Pairing modulations and phase separation instabilities in Bi2Sr2CaCu2O8 + δ

There is growing evidence that the unconventional spatial inhomogeneities in the doped high-_Tc$T_c$ superconductors are accompanied by the pairing of electrons, subsequent phase transitions and condensation into coherent states. We show that such pairing states can be obtained from phase separation instabilities near level crossings. Conditions for coherent pairing instabilities are examined using exact diagonalization of Hubbard-like pyramid structures under variation of coupling and interaction strengths. We also evaluate the behavior of the energy charge gap in the vicinity of level crossings using a parametrization of coupling to the apical site to represent out-of-plane effects. These results provide a simple microscopic explanation of (correlation induced) supermodulation of the coherent pairing gap observed in scanning tunneling microscopy measurements at atomic scale in Bi₂Sr₂CaCu₂O_8 + δ.     

Non-universal dielectric relaxation in SrFeO3 − δ

SrFeO_3 − δ compound is prepared by the thermal decomposition method followed by ball milling. Analysis of Mössbauer spectrum and X-ray diffraction study proves the presence of multi-phase nature, i.e., Sr₈Fe₈O₂₃ and Sr₄Fe₄O₁₁ phases at room temperature. Furthermore, the Mössbauer spectrum at room temperature evidenced the presence of major Fe^3.5+ which is the resultant of equal contributions of Fe⁴⁺ and Fe³⁺. The Nyquist plot at all measured temperatures (80–230 K) suggests that the dielectric response is well associated with single relaxation time (exponential parameter, n∼1$n\sim 1$) i.e., the Debye-type. Modulus analysis exhibits the non-universal dielectric behaviour (stretched exponential parameter, β>1$\beta >1$) below 230 K and the Debye-type responds (β∼1$\beta \sim 1$) at and above 230 K. The Debye-type behaviour exhibited by SrFeO_2.81 at around room temperature in its defect state offers a new opening for this material for multifunctional applications.     

Defect structure and oxide ion transport in Sr- and Cr-doped LaCoO3 − δ

The results of oxygen nonstoichiometry, δ, measured by means of coulometric technique as a function of oxygen partial pressure, p_o2, in temperature range 1223 ≤ T, K ≤ 1323 are presented for the perovskite-type doped with chromium solely LaCo_0.7Cr_0.3O_3 − δ and simultaneously doped both with strontium and chromium La_0.7Sr_0.3Co_0.7Cr_0.3O_3 − δ cobaltites. The limit stability of the latter was found to exceed that of undoped cobaltite LaCoO_3 − δ on six orders of magnitude of p_o2 at a given temperature. The modeling of the defect structure of these perovskites was carried out and its adequate model was found. Chemical and self-diffusion coefficients of oxygen vacancies and oxygen ionic conductivity and ionic transport numbers were measured for the first time for La_0.7Sr_0.3Co_0.7Cr_0.3O_3 − δ as a function of oxygen partial pressure p_o2and temperature in the ranges − 4 ≤ log(p_o2, atm) ≤ 0 and 1223 ≤ T, K ≤ 1323, respectively. The additional substitution of Sr for La in LaCo_0.7Cr_0.3O_3 − δ was shown to lead to noticeable increase of ionic conductivity and oxygen chemical diffusion coefficient at given values of oxygen partial pressure and temperature as compared to lanthanum cobaltite doped with chromium solely. Self-diffusion coefficient of oxygen vacancies and their mobility in La_0.7Sr_0.3Co_0.7Cr_0.3O_3 − δ were found to be dependent on oxygen partial pressure and nonstoichiometry unlike undoped and doped with chromium lanthanum cobaltites.     

Fabrication, sintering and electrical properties of cobalt oxide doped Gd0.1Ce0.9O2 − δ

Ceria-based electrolytes have been widely researched in intermediate-temperature solid oxide fuel cell (SOFC), which might be operated at 500~600 °C. Gd0.1Ce0.9O1.95(GDC10) powders were prepared by a modified chemical co-precipitation process with Gd(NO3)3 and Ce(NO3)3 as precursors, and ammonia and hydrogen peroxide as precipitants. The precursors of GDC10 were fired at 350 °C for 2 h, then the fluorite structure cerias were identified by X-ray diffraction. The powders are well crystallized, with the size about 5 nm and surface area of 148.3 m2/g. Loading 1mol% cobalt oxide as additive, the GDC10 were succeeded to densify at 950 °C by liquid phase sintering mechanism. The grain size of 1CoGDC10 is small, about 100 nm. The electrical conductivity of samples sintered at 950 °C is about 0.01S/cm at 600 °C. The existence of cobalt oxide and smaller grain size of 1CoGDC10 don't affect the electrical conductivity.     

Oxygen nonstoichiometry, defect structure and electrical properties of LaFe0.7Ni0.3O3 − δ

Oxygen nonstoichiometry (δ), total conductivity (σ) and thermoelectric power (S) of the LaFe_0.7Ni_0.3O_3 − δ sample have been studied as functions of temperature and oxygen partial pressure. Based on the results of the direct reduction of the sample in hydrogen flow at 1100 °C the absolute oxygen content (3 − δ) has been found to vary from 2.999 to 2.974 in the range of 1273-1373 K and 10^− 3-0.21 atm. The point defect equilibrium models have been proposed and fitted to the set of experimental data in the form of log p(O₂) = f(δ)_T dependences. The values of standard thermodynamic quantities of defect formation reactions have been assessed. The joint analysis of oxygen nonstoichiometry, total conductivity and thermoelectric power has been performed using a small-polaron approach. The values of partial conductivity, partial thermopower and mobilities of electronic charge carriers have been calculated. The p-type semiconducting behavior of LaFe_0.7Ni_0.3O_3 − δ has been explained by the higher mobility values of electron holes than those of electrons in the whole range of thermodynamic parameters studied.     

Antiferroelectric phase transition in pyrochlore-like (Dy1− xCax)2Ti2O7 − δ (x = 0, 0.1) high temperature conductors

Low-temperature ordering transitions in polycrystalline high temperature conductors (Dy_1 − xCa_x)₂Ti₂O_7 − δ (x = 0, 0.1) prepared using co-precipitation, mechanical activation and solid-state reactions at 1400 or 1600 °C have been studied by impedance spectroscopy at low frequencies and thermal mechanical analysis (TMA). The dielectric permittivity and loss tangent of the ceramics obtained have been measured as a function of temperature at low frequencies (0.5−500 Hz). The results provide evidence for the relaxation of point defects, most likely oxygen vacancies, at 500−600 °C and an antiferroelectric low-temperature phase transition of the second order, associated with re-arrangement process in the oxygen sublattice of pyrochlore structure. The temperature of the antiferroelectric transition is 700 to 800 °C, depending on the synthesis procedure and ceramic composition. Calcium doping of Dy₂Ti₂O₇ leads to the formation of additional oxygen vacancies and, in the case of the samples prepared via co-precipitation, increases the peaks in permittivity due to the relaxation process and ordering transition by three or six times, respectively.     

Oxygen deficiency, vacancy clustering and ionic transport in (La,Sr)CoO3 − δ

The equilibrium p(O₂)-T-δ diagrams of perovskite-type La_1 − xSr_xCoO_3 − δ (x = 0.3-0.7), collected at 873-1223 K in the oxygen partial pressure range 10^− 5-1 atm by coulometric titration and thermogravimetric analysis, were analyzed in order to appraise the effects of the point-defect interactions. The nonstoichiometry variations were adequately described combining the rigid-band approach for delocalized holes and the pair-cluster formation reaction involving oxygen vacancies and Co²⁺ cations, whilst coulombic repulsion between the positively charged vacancies can be neglected. The resultant relationships between the oxygen chemical potential and mobile vacancy concentration were used for numerical regression analysis of the steady-state oxygen permeation through dense La_1 − xSr_xCoO_3 − δ membranes, affected by the surface exchange kinetics when Sr²⁺ content is higher than 40-50%. The calculated ionic conductivity is strongly influenced by the defect association processes, and decreases with decreasing concentration of the mobile vacancies as clustering starts to prevail on reduction. The Mössbauer spectroscopy studies of La_1 − xSr_xCoO_3 − δ, doped with 1 mol% ⁵⁷Fe isotope and moderately reduced at p(O₂) ≈ 10⁻⁵ atm, show no long-range vacancy ordering at x ≤ 0.5.     

Oxygen nonstoichiometry, thermo-chemical stability and lattice expansion of La0.6Sr0.4FeO3 − δ

The oxygen nonstoichiometry of La_0.6Sr_0.4FeO_3 − δ was measured at intermediate temperatures (773 to 1173 K) between 1 bar and the decomposition oxygen partial pressure by thermogravimetry and coulometric titration. The decomposition of the ABO₃ perovskite phase was found to occur at low oxygen partial pressures (below 10^− 20 bar). Using an atmosphere-controlled high-temperature XRD setup, the rhombohedral lattice parameters were obtained between 10^− 4 and 1 bar at 773 to 1173 K. A phase transition from rhombohedral to cubic might be expected to occur at high temperatures and for δ near the plateau at δ = [Sr] / 2. The lattice expansion was separated into “pure” thermal and chemically induced expansion by combining the lattice parameters with the oxygen nonstoichiometry data. The linear thermal expansion was formulated with a “pure” thermal expansion coefficient of α_th = 11.052 · 10^− 6 K^− 1 and a chemical expansion coefficient of α_chem = 1.994 · 10^− 2.The results were compared with previous data obtained for La_0.6Sr_0.4Co_1 − yFe_yO_3 − δ with y = 0.2-0.8. La_0.6Sr_0.4FeO_3 − δ was confirmed to show the highest thermo-chemical stability. While the chemical expansion of La_0.6Sr_0.4Co_1 − yFe_yO_3 − δ seems little affected by the iron content, the thermal expansion coefficient was the lowest for La_0.6Sr_0.4FeO_3 − δ.     

High-temperature magnetic properties of noninteracting randomly oriented single-domain Fe3 − δO4 nanoparticles

Magnetic measurements have been performed on 40-nm sphere-like Fe_3 − δO₄ (δ=0.043) nanoparticles using a Quantum Design vibrating sample magnetometer. Coating Fe_3 − δO₄ nanoparticles with SiO₂ effectively eliminates magnetic interparticle interactions so that the coercive field HC in the high-temperature range between 300 K and the Curie temperature (855 K) can be well fitted by an expression for noninteracting randomly oriented single-domain particles. From the fitting parameters, the effective anisotropy constant K is found to be (1.38±0.11)×¹⁰⁵ erg/cm³, which is very close to the bulk magnetocrystalline anisotropy constant of 1.35×¹⁰⁵ erg/cm³. Moreover, the inferred mean particle diameter from the fitting parameters is in quantitative agreement with that determined from transmission electron microscope. Such a quantitative agreement between data and theory suggests that the ensemble of our SiO₂-coated sphere-like Fe_3 − δO₄ nanoparticles represents a good system of noninteracting randomly-oriented single-domain particles.     

Effect of quasiparticle spectral weight and consistency of energy gaps obtained from STM and ARPES spectra for underdoped superconductor Bi2Sr2CaCu2O8 + δ

By comparing the recently obtained superconducting energy gaps from the scanning tunneling microscopy (STM) and the angle-resolved photoemission spectroscopy (ARPES) for underdoped superconductor Bi₂Sr₂CaCu₂O_8 + δ, significant distinctions were observed. By properly taking the effect of quasiparticle spectral weight in the STM spectra into account, good consistency between both energy gaps obtained by STM and ARPES is unveiled.     

Flame spray deposition of nanocrystalline dense Ce0.8Gd0.2O2 − δ thin films: Deposition mechanism and microstructural characterization

Nanocrystalline dense sub-micron thin films of Ce_0.8Gd_0.2O_2 − δ have been successfully deposited by flame spray deposition. The deposition mechanism has been identified as droplet deposition. The deposition temperature of the substrate was as low as 200 °C and the deposition rate ∼ 30 nm/min. Under these conditions the droplets have a very limited residence time in the hot zone of the flame and are deposited as liquid, forming smooth films free of particles. They exhibited a dense and crack-free microstructure. Grain growth, lattice constant, crystallographic density and surface roughness have been investigated as a function of annealing temperature. The good quality of the films, in association with the high deposition rates at low deposition temperatures shows the preeminence of the flame spray method for depositing thin films for micro-solid oxide fuel cells.     

The changes of capacitance-loss and current-voltage characteristics of LaMnO3 + δ/SrTiO3:Nb heterojunctions exposed to ambient air

Effects of moisture absorption on capacitance-loss and current-voltage characteristics of LaMnO_3 + δ/SrTiO₃:Nb heterojunction had been investigated after the heterojunctions were exposed to ambient air. The moisture-absorption-induced increases in loss tangent and breakdown voltage were observed, whereas no changes were found on capacitance and diffusion voltage. These results were discussed by the decrease of oxygen ions in LaMnO_3 + δ and the generation of hydroxide ions at grain boundaries. This work will favor both electronic transport analysis and future device applications.     

Stability, oxygen permeability and chemical expansion of Sr(Fe,Al)O3 − δ- and Sr(Co,Fe)O3 − δ-based membranes

Perovskite-type SrFe_0.7Al_0.3O_3 − δ and SrCo_0.8Fe_0.2O_3 − δ, and two related dual-phase composites with nominal compositions (SrFeO_3 − δ)_0.7(SrAl₂O₄)_0.3 and (SrCo_0.8Fe_0.2O_3 − δ)_0.7(SrAl₂O₄)_0.3, were comparatively studied employing controlled-atmosphere dilatometry, thermogravimetry, Mössbauer spectroscopy, and measurements of steady-state oxygen permeation fluxes through dense ceramic membranes. The composite materials display lower thermal and chemical expansion compared to the parent single-phase perovskites. The thermal expansion coefficients at 1023-1223 K are however still high, (20-23) × 10^− 6 K^− 1 at atmospheric oxygen pressure and (17-18) × 10^− 6 K^− 1 at p(O₂) = 10 Pa, thus limiting the range of possible membrane reactor configurations. Sr(Co,Fe)O_3 − δ-based materials exhibit extensive vacancy-ordering processes in inert atmospheres, resulting in a slow relaxation of the oxygen nonstoichiometry, chemical expansion and oxygen permeation fluxes. In comparison to Sr(Fe,Al)O_3 − δ, the stability of cobalt-containing ceramics in CO₂ is also poor, which leads to a partial blocking of the membrane surface by decomposition products and degradation of the oxygen transport. Thermogravimetric analysis showed that the interaction with carbon dioxide occurs even at elevated temperatures, up to 1223 K. Under high oxygen chemical potential gradients such as air/(H₂-H₂O), the composite membranes showed kinetically stable operation without bulk decomposition at 1073 K. The kinetic stabilization associated with surface-limited oxygen permeation was confirmed by the conversion-electron Mössbauer spectroscopy analysis of one (SrFeO_3 − δ)_0.7(SrAl₂O₄)_0.3 membrane exposed to dry CH₄ at 1173 K, where no traces of Fe²⁺ and metallic iron were detected in the reduced surface layer.     

High resolution infrared spectrum and global analysis of ν5, ν12, and ν12 + ν6 − ν6 in CH3SiH3

The vibration-torsion-rotation spectrum of CH₃SiH₃ has been measured from 470 to 725 cm⁻¹ at near-Doppler resolution. The full-width at half - maximum of the lines observed near 600 cm⁻¹ was 0.0011 cm⁻¹. The spectra were obtained using a Bruker IFS 125 HR Fourier transform spectrometer with the broadband source radiation being supplied from the synchrotron emission of the storage ring at the Canadian Light Source. Three vibrational bands were investigated: the lowest lying perpendicular fundamental ν₁₂ centred near 524 cm⁻¹, the lowest lying parallel fundamental ν₅ near 703 cm⁻¹, and the torsional hot band ν₁₂ + ν₆ − ν₆ near 534 cm⁻¹. For ν₁₂ and ν₅, the resolution and sensitivity are much improved over those in earlier studies, with many of the torsional multiplets now being resolved even in the cases where the upper levels are unperturbed. The primary motivation for the present work was the hot band, here reported for the first time, where the dependence of the silyl rock in ν₁₂ on the torsional motion is much more pronounced. In addition, for the vibrational ground state (gs), two “forbidden” high torsional overtones v₆ = 3 ← 0 and 5 ← 0 have been observed that become allowed through resonant mixing of the upper states with ν₁₂ and ν₅, respectively. In each case, two (K, σ) series have been measured where the mixing is largest. Here σ = 0, 1, −1 labels the torsional sub-levels. Using the Fourier transform waveguide spectrometer at E. T. H., the three σ-components of the (J = 1 ← 0) transition in ν₁₂ + ν₆ were observed, and a series of direct l-doubling transitions in ν₁₂ + ν₆ were measured for σ = 0. In a global fit, all the new data have been analysed along with the frequencies for other transitions obtained in earlier investigations. The analysis takes into account the relevant interactions among the torsional stacks of levels in the gs, ν₁₂, and ν₅. These include the previously known (gs, ν₁₂) Coriolis-like and (gs, ν₅) Fermi-like interactions along with a higher order (ν₁₂, ν₅) Coriolis-like coupling introduced here. This last is responsible for the strong perturbation of the ν₅ series with K = 10, 11, and 12, and of the corresponding hot band series. A good fit to 9282 frequencies including 7942 new measurements was obtained both with the Free Rotor model in which the torsion is classified as a rotation, and with the High Barrier model in which the torsion is classified as a vibration. The Hamiltonian is discussed with emphasis on the new terms required for treating ν₁₂ + ν₆ − ν₆.     

Ferromagnetism in diluted magnetic Zn-Co-doped CeO2−δ

Several oxides doped with transition metals can be used in spintronics devices due to their conductive and magnetic properties at room temperature. In this work, samples of Ce_1−2xZn_xCo_xO_2−δ were obtained by an alternative sol–gel proteic process for x=0.01, 0.05 and 0.1. The structural properties of samples were analyzed by XRD and Raman spectroscopy. Magnetization measurements revealed a ferromagnetic behavior at room temperature probably induced by oxygen vacancies.     

Structural and optical properties of Ga2(1−x)In2xO3 films prepared on α-Al2O3 (0 0 0 1) by MOCVD

Ga_2(1−x)In_2xO₃ thin films with different indium content x [In/(Ga + In) atomic ratio] were prepared on α-Al₂O₃ (0 0 0 1) substrates by the metal organic chemical vapor deposition (MOCVD). The structural and optical properties of the Ga_2(1−x)In_2xO₃ films were investigated in detail. Microstructure analysis revealed that the film deposited with composition x = 0.2 was polycrystalline structure and the sample prepared with x up to 0.8 exhibited single crystalline structure of In₂O₃. The optical band gap of the films varied with increasing Ga content from 3.72 to 4.58 eV. The average transmittance for the films in the visible range was over 90%.     

The ν4 and ν2 + ν5 high resolution infrared bands of FClO3 and FClO3

The high resolution infrared spectra of monoisotopic F³⁵Cl¹⁸O₃ and F³⁷Cl¹⁸O₃ have been studied in the region of the ν₄ fundamentals, centered at 1278.3 and 1263.3 cm⁻¹, respectively. Large perturbations are observed in both bands due to a Fermi type anharmonic resonance with the ν₂ + ν₅ combination bands, centered at 1270.7 cm⁻¹ in F³⁵Cl¹⁸O₃ and 1257.3 cm⁻¹ in F³⁷Cl¹⁸O₃. In particular, they affect the kl > 0 levels of the v₄ = 1 and v₂ = v₅ = 1 states which cross at kl ? 18 in F³⁵Cl¹⁸O₃ and kl ? 3 in F³⁷Cl¹⁸O₃, due to the opposite values of and . The Δl = Δk = ±2 and Δl = 0, Δk = ±3 essential resonances are also effective in the excited states of the dyad in F³⁵Cl¹⁸O₃, while in F³⁷Cl¹⁸O₃ only the Δl = Δk = ±2 one is active. In the spectrum of F³⁵Cl¹⁸O₃ 3423 transitions have been assigned, 10% of them belonging to ν₂ + ν₅. The rovibrational parameters and the interaction constants between the v₄ = 1 and v₂ = v₅ = 1 levels have been obtained. The depertubed band origins of ν₄ and ν₂ + ν₅ are 1277.310567(165) and 1271.753733(195) cm⁻¹, respectively, and the anharmonic resonance constant is 2.804416(153) cm⁻¹. For F³⁷Cl¹⁸O₃, 3022 transitions have been assigned, 38% belonging to the ν₂ + ν₅ combination band. The depertubed band origins are 1260.856338(123) and 1259.872338(134) cm⁻¹, for ν₄and ν₂ + ν₅ and the constant is 2.9350669(405) cm⁻¹. The equilibrium geometry of perchloryl fluoride, r_e (ClO) = 139.7(3) pm, r_e (ClF) = 161.0(5) pm, and α_e (OClO) = 115.7(4) degree, has been determined using the A_e and B_e equilibrium constants of the four symmetric isotopologues of perchloryl fluoride, F^35/37Cl¹⁶O₃ and F^35/37Cl¹⁸O₃.     

Surface and redox chemistry of Sm0.95Ce0.05Fe1 − xNixO3 − δ perovskites

A new series of perovskite materials with formula Sm_0.95Ce_0.05Fe_1 − xNi_xO_3 − δ (0 ≤ x ≤ 0.10) has been prepared by sol-gel combustion via a citrate precursor route. X-ray diffraction data showed that materials prepared by this method had a single orthorhombic phase belonging to the Pnma (62) space group. The study of powders sintered in air and in reducing atmospheres reveals that these materials do not show phase separation in air (up to 1350 °C) nor under 5% v/v H₂/N₂ (up to 700 °C), but a phase separation of Sm₂O₃ does occur at and above 800 °C under 5% v/v H₂/N₂ without deterioration of the perovskite phase. The surfaces of all the powders (fresh, in-situ reduced and ex-situ reduced) were Sm rich, and multiple oxidation states for Fe were observed. XP analysis of in-situ reduced samples (800 °C and above) shows that metallic Fe forms in all nickel doped materials except x = 0.07. The surface oxygen vacancies and percentages of lattice and adsorbed oxygen for this series of Ni doped materials were determined and the oxygen recapturing ability is explained in terms of the multiple oxidation states of Fe.