Annealing effect on the superconductivity of In2O3–ZnO thin films

We have investigated the relation among ρ–T characteristics, superconductivity, annealing conditions and the crystallinity of polycrystalline (In₂O₃)_1−x–(ZnO)_x films. We annealed as-grown amorphous films in air by changing annealing temperature and time. It is found that the films annealed at 200 °C or 300 °C for a time over 0.5 h shows the superconductivity. Transition temperature T_c and the carrier density n are T_c < 3.3 K and n ≈ 10²⁵–10²⁶ m⁻³, respectively. Investigations for films with x = 0.01 annealed at 200 °C have revealed that the T_c, n and crystallinity depend systematically on annealing time. Further, we consider that there is a suitable annealing time for sharp resistive transition because the transition width becomes wider with longer annealing times. We studied the upper critical magnetic field H_c2(T) for the film with different annealing time. From the slope of dH_c2/dT for all films, we have obtained the resistivity ρ dependence of the coherence length ξ(0) at T = 0 K.     

Growth of single crystal PrFeAsO1−y and its characterization

We have successfully grown single crystals of oxygen deficient oxypnictide superconductor PrFeAsO_1−y using high pressure synthesis technique. Typical crystal size is about 600 × 800 × 30 μm³, with its T_c = 44 K. Their resistivity measurements under magnetic field yield the anisotropic factor Γ  5, consistent with previous results on smaller single crystals.     

Spectral characterization and energy levels of Cr:Sc2(MoO4)3 crystal

This paper reports the spectral properties and energy levels of Cr³⁺:Sc₂(MoO₄)₃ crystal. The crystal field strength Dq, Racah parameter B and C were calculated to be 1408 cm⁻¹, 608 cm⁻¹ and 3054 cm⁻¹, respectively. The absorption cross sections σ_α of ⁴A₂→⁴T₁ and ⁴A₂→⁴T₂ transitions were 3.74×10⁻¹⁹ cm² at 499 nm and 3.21×10⁻¹⁹ cm² at 710 nm, respectively. The emission cross section σ_e was 375×10⁻²⁰ cm² at 880 nm. Cr³⁺:Sc₂(MoO₄)₃ crystal has a broad emission band with a broad FWHM of 176 nm (2179 cm⁻¹). Therefore, Cr³⁺:Sc₂(MoO₄)₃ crystal may be regarded as a potential tunable laser gain medium.     

Kerr property of cubic K0.95Li0.05Ta0.60Nb0.40O3 single crystal

The Kerr (quadratic electro-optic) property of K_0.95Li_0.05Ta_0.60Nb_0.40O₃ was measured by using an automated scanning Mach–Zehnder interferometer. K_0.95Li_0.05Ta_0.60Nb_0.40O₃ has large Kerr effect with R₁₁ = 7.2 × 10⁻¹⁶ m²/V² and R₁₂ = −1.2 × 10⁻¹⁶ m²/V² at 632.8 nm near its phase-transition temperature. The dielectric and Kerr properties as function of temperature were also investigated, thus the quadratic polarization-optic coefficients were calculated. The values of g₁₁ and g₁₂ are 0.083 m⁴/C² and −0.014 m⁴/C², respectively, and do not depend on temperature within the measurement accuracy of 5%.     

Structure and properties of the one-dimensional cobalt oxide CaCo2O4

We have studied crystal structure and transport properties of the quasi one-dimensional cobalt oxide CaCo₂O₄. The CaCo₂O₄ phase crystallizes in calcium-ferrite type structure, which consists of a corner- and edge-shared CoO₆ octahedron network including one-dimensional double chains. Large thermoelectric power (S  150 μV/K at 390 K) with metallic temperature dependence of S, moderate resistivity (ρ  2.9 × 10⁻¹ Ω cm at 390 K) with carrier localization at low temperature, and normal thermal conductivity (κ  6.3 W/Km at 390 K) were observed. The phonon mean-free path was calculated from the observed data, as a function of temperature. The long phonon mean-free path (l  24 Å at 300 K) implies that the thermal conductivity could be suppressed by impurity scattering of phonons with partial element substitution.     

Pyroelectric properties in three phases coexistence Pb[(Mn0.33Nb0.67)0.5(Mn0.33Sb0.67)0.5]0.08(ZrxTi1−x)0.92O3 lead ceramics

The bulk dense Pb[(Mn_0.33Nb_0.67)_0.5(Mn_0.33Sb_0.67)_0.5]_0.08(Zr_xTi_1−x)_0.92O₃ pyroelectric ceramics have been successfully prepared by the conventional solid method. The effect of three phases coexistence in the ceramics is studied. When x = 0.95 and 0.85 in the ceramics, the maximum pyroelectric coefficient peaks appear at 23 °C and 45 °C, and the maximum values are 26.5 × 10⁻⁴ C/m² °C and 25.5 × 10⁻⁴ C/m² °C, respectively. The maximum pyroelectric coefficient appears large while the peaks widths are small. When the two kinds of ceramic powders mixed with the mol ratio of 2:1, the pyroelectric coefficient of the ceramics is above 10.0 × 10⁻⁴ C/m² °C in a broad temperature range from 20 °C to 55 °C. The possible physical mechanism of the temperature broadened phenomenon is briefly discussed.     

Line strength measurements of carbonyl sulfide (OCS) in the 2v3, v1+2v2+v3, and 4v2+v3 bands

To support planetary studies of the Venus atmosphere, we measured line strengths of the 2v₃, v₁+2v₂+v₃, and 4v₂+v₃ bands of the primary isotopologue of carbonyl sulfide (¹⁶O¹²C³²S), whose band centers are located at 4101.387, 3937.427, and 4141.212 cm⁻¹, respectively. For this, infrared absorption spectra in normal carbonyl sulfide (OCS) sample gas were recorded at an unapodized resolution of 0.0033 cm⁻¹ at ambient room temperatures using a Bruker Fourier transform spectrometer (FTS) at the Jet Propulsion Laboratory. The FTS instrumental line shape (ILS) function was investigated, which revealed no significant instrumental line broadening or distortions. Various custom-made short cells and a multi-pass White cell were employed to achieve optical densities sufficient to observe the strong 2v₃ and the weaker bands in the region. Gas sample impurities and the isotopic abundances were determined from mass spectrum analysis. Line strengths were retrieved spectrum by spectrum using a non-linear curve fitting algorithm adopting a standard Voigt line profile, from which Herman–Wallis factors were derived for the three bands. The band strengths of 2v₃, v₁+2v₂+v₃, and 4v₂+v₃ of ¹⁶O¹²C³²S (normalized at 100% of isotopologue) are observed to be 6.315(13)×10⁻¹⁹, 1.570(2)×10⁻²⁰, and 7.949(20)×10⁻²¹ cm⁻¹/molecule cm⁻², respectively, at 296 K. These results are compared with earlier measurements and the HITRAN 2004 database.     

Rotational absorption spectrum of methylene fluoride in the 20–100 cm region

The pure rotational spectrum of CH₂F₂ was recorded in the 20–100 cm⁻¹ spectral range and analyzed to obtain rotation and centrifugal distortion constants. Analysis of the data yielded rotation constants: A = 1.6392173 ± 0.0000015, B = 0.3537342 ± 0.00000033, C = 0.3085387 ± 0.00000027, τ_aaaa = −(7.64 ± 0.46) × 10⁻⁵, τ_bbbb = −(2.076 ± 0.016) × 10⁻⁶, τ_cccc = −(9.29 ± 0.12) × 10⁻⁷, T₁ = (4.89 ± 0.20) × 10⁻⁶, and T₂ = −(1.281 ± 0.016) × 10⁻⁶cm⁻¹.     

The bending energy levels of C2H2

Absorption spectra of C₂H₂ have been recorded between 50 and 1450 cm⁻¹, with a resolution always better than 0.005 cm⁻¹, using two different Fourier transform spectrometers. Analysis of the data provided two sets of results. First, the bending levels with Σ_t V_t(t = 4, 5) ≤ 2 were characterized by a coherent set of 34 parameters derived from the simultaneous analysis of 15 bands, performed using a matrix Hamiltonian. The following main parameters were obtained (in cm⁻¹): ω₄⁰ = 608.985196(14), ω₅⁰ = 729.157564(10); B₀ = 1.17664632(18), α₄ = −1.353535(86) × 10⁻³, α₅ = −2.232075(40) × 10⁻³; q₄⁰ = 5.24858(12) × 10⁻³, and q₅⁰ = 4.66044(12) × 10⁻³, with the errors (1σ) on the last quoted digit. Second, a more complete set of bending levels with Σ_t V_t ≤ 4, some of which have never previously been reported, and also including V₂ = 1 have been fitted to 80 parameters. This simultaneous fit involved 43 bands and used the same full Hamiltonian matrix. Some perturbations which affect the higher excited levels are discussed.     

The reaction of CH3 + O2: experimental determination of the rate coefficients for the product channels at high temperatures

The reaction of methyl radicals (CH₃) with molecular oxygen (O₂) has been investigated in high-temperature shock tube experiments. The overall rate coefficient, k₁ = k_1a + k_1b, and individual rate coefficients for the two high-temperature product channels, (1a) producing CH₃O + O and (1b) producing CH₂O + OH, were determined using ultra-lean mixtures of CH₃I and O₂ in Ar/He. Narrow-linewidth UV laser absorption at 306.7 nm was used to measure OH concentrations, for which the normalized rise time is sensitive to the overall rate coefficient k₁ but relatively insensitive to the branching ratio of the individual channels and to secondary reactions. Atomic resonance absorption spectroscopy measurements of O-atoms were used for a direct measurement of channel (1a). Through the combination of measurements using the two different diagnostics, rate coefficient expressions for both channels were determined. Over the temperature range 1590–2430 K, k_1a = 6.08 × 10⁷T^1.54 exp (−14005/T) cm³ mol⁻¹ s⁻¹ and k_1b = 68.6 T^2.86 exp (−4916/T) cm³ mol⁻¹ s⁻¹. The overall rate coefficient is in close agreement with a recent ab initio calculation and one other shock tube study, while comparison of k_1a and k_1b to these and other experimental studies yields mixed results. In contrast to one recent experimental study, reaction (1b) is found to be the dominant channel over the entire experimental temperature range.     

Structural and physical properties of ZnO:Al films grown on glass by direct current magnetron sputtering with the oblique target

ZnO:Al films were deposited on glass substrates at 300 K and 673 K by direct current magnetron sputtering with the oblique target. The Ar pressure was adjusted to 0.4 Pa and 1.2 Pa, respectively. All the films have a wurtzite structure and grow with a c-axis orientation in the film growth direction. The films grow mainly with columnar grains perpendicular to the substrate and some granular grains also exist in the films. The film deposited at 673 K and 0.4 Pa has the largest grains whereas that prepared at 300 K and 0.4 Pa consists of the smallest grains and is porous. The films exhibit an n-type semiconducting behavior at room temperature. The ZnO:Al film deposited at 673 K and 0.4 Pa has the lowest resistivity (3.40 × 10⁻³ Ω cm), the highest free electron concentration (4.63 × 10²⁰ cm⁻³) and a moderate Hall mobility (4.0 cm² V⁻¹ s⁻¹). The film deposited at 300 K and 0.4 Pa has the highest resistivity and the lowest free electron concentration and Hall mobility. A temperature dependence of the resistivity reveals that the carrier transport mechanism is Mott’s variable range hopping in the temperature region below 100 K and thermally activated band conduction above 215 K. The activation energy for the film deposited at 300 K and 0.4 Pa is 41 meV and that for the other films is about 35 meV. All the films have an average optical transmittance of over 85% in the visible wavelength range. The absorption edge of the film deposited at 300 K and 0.4 Pa shifts to the longer wavelength (redshift) relative to the films prepared under the other conditions.     

Study of the interaction of Na9[SbW9O33]·19.5H2O with bovine serum albumin: Spectroscopic and voltammetric methods

The interaction of Na₉[SbW₉O₃₃]·19.5H₂O (SbW) with bovine serum albumin (BSA) is studied by spectroscopic and voltammetric methods. Absorption spectroscopy of BSA and the linear sweep voltammetry of SbW proved the formation of ground-state SbW–BSA complex. Fluorescence quenching of serum albumin by SbW is also found to be a static quenching process. The binding constant K_a is 4.13×10⁴ L mol⁻¹ for SbW–BSA at pH 7.40 Tris–HCl buffer at 295 K. The number of binding sites and the apparent binding constants at different temperatures are obtained from the analysis of the fluorescence quenching data. The thermodynamic parameters determined by the Van’t Hoff analysis of the binding constants (ΔH=−80.01 kJ mol⁻¹ and ΔS=−182.85 J mol⁻¹ K⁻¹) clearly show that the binding is absolutely entropy driven. Hydrogen bonding and van der Waals interaction force play major role in stabilizing the complex. The effect of SbW on the conformation of BSA is analyzed using synchronous fluorescence spectroscopy.     

Effect of oxygen partial pressure on the structural and optical properties of dc reactive magnetron sputtered molybdenum oxide films

Molybdenum oxide films (MoO₃) were deposited on glass and crystalline silicon substrates by sputtering of molybdenum target under various oxygen partial pressures in the range 8 × 10⁻⁵–8 × 10⁻⁴ mbar and at a fixed substrate temperature of 473 K employing dc magnetron sputtering technique. The influence of oxygen partial pressure on the composition stoichiometry, chemical binding configuration, crystallographic structure and electrical and optical properties was systematically studied. X-ray photoelectron spectra of the films formed at 8 × 10⁻⁵ mbar showed the presence of Mo⁶⁺ and Mo⁵⁺ oxidation states of MoO₃ and MoO_3−x. The films deposited at oxygen partial pressure of 2 × 10⁻⁴ mbar showed Mo⁶⁺ oxidation state indicating the films were nearly stoichiometric. It was also confirmed by the Fourier transform infrared spectroscopic studies. X-ray diffraction studies revealed that the films formed at oxygen partial pressure of 2 × 10⁻⁴ mbar showed the presence of (0 k 0) reflections indicated the layered structure of α-phase MoO₃. The electrical conductivity of the films decreased from 3.6 × 10⁻⁵ to 1.6 × 10⁻⁶ Ω⁻¹ cm⁻¹, the optical band gap of the films increased from 2.93 to 3.26 eV and the refractive index increased from 2.02 to 2.13 with the increase of oxygen partial pressure from 8 × 10⁻⁵ to 8 × 10⁻⁴ mbar, respectively.     

Lithium ion conductive glass–ceramics with Li3Fe2(PO4)3 and YAG laser-induced local crystallization in lithium iron phosphate glasses

The glasses with the composition of 37.5Li₂O–(25 − x)Fe₂O₃–xNb₂O₅–37.5P₂O₅ (mol%) (x = 5,10,15) are prepared, and it is found that the addition of Nb₂O₅ is effective for the glass formation in the lithium iron phosphate system. The glass–ceramics consisting of Nasicon-type Li₃Fe₂(PO₄)₃ crystals with an orthorhombic structure are developed through conventional crystallization in an electric furnace, showing electrical conductivities of 3 × 10^− 6 Scm^− 1 at room temperature and the activation energies of 0.48 eV (x = 5) and 0.51 eV (x = 10) for Li⁺ ion conduction in the temperature range of 30–200 °C. A continuous wave Nd:YAG laser (wavelength: 1064 nm) with powers of 0.14–0.30 W and a scanning speed of 10 μm/s is irradiated onto the surface of the glasses, and the formation of Li₃Fe₂(PO₄)₃ crystals is confirmed from XRD analyses and micro-Raman scattering spectra. The crystallization of the precursor glasses is considered as new route for the fabrication of Li₃Fe₂(PO₄)₃ crystals being candidates for use as electrolyte materials in lithium ion secondary batteries.     

Large nonlinear optical properties of Fe2O3 nanoparticles

Nonlinear optical properties of Fe₂O₃ nanoparticles were investigated by the signal-beam Z-scan technique with Ar⁺ and Ne–He lasers. The largest reported effective nonlinear coefficient, n₂=−8.07×10⁻⁷ cm²/W, was obtained. It is demonstrated that the nonlinear optical response originals from quantum confinement effect.     

High-resolution infrared study of the 2ν3 (A1, E) and ν1 + ν3 (E) bands of NF3

The 2ν₃ overtone (A₁, E) and the ν₁ + ν₃ (E) combination bands of the oblate symmetric top ¹⁴NF₃ were studied by FTIR spectroscopy with a resolution of 2.5 × 10⁻³ cm⁻¹. Nearly 500 lines up to K_max/J_max = 30/43 were observed for the weak A₁ component reaching the v₃ = 2⁰ substate (1803.1302 cm⁻¹), the majority of which corresponded to reinforced K = 3p-type transitions. For the strong E component reaching the v₃ = 2^±2 substate (1810.4239 cm⁻¹), about 3550 transitions were assigned up to K_max/J_max = 65/69, favoring a clear observation of the ℓ(4, −2) and ℓ(4, 4) splittings within the kℓ = −2 and +4 sublevels, respectively. The two v₃ = 2 substates are linked by the ℓ(2, 2)- and ℓ(2, −1)-type interactions, providing severe crossings, respectively, at K′ = 6 and near K′ = 24 on the v₃ = 2⁺² side. A model working in the D-reduction and including all these ℓ-type interactions could reproduce together 3695 nonzero weighted experimental data (NZW) through 33 free parameters with a standard deviation of σ = 0.357 × 10⁻³  cm⁻¹. As for the ν₁ + ν₃ (E) combination band, about 3690 lines were assigned up to K_max/J_max = 45/55. Its v₁ = v₃ = 1 upper state (1931.577 5 cm⁻¹) was treated using the same model recently applied to the v₃ = 1 (E, 907.5413 cm⁻¹) state. It yielded 21 free parameters through 3282 NZW experimental data, adjusted with σ = 0.344 × 10⁻³  cm⁻¹ in the D-reduction. For the two excited states, the small and unobserved ℓ(0, 6) interaction was tested as useless. To confirm the adequacy of the vibrationally isolated models used, some other reductions of the Hamiltonian were tried. For the v₃ = 2 state, the D-, L-, and LD-reductions led to similar σ’s, while the Q one was not successful. For the v₁ = v₃ = 1 state, the D- and Q-reductions gave comparable σ’s, while the QD-reduction was not as good. The corresponding unitary equivalence relations are generally more nicely fulfilled for the v₃ = 2 state than for the v₁ = v₃ = 1 state. The three derivable anharmonicity constants in cm⁻¹ are x₃₃ = −4.1528, g₃₃ = +1.8235 and x₁₃ = −7.9652.     

Fe3O4(111) termination of α-Fe2O3(0001)

Scanning tunnelling microscopy (STM) has been used to investigate the structure formed on an α-Fe₂O₃(0001) substrate after argon ion bombardment and annealing in 1 × 10⁻⁶ mbar of O₂ at 1000 K. The STM images recorded at positive sample bias reveal an hexagonal array, with a distance between (Fe) atoms of 6.0 ± 0.1 rA and steps in multiples of 4.8 Å. These results are consistent with formation of an Fe₃O₄(111) epitaxial layer terminating in a monolayer of Fe atoms.     

New ferromagnetic La3Co2TaO9 double perovskite: Structural and magnetic properties

The new double perovskite La₃Co₂TaO₉ has been prepared by a solid-state procedure. The crystal and magnetic structures have been studied from X-ray powder diffraction (XRPD) and neutron powder diffraction (NPD) data. Rietveld refinements were performed in the monoclinic space group P2₁/n. The structure consists of an ordered array of alternating B′O₆ and B″O₆ octahedra sharing corners, tilted along the three pseudocubic axes according to the Glazer notation a⁻b⁻c⁺. Rietveld refinements show that at RT the cell parameters are a=5.6005(7) Å, b=5.6931(7) Å, c=7.9429(9) Å and β=89.9539(7)°, and the refined crystallographic formula of this “double perovskite” can be written as La₂(Co)_2d(Co_1/3Ta_2/3)_2cO₆. Magnetization measurements and low-temperature NPD data show that the perovskite is a ferromagnet with T_C=72 K. At high T it follows the Curie–Weiss law with an effective magnetic moment of 3.82μ_B per Co ion which is very close to spin only Co²⁺ (HS).     

Magnetic behaviour of Cu2FeGeSe4

Measurements of magnetic susceptibility χ as a function of temperature T and of magnetisation M as a function of applied magnetic field H at a number of fixed temperatures were made on polycrystalline samples of Cu₂FeGeSe₄. The χ versus T data show that an antiferromagnetic transition occurs at 20 K and that a second transition occurs at 8 K, indicating a transition to weak ferromagnetic form. The M versus H curves indicated that at all temperatures below 70 K bound magnetic polarons (BMP) occur, in the paramagnetic, antiferromagnetic and weak ferromagnetic ranges. Below 8 K, the M versus H curves exhibited magnetic hysteresis, and this is attributed to the interaction of the BMPs with tetragonally anisotropic matrix. The B versus H curves were well fitted by a Langevin-type of equation, and the variation of the fitting parameters determined as a function of temperature. These showed that above 20 K the total BMP magnetisation fell almost linearly with increasing temperature and effectively disappeared at 70 K. The number of BMPs remained practically constant with temperature having a mean value of 6.55×10¹⁸/cm³. The analysis gave a value of 213 μ_B for the average magnetic moment of a BMP, corresponding to 42.4 Fe atoms. Using a simple spherical model, this gives the radius of a BMP as 12.0 Å.     

Preparation and electrical properties of a pyrochlore-related Ce2Zr2O8−x phase

A pyrochlore-related Ce₂Zr₂O_8−x phase has been prepared in a reduction reoxidation process from Ce_0.5Zr_0.5O₂ powders. Ce₂Zr₂O_8−x, based on a cubic symmetry with a=1.053 nm, decomposes in nitrogen at 800 °C, but remains stable up to 900 °C in air. It shows mixed oxygen ionic and electronic conductivity. The bulk conductivity at 700 °C is 4×10⁻⁴ S cm⁻¹ in air and 1×10⁻² S cm⁻¹ in nitrogen, and the activation energy is 1.27 eV in air. In nitrogen, the Arrhenius law is not obeyed, and a curved plot was obtained from 400 to 700 °C; then, the conductivity decreased rapidly due to the thermal decomposition of Ce₂Zr₂O_8−x.