing atmospheres is also discussed with respect to the formation of carbonates and sulphates. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

An investigation of the Al2O3-CdSe interface in accumulation

The Al₂O₃−CdSe interface of a thin-film transistor is investigated in the frequency range 30 Hz-30 kHz under weak depletion and accumulation. The surface states are, most likely, located in the insulator Al₂O₃ with a concentration varying from 4·10¹⁸ to 10¹⁹ cm⁻³ eV⁻¹. The surface states have a negligible influence on the thin-film transistor operation.     

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.     

AC-Conductivity and proton transport number of BaZr0.90Al0.10O3-δ

AC-conductivity measurements of BaZr_0.90Al_0.10O_3−δ (where δ describes the number of oxygen ion vacancies per unit cell) in wet and dry N₂ have been carried out over the temperature range from 400 to 900 °C. Both atmospheres showed the usual Arrhenius behavior of BaZr_0.90Al_0.10O_2.95. The proton transport number,t _H, was also determined from the conductivity measurements of BaZr_0.90Al_0.10O_2.95 in wet and dry N₂ and takes up values of 0.97 and 0.78 in the temperature range 400 – 900 °C, respectively.     

Mechanisms of creation and destruction of polyhalide V centers in irradiated AHC

The mechanisms of creation and destruction of polyhalide V centers in AHC were modeled by the MNDO semiempirical quantum-chemical method. It is shown that X ₃ ⁻ molecules dissociate from the ground state into X ₂ ⁰ and X⁻ and from the triplet state into X ₂ ⁻ and X⁰, whereas X ₅ ⁻ and X ₇ ⁻ molecules dissociate into X ₃ ⁻ and X ₂ ⁰ and X ₅ ⁻ and X ₂ ⁰ , respectively. At room temperatures, X ₃ ⁻ or larger aggregates, which consist only of X ₃ ⁻ centers, form stable polyhalide V centers. It is shown that the thermal stability decreases when going along the series X ₃ ⁻ , X ₅ ⁻ , and X ₇ ⁻ . The radiation-induced instability of stable F centers in AHC at room temperatures is associated with the destruction of X ₃ ⁻ centers and the thermal instability of X ₅ ⁻ and X ₇ ⁻ centers. E. A. Buketov Karaganda State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 50–54, March, 2000.     

Study on structural, thermal, sintering and conductivity of Cu-Co doubly substituted Bi4V2O11

Doubly substitution of vanadium by Cu and Co in the limit of 10% in Bi₄V₂O₁₁, has led to the formation of the Bi₄V_1.8Cu_0.2−xCo_xO_10.7 solid solution. X-ray diffraction shows that all the compositions present a tetragonal symmetry. The thermal analysis has revealed that the polymorph γ' phase, which is formed by a partial ordering of oxygen ions in the γ high temperature form, is stabilized at room temperature. The influence of sintering temperature on the microstructure of the samples was investigated by the scanning electron microscopy (SEM). The ceramics sintered at 820 °C for more than 3 hours present micro-craks. The evolution of the electrical conductivity with temperature and the degree of substitution has been investigated by impedance spectroscopy. The sample with x=0.1 presents the highest value of the conductivity ≈4.6×10⁻² S·cm⁻¹ at 600 °C.     

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 ⁻).     

Fluorescent Method for the Determination of Sulfide Anion with ZnS:Mn Quantum Dots

Water-soluble Mn²⁺-doped ZnS quantum dots (QDs) were prepared using mercaptoacetic acid as the stabilizer. The optical properties and structure features were characterized by X-Ray, absorption spectrum, IR spectrum and fluorescence spectrum. In pH 7.8 Tris-HCl buffer, the QDs emitted strong fluorescence peaked at 590 nm with excitation wavelength at 300 nm. The presence of sulfide anion resulted in the quenching of fluorescence and the intensity decrease was proportional to the S²⁻ concentration. The linear range was from 2.5 × 10⁻⁶ to 3.8 × 10⁻⁵ mol L⁻¹ with detection limit as 1.5 × 10⁻⁷ mol L⁻¹. Most anions such as F⁻, Cl⁻, Br⁻, I⁻, CH₃CO₂ ⁻, ClO₄ ⁻, CO₃ ²⁻, NO₂ ⁻, NO₃ ⁻, S₂O₃ ²⁻, SO₃ ²⁻ and SO₄ ²⁻ did not interfere with the determination. Thus a highly selective assay was proposed and applied to the determination of S²⁻ in discharged water with the recovery of ca. 103%.     

Synthesis,structural characterization and electrical property of new oxide ion conductors: La3MMo2O12 (M = In,Ga and Al)

New series of oxides, La₃MMo₂O₁₂ (M = In, Ga and Al), have been prepared by the solid-state reaction. The composition and elemental distribution were analyzed by the energy-dispersive X-ray (EDX) analysis. As determined by the X-ray diffraction (XRD), these compounds have similar crystal structures that can be indexed on a monoclinic cell at room temperature. AC impedance spectra and the DC electrical conductivity measurements in various atmospheres indicate that they are oxide ion conductors with ionic conductivities between 10^− 2 and 10^− 3 S/cm at 800 °C. The conductivity decreases in the order of La₃GaMo₂O₁₂ > La₃AlMo₂O₁₂ > La₃InMo₂O₁₂, implying that the effect of cell volume and polarization associated with In³⁺, Ga³⁺ and Al³⁺ play an important role in the anion transport of these materials. The reversible phase transition was observed in all these compounds as confirmed by the differential thermal analysis (DTA) and dilatometric measurements.     

Effect of B-site substitution of (Li,La)TiO3 perovskites by di-, tri-, tetra- and hexavalent metal ions on the lithium ion conductivity

We report the synthesis and lithium ion conductivity of di-, tri-, tetra- and hexavalent metal ion B-site substituted (Li,La)TiO₃(LLT) perovskites. All 5–10 mol% Mg, Al, Mn, Ge, Ru and W ion substituted LLTs crystallize in a simple cubic or tetragonal perovskite structure. Among the oxides investigated, the Al-substituted perovskite La_0.55Li_0.36□_0.09Ti_0.995Al_0.005O₃ (□=vacancy) exhibits the highest lithium ion conductivity of 1.1 × 10⁻³ S/cm at room temperature which is slightly higher than that of the undoped (Li,La)TiO₃ perovskite (8.9 × 10⁻⁴ S/cm) at the same temperature. The lithium ion conductivity of substituted LLTs does not seem to depend on the concentration of the A-site ion vacancies and unit cell volume. The high ionic conductivity of Al-substituted LLT is attributed to the increase of the B(Al)-O bond and weakening of the A(Li,La)-O bond. The conductivity behavior of the doped LLT is being described on the basis of Gibbs free energy considerations.     

Interaction of high-power x rays with sapphire crystals and quartz based materials

The interaction of high-power (10¹¹ W/cm²) soft (1–3 keV) x-rays with inorganic oxides (Al₂O₃ and SiO₂) is studied. It is found that when the wavelength of the x rays is comparable to the lattice constant of the crystal, besides generation of a high concentration of hot electrons and holes, there is broadening of the 2 p O²⁻-subband in the upper valence band owing to the local action of the strong x-ray field on regular oxygen sites. As a consequence, depending on the intensity of the x-ray pulses, a broadening of the fast (<1 ns) core-valence x-ray luminescence spectra is observed. Fiz. Tverd. Tela (St. Petersburg) 39, 286–289 (February 1997)