Preparation of complex oxide thin films under hydrothermal and hydrothermal-electrochemical conditions

Thin-film growth of complex oxides including BaTiO₃, SrTiO₃, BaZrO₃, SrZrO₃, KTaO₃, and KNbO₃ were studied by the hydrothermal and the hydrothermal-electrochemical methods. Hydrothermal-electrochemical growth of ATiO₃ (A = Ba, Sr) thin films was investigated at temperatures from 100° to 200°C using a three-electrode cell. Current efficiency for the film growth was in the range from ca. 0.6% to 3.0%. Tracer experiments revealed that the ATiO₃ film grows at the film/substrate interface. AZrO₃ (A = Ba, Sr) thin films were also prepared on Zr metal substrates by the hydrothermal-electrochemical method. By applying a potential above ca. +2 V vs. Ag/AgCl to the Zr substrates, AZrO₃ thin films were formed uniformly. KMO₃ (M = Ta, Nb) thin films were prepared on Ta metal substrates by the hydrothermal method. Perovskite-type KTaO₃ thin films were formed in 2.0 M KOH at 300°C. Pyrochlore-type K₂Ta₂O₆ thin films were formed at lower temperatures and lower KOH concentrations. Morphotropic phase changes were also revealed in the hydrothermal system KTaO₃-KNbO₃.     

Effect of salts on oxidation of Np(VI) with Fe(CN)<Stack><Subscript>6</Subscript><Superscript>3−</Superscript></Stack> Ions in 0.1–1 M alkali solutions

The potential of the Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ couple in solutions containing 0.5–1 M alkali and high concentrations of Li, Na, and K salts was estimated potentiometrically. The reactions of Fe(CN)₆³⁻ with Np(VI) in such media were studied by spectrophotometry. In 0.5–1 M KOH + 7 M KF or 0.5–1 M KOH + 8 solutions, Np(VI) is oxidized to the heptavalent state with a small excess of Fe(CN)₆³⁻. In the presence of lithium or sodium salts, a larger excess of the oxidant is required for complete oxidation of Np(VI). Carbonate ions in concentrations exceeding 2 M prevent the Np(VI) oxidation.     

Very low-temperature search for superconductivity in semiconducting KTaO3

A series of attempts have been made to detect the presence of superconductivity in semiconducting potassium tantalate (KTaO₃) single crystals. Semiconducting potassium tantalate has a number of properties in common with semiconducting SrTiO₃, which is superconducting below 0.3 K, with a critical temperatureT _c that varies as a function of the carrier concentration. Both KTaO₃ and SrTiO₃ are perovskite-structure oxides and both materials are so-called incipient ferroelectrics that are characterized by high dielectric constants at low temperature. These common properties suggest that superconductivity might also be observed in semiconducting potassium tantalate. In the temperature ange from 0.01 to 4.0 K, however, no evidence was found for superconductivity in KTaO₃ in the presence of magnetic fields of 10^–5–10^–4 T (i.e., 0.1–1 Oe). Below 1.5 K, the search for superconductivity in KTaO₃ was carried out using a³He-⁴He dilution refrigerator equipped with a SQUID magnetometer and an ac magnetometer. The system response was verified by measuring the paramagnetic susceptibility of Dy₂O₃-doped KTaO₃. The failure to observe superconductivity in KTaO₃, while SrTiO₃ is an established superconducting material, may be related to the fact that the latter substance assumes a tetragonal symmetry phase at 105 K, while KTaO₃ remains cubic to low temperatures.Operated by Union Carbide Corporation for the U.S. Department of Energy under contract w-7405-eng-26.     

Controlled Modifications of HTSC Thin-Film Properties by Tailoring Substrate Surfaces

This chapter introduces the use of substrates for high-temperature superconductor (HTSC) thin-film deposition beyond their usual purpose as chemically inert, lattice-matched support for the films. Substrates are used as functional elements in order to controllably modify the growth mode of YBa₂Cu₃O_7–x thin films in the case of vicinal-cut SrTiO₃ single crystals or to locally modify the surface morphology and film/substrate lattice mismatch in the case of ion implanted SrTiO₃. Furthermore, the use of biaxial epitaxial strain is briefly reviewed for HTSC thin films, and the application of this concept to tailor the properties of perovskite thin films in general is shown.     

Growth and characterization of Pb0.97La0.02(Zr0.66Sn0.27Ti0.07)O3 antiferroelectric single crystals

Single crystals of Pb_0.97La_0.02(Zr_0.66Sn_0.27Ti_0.07)O₃ (PLZST) with the composition near the morphotropic phase boundary were grown by the flux method. The PbO–PbF₂–B₂O₃ system was used as a solvent. PLZST single crystals with the size of 4–6 mm are obtained and these crystals are slightly translucent after polishing. The splitting of (200) reflection peak indicates that the obtained crystals are of a single phase with tetragonal perovskite structure. The element contents of the grown crystals were measured by inductively coupled plasma atomic emission spectrometry. The chemical composition of the crystals is Pb_0.979La_0.014(Zr_0.666Sn_0.285Ti_0.049)O₃. Thermal properties and dielectric properties of PLZST single crystals were studied. The results show that flux-grown PLZST single crystals exhibit obvious endothermic processes and relaxor behaviors near the phase transition temperatures.     

Superconducting Properties of Zn-Doped Cu0.5Tl0.5Ba2Ca2Cu3?yZnyO10?δ Superconductors

A reproducible synthesis and characterization of Zn-doped Cu_0.5Tl_0.5Ba₂Ca₂Cu_3−y Zn _y O_12−δ (y=0, 0.5, 1.0, 1.5) superconductors at a relatively lower synthesis temperature of 840°C are studied by using X-ray diffraction, resistivity, ac-susceptibility and FTIR absorption measurements. The X-ray diffraction (XRD) studies of these samples have shown a tetragonal structure in which the c-axis length has been found to decrease with increased Zn doping. The critical temperature and magnitude of diamagnetism have not been significantly affected with the doping of Zn at this synthesis temperature. The magnitude of diamagnetism in the as-prepared undoped samples is decreased, whereas it remains stable (unchanged) in oxygen post-annealed samples. The apical oxygen phonon’s modes of type Tl–O_A–M(2) and Cu(1)–O_A–M(2) {where M=Cu/Zn} and the planar oxygen phonon modes of type M(2)–O_P–M(2) are also softened with the increase of Zn doping. We interpreted the softening of these oxygen related phonon modes linked with the decreased c-axis length, reduced John–Teller distortions and increased mass of Zn (65.38 amu) as compared to that of Cu (63.54 amu) (Kaplan et al., Phys. Rev. B 65, 214509, 2002).     

Preparation of SrTiO<Subscript>3</Subscript> nanomaterial by a sol–gel-hydrothermal method

A new synthetic route to obtain high-purity strontium titanate, SrTiO₃, using the sol–gel-hydrothermal reaction of TiCl₄ and a SrCl₂ solution in an oxygen atmosphere has been developed. In the synthesized products the SrTiO₃ nanoparticles are nearly spherical and decrease in size with the reaction time (48 h) down to a diameter of about 40 nm. The microstructure and composition of the as-synthesized samples were investigated by X-ray diffraction (XRD), high-resolution TEM (HRTEM), Raman spectroscopy, atomic force microscopy (AFM), and energy-dispersive X-ray spectroscopy (EDX). All the samples were identified as cubic perovskite phase.     

Ferroelectric and antiferroelectric polarisation switching characteristics of Bi(Mg<Subscript>0.5</Subscript>Ti<Subscript>0.5</Subscript>)O<Subscript>3</Subscript>–PbTiO<Subscript>3</Subscript> ceramics

Bi(Mg_0.5Ti_0.5)O₃–PbTiO₃ (BMT–PT) ceramics, with BMT–PT ratios ranging from 70-30 to 50-50, were prepared by a conventional solid state reaction process. The 50-50 BMT–PT ceramic possessed a tetragonal perovskite structure with a c/a ratio of ~1.037. Increasing BMT content led to a reduction of tetragonality and a change of structure to a rhombohedral or pseudo-cubic phase. Dielectric measurements, carried out during heating, indicated the occurrence of two phase transformations, which were identified as relaxor ferroelectric to antiferroelectric (at a temperature in the range from 150–300 °C) and antiferroelectric to paraelectric (at a temperature around 500 °C). The antiferroelectric nature of the 60-40 and 70-30 BMT–PT ceramics in the intermediate temperature range was confirmed by polarisation-electric field hysteresis measurements.     

Reaction of Np(VI) with H<Subscript>2</Subscript>O<Subscript>2</Subscript> in carbonate solutions

The kinetics and stoichiometry of the reaction of Np(VI) with H₂O₂ in carbonate solutions were studied by spectrophotometry. In the range 1–0.02 M Na₂CO₃, the reaction 2Np(VI) + H₂O₂ = 2Np(V) + O₂ occurs, as Δ[Np(VI)]/Δ[H₂O₂] ≈ 2. In Na₂CO₃ + NaHCO₃ solutions, the stoichiometric coefficient decreases, which is caused by side reactions. The reduction at low (1 mM) concentrations of Np(VI) and H₂O₂ follows the first-order rate law with respect to Np(VI), which suggests the formation of a Np(VI) peroxide-carbonate complex, followed by intramolecular charge transfer. Addition of Np(V) in advance decreases the reaction rate. An increase in the H₂O₂ concentration leads to the reaction deceleration owing to formation of a complex with two peroxy groups. In a 1 M Na₂CO₃ solution containing 1 mM H₂O₂, the first-order rate constant k increases with a decrease in [Np(VI)] from 2 to 0.1 mM. For solutions with [Np(VI)] = [H₂O₂] = 1 mM, k passes through a minimum at [Na₂CO₃] = 0.5–0.1 M. The activation energy in a 0.5 M Na₂CO₃ solution is 48 kJ mol⁻¹.     

Preparation of K<Subscript>2</Subscript>Ti<Subscript>6</Subscript>O<Subscript>13</Subscript>/TiO<Subscript>2</Subscript> bio-ceramic on titanium substrate by micro-arc oxidation

K₂Ti₆O₁₃/TiO₂ bio-ceramic coatings are prepared successfully by micro-arc oxidation on titanium substrate in pure KOH electrolyte solution. The coating is prepared at various applied current density (150–500 mA/cm²) and in KOH electrolyte with different concentrations (0.5–1.2 mol/L). The composition and surface morphologies of coatings are strongly dependent on the applied current density and the electrolyte concentration. On the condition of lower current density and electrolyte concentration, K₂Ti₆O₁₃ phase almost cannot be formed. The phase is mainly composed of rutile and K₂Ti₆O₁₃ with increasing current density and electrolyte concentration. The surface morphologies are composed of whiskers and porous structures. The ability of K₂Ti₆O₁₃/TiO₂ bio-ceramic films inducing apatite deposition is evaluated by soaking it in biological model fluids. The results show the K₂Ti₆O₁₃/TiO₂ bio-ceramic coatings possess excellent capability of inducing bone-like apatite to deposit.     

Growth of epitaxial sodium-bismuth-titanate films by metal-organic chemical vapor phase deposition

The liquid-delivery spin metal-organic chemical vapor phase deposition method was used to grow epitaxial sodium-bismuth-titanate films of the system Bi₄Ti₃O₁₂ + xNa_0.5Bi_0.5TiO₃ on SrTiO₃(001) substrates. Na(thd), Ti(OⁱPr)₂(thd)₂ and Bi(thd)₃, solved in toluene, were applied as source materials. Depending on the substrate temperature and the Na/Bi ratio in the gas phase several structural phases of sodium-bismuth-titanate were detected. With increasing temperature and/or Na/Bi ratio, phase transitions from an Aurivillius phase with m = 3 to m = 4 via an interleaved state with m = 3.5, and, finally, to Na_0.5Bi_0.5TiO₃ with perovskite structure (m = ∞) were established. These phase transitions proceed at remarkably lower temperatures than in ceramics or bulk crystals for which they had been exclusively observed so far.     

Crystal structure and IR spectra of Sr1? x La x Fe1? x Cd x O3?δ

Sr_1−x La _x Fe_1−x Cd _x O_3−δ solid solutions with x = 0.1 and 0.5 prepared at 1270 K are shown to have a cubic perovskite structure and the SrLaFeO₄ structure, respectively. In the range x = 0.25-0.4, the samples consist of a perovskite phase and SrLaFeO₄. As x increases from 0.2 to 0.5, the content of the perovskite phase gradually decreases, and that of the phase isostructural with SrLaFeO₄ increases. The IR spectra of the samples with x = 0.3−0.5 are similar to the spectrum of SrLaFeO₄. The Sr_2/3La_1/3FeO_3−δ ferrite has the perovskite structure, rather than the Sr₂LaFe₃O₈ structure. The synthesis of this ferrite proceeds through the formation of SrFeO_3−δ and LaFeO₃, followed by the mutual dissolution of these orthoferrites. Original Russian Text ? S.V. Smolenchuk, L.A. Bashkirov, M.V. Bushinskii, S.S. Dorofeichik, 2007, published in Neorganischeskie Materialy, 2007, Vol. 43, No. 5, pp. 621–625.     

Ferromagnetism in Electrospun Co-doped SrTiO3 Nanofibers

By employing electrospinning technique, subsequent calcination in air and annealing process in hydrogen, uniform Co-doped SrTiO₃ nanofibers with concentrations of Co between 0 and 0.20 were successfully produced. Their morphologies and detailed structures were characterized by scanning electron microscopy, transmission electron microscopy, and X-ray powder diffraction. And, the chemical states of Co were determined by X-ray photoelectron spectroscopy. It was shown that, after calcination, Co²⁺ was well incorporated into the perovskite structure of SrTiO₃, and the nanofibers possessed smooth surface with diameters of 50–100 nm. Magnetic properties of the hydrogen-annealed and -unannealed nanofibers were both measured by physical property measurement system from 50 to 300 K. It was explored that the Co addition and the hydrogen annealing process were both very important to the generation of the observed ferromagnetism in SrTi_1−x Co _x O₃:H₂ nanofibers. In hydrogen-annealed SrTi_0.80Co_0.20O₃:H₂ nanofibers, a saturation magnetization of 0.74 emu/g and an average moment of 0.122 μ_B/Co were obtained. The origins of the enhanced ferromagnetism in SrTi_1−x Co _x O₃:H₂ nanofibers were analyzed according to the chemical state of Co and the mediation of oxygen vacancies.     

Preparation of thin epitaxial multilayer YBa2Cu3O7−x (Ag) films by aerosol deposition

Thin-textured YBa₂Cu₃O _y (Ag) films were prepared by a new CVD process consisting of aerosol deposition and low temperature annealing, both operations not exceeding 600°C. MgO and SrTiO₃ single crystals were used as substrates. The stoichiometry of the prepared films was not ideal 1–2–3, having the atomic quotient of copper always lower than 3. For an unoptimized preparation process, the onset temperatures were around 80 K and the zero resistanceT _c values around 70K. Properties of samples obtained by low-temperature annealing are compared with those obtained by high temperature annealing. “Cleaning” effect of vacuum-annealing upon removing the nitrate and hydroxide groups from the prepared films is supposed.     

Oxidation behavior and electrochemical corrosion performance of Ti<Subscript>3</Subscript>Al alloy with TiAl coating

Magnetron-sputter deposition was used to produce a Ti–48Al–8Cr–2Ag (at. %) coating on a Ti–24Al– 17Nb–0.5Mo (at. %) alloy substrate. Oxidation behavior was studied in air at 900–1000°C. The results indicated that the oxidation rate of sputtered Ti–48Al–8Cr–2Ag nanocrystalline coating was lower than that of the Ti₃Al alloy at 900°C. The former formed a scale of merely Al₂O₃, and the latter formed a scale of TiO₂. However, the Ti–48Al–8Cr–2Ag nanocrystalline coating showed a little bit higher oxidation rate than Ti₃Al alloy at 1000°C because the outer TiO₂ scale formed and columnar boundaries of the coating gave a larger actual oxidation area than the original alloy. The electrochemical corrosion behavior was investigated in a 3.5% NaCl solution at room temperature. The coating showed excellent electrochemical corrosion resistance in 3.5% NaCl solution because it exhibited stable passive polarization behavior without any overpassivation phenomena.     

Dielectric properties of Yb<Subscript>2</Subscript>O<Subscript>3</Subscript>-doped barium strontium calcium titanate thick films for microwave device applications

(Ba_0.56Sr_0.34Ca_0.10)TiO₃ (BSCT) thick films doped with 0.1 mol% MnCO₃ and Yb₂O₃ (0.1–0.7 mol%) were fabricated by the screen-printing method on the alumina substrate. The structural and electrical properties as a function of Yb₂O₃ amount were investigated. All BSCT thick films showed the formation of a complete solid solution in a cubic perovskite polycrystalline structure. Average grain size of the specimen doped with 0.7 mol% Yb₂O₃ was about 2.7 μm. The thickness of all BSCT thick films was approximately 50–55 μm. The relative dielectric constant, dielectric loss, and tunability of the BSCT thick films doped with 0.3 mol% Yb₂O₃ were 2,966, 0.7, and 14.3%, respectively.     

Hydrothermal synthesis and magnetic properties of CoxFe1−x/CoyLazFe3−y−zO4 composites

A series of iron–cobalt alloy and cobalt–ferrite composites doped with La³⁺ (Co_xFe_1−x/Co_yLa_zFe_3−y−zO₄) in which the Fe–Co alloy has either a bcc or a fcc structure and the oxide is a spinel phase, have been synthesized by using the disproportionation of Fe (OH)₂ and the reduction of Co (II) by Fe⁰ in a concentrated and hot KOH solution. when x ≤ 0.1, the structures of the Fe_xCo_1−x alloy and cobalt–ferrite are fcc structure; and when x ≥ 0.25, the structures of the Fe_xCo_1−x alloy is bcc structure. The fcc structure of alloy is favored for [KOH] close to 9 N, Co(II)/Fe(II) ratios between 0.5 and 0.9 and short reaction time of synthesis. And the bcc structure of the alloy is favored for [KOH] close to 1 N, Co(II)/Fe(II) ratios between 0.1 and 0.5 and long reaction time of synthesis. A low [KOH] favors nucleation leading to octahedral of 1 μm. And [KOH] of 9–12 N favors particle growth. The metal occurs in square particles of 100–150 nm included within the spinel. Powder X-ray diffraction (XRD), thermal gravity analysis (TGA) and different thermal analysis (DTA), scanning electron microscope (SEM), transmission electron micrograph (TEM) and vibrating sample magnetometer (VSM) were employed characterize the crystallite sizes, structure, morphology and magnetic properties of the composites. And the effect of the Co(II)/Fe (II) ratio (0 ≤ Co/Fe ≤ 1), concentration of KOH, reaction time and substitution Fe³⁺ ions by La³⁺ ions on structure, magnetic properties of the composites were investigated.     

Physicochemical properties of La<Subscript>3</Subscript>Ga<Subscript>5.5</Subscript>Ta<Subscript>0.5</Subscript>O<Subscript>14</Subscript>

We report the optical and dielectric properties and microhardness of La₃Ga_5.5Ta_0.5O₁₄ lanthanum gallium tantalate (langatate) crystals. Analysis of the optical transmission spectra of the crystals in relation to their refined compositions indicates that the bands at 34000–35000 and 27000–28000 cm⁻¹ are due to lanthanum and oxygen vacancies, respectively, and that the band at 20000–21000 cm⁻¹ is responsible for the yellow (orange) coloration of the crystals. Their resistivity and microhardness decrease with increasing oxygen vacancy concentration.     

Synthesis of hexagonal Al2−x Cr x O3 nanodisks by a thermal decomposition of mesoporous Cr4+:Al2O3 powders

Monodispersed hexagonal Al_2−x Cr _x O₃ nanodisks are synthesized through a reactive doping of Cr⁶⁺ cations in a hydrogenated mesoporous AlO(OH)·αH₂O powder followed by annealing at 1,200 °C in air. The reaction was carried out by a drop wise addition of an aqueous Cr⁶⁺ solution (0.5–1.0 M) to AlO(OH)·αH₂O, at room temperature. Al_2−x Cr _x O₃ nanostructure formation was controlled by the nucleation and growth from the intermediate amorphous mesoporous Cr⁴⁺:Al₂O₃ composites in the temperature range 400–1,000 °C. The nanodisks of ∼50 nm diameter and thickness of ∼16 nm is observed in the sample with x of 0.2 and similar nanodisks with a low dimension is observed at a higher value of x of 1.6 (after 2 h of heating at 1,200 °C). The Cr³⁺ ↔ Al³⁺ substitution, x ≤ 1.2, inhibits grain growth in small crystallites. The crystallites in x = 0.2 composition have 43 nm diameter while it is 15 nm in those with x = 1.2 composition.