Effects of protons and acceptor substitution on the electrical conductivity of La6WO12

Transport properties and non-stoichiometry of La_1−xCa_xW_1/6O₂ and La_1−yW_1/6O₂ (x=0, 0.005, 0.05; y=0.05, 0.1) have been characterized by means of impedance spectroscopy, the EMF-technique, H⁺/D⁺ isotope exchange, and thermogravimetry in the temperature range 300-1200 °C as a function of oxygen partial pressure and water vapor partial pressure. The materials exhibit mixed ionic and electronic conductivities; n- and p-type electronic conduction predominate at high temperatures under reducing and oxidizing conditions, respectively. Protons are the major ionic charge carrier under wet conditions and predominates the conductivity below ∼750 °C. The maximum in proton conductivity is observed for LaW_1/6O₂ with values reaching 3×10⁻³ S/cm at approximately 800 °C. The high proton conductivity for the undoped material is explained by assuming interaction between water vapor and intrinsic (anti-Frenkel) oxygen vacancies.     

Surface electronic structure–catalytic activity relationship of partially reduced WO3 bulk or deposited on TiO2

Catalytic reactions of n-pentane and 1-pentene were carried out as a function of the reduction process of WO₃ as bulk or supported on TiO₂. In situ characterization by XPS–UPS techniques of the different chemical species formed following the reduction processes was performed. At reduction temperatures up to 773 K, two distinct W⁵⁺ and W⁴⁺ states were obtained. The acid functions associated with W⁵⁺, mainly of Brönsted type, enabled to isomerize only 1-pentene to unsaturated products. Dual metal–acid functions (bifunctional) of the W⁴⁺ state perform the isomerization processes of 1-pentene and n-pentane to isopentane in similar way to highly dispersed platinum on alumina catalysts. A conversion of 56% of n-pentane and a selectivity of 87% to isopentane were obtained at 623 K reaction temperature.     

Partial-wave analysis of the dilatation-invariant relativistic S-matrix I Clebsch-Gordan coefficients for the Weyl group

As a first step towards partial wave analysis of a dilatation invariant S-operator, the Clebsch-Gordan coefficients for the Weyl group W (i.e. Poincaré group extended by dilatations) are derived using Mackey's theory of induced representations. Three cases of helicity coupling of two physical irreducible representations of W with any spin are treated: (a) m²₁>0, m²₂>0, (b) m²₁>0, m²₂=0, (c) m²₁=0, m²₂=0.     

The temperature dependence of impurity-assisted tunneling

The temperature dependence of impurity-assisted tunneling in Al−Al oxide-Pb tunnel junctions has been studied. Impurity-caused peaks in the second derivative of the I–V characteristics of these junctions have been studied at temperatures from 4·2 to 148K. In agreement with previous predictions it was found that the width W of such a peak was related to the temperature T by W=[(5·4 kT)²+W₀²]^1/2 where W₀ is the width of the peak at T=0. The amplitude of a peak was found to be proportional to W⁻¹, and the intensity of a peak (area under the peak) was independent of T.     

Phase relations and transformations in the system PbTe-GeTe

Results of a study of the pseudobinary system PbTe-GeTe are reported and discussed. A new phase diagram, the dependence of the lattice constants on alloy composition, and measurements of a phase transformation in Pb_1−xGe_xTe are presented. Complete solid solubility is found above 570°C. An exsolution dome extends from a maximum at 570°C (near 60 mole % GeTe) to about 5 and 96 mole % GeTe at 300°C. For alloys with compositions near GeTe the unit cell parameters depend markedly on the concentration of cation vacancies. The temperature for the cubic to trigonal phase transformation depends on alloy composition, decreasing from about 670°K for x = 1 to 0°K for x ≈ 0·01. The variation of lattice parameters at the transition temperature is continuous within experimental precision.     

Thermal evolution of vacancy defects induced in sintered UO2 disks by helium implantation

A slow positron beam coupled with Doppler broadening (DB) spectrometer was used to measure the low- and high-momentum annihilation fractions, S and W, respectively, as a function of positron energy in UO₂ disks implanted with different 1 MeV ³He fluences and annealed in ArH₂ or in vacuum. The S(E) and W(E) behaviors indicate that for fluences in the range from 2 × 10¹⁴ to 2 × 10¹⁶³He cm⁻², the vacancy defects distribution evolves with the annealing temperature in the range from 264 to 700 °C under ArH₂. This evolution is found to be dependent on the ³He fluence implanted in the sintered UO₂ disks. For the lowest fluence of 2 × 10¹⁴³He cm⁻², the S(W) plot with positron energy as the running parameter suggests that only the concentration of vacancy defects decreases when annealing temperature increases. For the highest implantation fluences (from 5 × 10¹⁵ to 2 × 10¹⁶³He cm⁻²) the S(W) plot suggests that the nature of the vacancy defects changes in the annealing temperature range from 260 to 400 °C. Measurements performed in implanted UO₂ disks annealed in vacuum have revealed a partial recovery of the vacancy defects possibly due to their recombination with mobile oxygen interstitials. The role of the hydrogen infusion into the disk is also discussed.     

Microstructural and electrochromic properties of tungsten oxide thin films produced by surfactant mediated electrodeposition

By electrochemically controlling the structure of the surface aggregates, the grain microstructure has been optimized to yield mesoporous thin films of tungsten oxide (WO₃) at the electrode-electrolyte interface in a peroxotungstate sol in the presence of a structure-directing agent (Triton) at room temperature. Apart from the dominant ultrafine nanocrystallites and pores (5-10 nm), well-developed abutting grains (25-100 nm) and nanofibrils also constitute an integral part of the film matrix. X-ray photoemission spectra reveal the as-deposited film (WO_3−x) to be constituted by a high proportion of W⁶⁺ states with a low oxygen deficiency (x = 0.02). A relatively high W⁵⁺ content in the film, upon intercalation of 18 mC cm⁻² charge translates into a large coloring efficiency (η_VIS ∼ 70 cm² C⁻¹) and transmission modulation. At a lithium intercalation level of 22 mC cm⁻², in addition to W⁵⁺ and W⁶⁺ states, the film also comprises of W⁴⁺ states. The extremely fast color-bleach kinetics (3 and 2 s, respectively, for a 50% change in transmittance) shown by the as-deposited WO₃ film are repercussions of the mesopore morphology, the multiple nanostructures and the sixfold channels of its hexagonal modification. The film shows a high cycling stability as the switching times do not show any significant decline even after 3500 repetitive cycles. Coloration efficiency over the solar and photopic regions and current density for lithium intercalation for the as-deposited film are superior to that observed for the films annealed at 100, 250 and 500 °C. The abysmal electrochromic response of the annealed films is a consequence of surface defects like cracks and uncontrolled densification and pore shrinkage.     

Modifications of He implantation induced cavities in silicon by MeV silicon implantation

Doppler broadening spectroscopy (DBS) coupled to a slow positron beam has been used to investigate the formation of He-cavities in the presence of high vacancy concentrations in Cz-Si (1 1 1). Si samples were first implanted with MeV Si ions in order to create a damaged Si layer. DBS measurements show the presence of divacancy (SV₂/SSi lattice=1.052,WV₂/WSi lattice=0.83) from the surface up to 4.2 μm depth with a concentration higher than 10¹⁸ cm⁻³. The thickness of this damaged layer was confirmed by spreading resistance measurements. In the second step, samples were implanted with 50 keV ³He with fluence of 10¹⁶ cm⁻². DBS results show that the apparent divancancy concentration decreases at ³He implantation depth ∼435 nm due to ³He passivation of vacancies that occurs during the implantation process. After 900 °C annealing, large defects are detected at depth up to 2 μm and (S, W) values suggest the detection of cavities at the implantation depth. We also report the possible presence of impurity complexes. The formation of these complexes is attributed to the gettering of metallic impurities present in the Si sample.     

Highly cation-deficient manganese perovskite, La1−xMn1−yO3 with x=y

Oxidative (δ>0) nonstoichiometry in the perovskite ‘LaMnO_3+δ’ has been known to be manifested not with O interstitials but rather with cation vacancies of equal amounts at the two cation sites, La and Mn, i.e. La_1−xMn_1−yO₃ with x=y. Here, we report the fabrication of samples with record-high cation-vacancy concentrations (x>0.12 or δ>0.4) by means of a variety of high-pressure oxygenation techniques. Linear (negative) dependence of the cell volume on x was observed within the whole x range investigated, down to 56.9 Å³ (per formula unit) for a sample oxygenated at 5 GPa and 1100 °C using Ag₂O₂ as an excess oxygen source. With increasing degree of cation deficiency in La_1−xMn_1−xO₃, the ferromagnetic transition temperature was found to follow a bell shape with respect to x exhibiting a maximum of ∼250 K about x≈0.1. For moderately oxygenated samples large magnetoresistance effect was evidenced.     

Variable-temperature FT-IR studies on the thermodynamics of carbon dioxide adsorption on a faujasite-type H-Y zeolite

Adsorption of carbon dioxide on a faujasite-type H-Y zeolite (Si:Al = 2.6:1) was studied by variable-temperature (200-290 K range) infrared spectroscopy. Adsorbed CO₂ molecules interact with the Brønsted acid Si(OH)Al groups located inside the zeolite supercage, bringing about a characteristic bathochromic shift of the O-H stretching mode from 3645 cm⁻¹ (free OH group) to 3540 cm⁻¹ (hydrogen-bonded CO₂ adsorption complex). Simultaneously, the asymmetric (ν₃) mode of adsorbed CO₂ is observed at 2353 cm⁻¹. From the observed variation of the integrated intensity of the 3645 and 2353 cm⁻¹ IR absorption bands upon changing temperature, corresponding values of standard adsorption enthalpy and entropy were found to be ΔH° = −28.5(±1) kJ mol⁻¹ and ΔS° = −129(±10) J mol⁻¹ K⁻¹. Comparison with the reported values of ΔH° for CO₂ adsorption on other zeolites is briefly discussed.     

Magneto-resistance above 300 K in nano-crystalline Co–Ag metastable solid solutions

A series of nano-crystalline Co_xAg_100−x solid solutions have been prepared by NaBH₄ reduction of the corresponding metal salts at room temperature in Ar gas flow. Alloys heat-treated at 600 °C in Ar/H₂ (5%) show the evolution of metastable fcc Co precipitates in Ag. Magnetic studies indicate that all the compositions are ferromagnetic with Curie temperatures >400 K. For a nominal composition of Co₆₀Ag₄₀, heat-treated at 600 °C, an effective negative magneto-resistance (MR) ratio of the order of ∼21% at 350 K, at 2 T is observed. This could arise from the influence of magnetic field on the electron–phonon scattering effects near to T_c and to the spin-mixing scattering by magnons.     

Composition stability limits for the rocksalt-structure phase (Pb1−ySny)1−xTex from lattice parameter measurements

The lattice parameters at 25°C have been measured on powders with a precision of one part in 3(10⁴) for (Pb_1−ySn_y)_1−xTe_x for y = 1·0, 0·90, 0·80,and0·00 and values of x both without and, for the first threey-values, within the composition stability range. For the first threey-values, the composition stability limits for samples metal-saturated at 400°C is 0·5000 ± 0·0002, while those for samples Te-saturated at 356°C is x = 0·5070fory = 1·0, x = 0·5056fory = 0·90,andx = 0·5038fory = 0·80. The fine powders pick up oxygen quickly in air, which reacts with the Pb and Sn upon heating to deplete the telluride solid-solution of metal and consequently reduce its parameter by 2–3(10⁻³)Å. The metals are substantially all returned to the telluride phase upon H₂-reduction at 500–600°C. The present results for SnTe are used to extend the sources of data used in an analysis of SnTe. This analysis shows that the ratio of the number of valence band holes per Sn-vacancy, c, to the 77°K Hall factor, r, is 3·2 ± 0·3 over the entire range of 3(10¹⁹) to 1·8(10²¹) cm⁻³ in the apparent hole concentration. The results for the solid solutions are extrapolated to give the atomic fraction of Te in the 356°C, Te-saturated solid solution for y < 0·8. Comparison with the electrical measurements of others gives c/r equal to about unity for y = 0·27and0·13.     

Magnetic properties of cobalt substituted M-type barium hexaferrite prepared by co-precipitation

The co-precipitation and solid state methods were used in the synthesis of barium hexaferrite (BaM). Phase pure BaM was obtained with 1, 2, 3, 5, 10, 15, 20 and 30 wt% cobalt oxide (Co₃O₄). The addition of Co^2+/3+ ions to the BaM increased the permeability and magnetic loss tangent to a value of 3.5 at 5% and reduced to 1 at 30% doping. With increased Co doping, M_s was reduced from 87-58 emu/g, M_r increased from 11 to 40 emu/g with 3–5 wt% Co and 9 emu/g for 30% doping. H_c sharply increased from 540 to 2200 Oe with a reduction to 280 Oe at 10 K with increasing temperature to 300 K. T_c increased from 740 to 750 K for 30% Co doping. DTA–TGA studies of green body showed decarboxilation to occur at around 825 °C and the transformation of residual Co₃O₄ to Co₂O₃ at around 577 °C. The XRD data confirmed the Co ions substituting into Fe sites until a 10–15% doping level where the structure altered to W-type hexaferrite. The densities of the compounds varied with doping to a maximum of 4.45 g/cm³.     

Nuclear magnetic resonance of 55Mn and 75As in MnAs

Four sets of NMR signals, two each, from ⁵⁵Mn and ⁷⁵As nuclei have been observed. The temperature dependences of ⁵⁵Mn resonances have been studied from 77 to 311 K and that of ⁷⁵As, from 77 K to about 250 K. The results show that there is a phase transition at T₁ ≈ 220 K. This transition may be due to introduction of a local spontaneous distortion in the region of the domain walls in the lattice, resulting in lowering of symmetry at low temperatures. Another possibility is the canting of spins which would lower the magnetic group symmetry. The observed resonances have been assigned to arise from the nuclei at the edge and the centre of the domain walls at temperatures T >T₁ and from two types of wall edges with inequivalent orientation of atomic spins at T < T₁. The isotropic hyperfine field at 0 K obtained by extrapolating the resonance frequencies are 227 and 285.1 kOe at ⁵⁵As nuclei, respectively. The anisotropy in the hyperfine field is nearly zero at ⁵⁵Mn nuclei and about 5.8 kOe at ⁷⁵As nuclei at 0 K.     

Ferromagnetism at 300 K in spin-coated films of Co doped anatase and rutile-TiO2

Thin films of Ti_1−xCo_xO₂ (x=0 and 0.03) have been prepared on sapphire substrates by spin-on technique starting from metalorganic precursors. When heat treated in air at 550 and 700 °C, respectively, these films present pure anatase and rutile structures as shown both by X-ray diffraction and Raman spectroscopy. Optical absorption indicate a high degree of transparency in the visible region. Such films show a very small magnetic moment at 300 K. However, when the anatase and the rutile films are annealed in a vacuum of 1×10⁻⁵ Torr at 500 and 600 °C, respectively, the magnetic moment, at 300 K, is strongly enhanced reaching 0.36μ_B/Co for the anatase sample and 0.68μ_B/Co for the rutile one. The ferromagnetic Curie temperature of these samples is above 350 K.     

Self-implantation of Cz-Si: Clustering and annealing of defects

Observations of vacancy clusters formed in Czochralski (Cz) Si after high energy ion implantation are reported. Vacancy clusters were created by 2 MeV Si ion implantation of 1 × 10¹⁵ ions/cm² and after annealing between 600 and 650 °C. Doppler broadening measurements using a slow positron beam have been performed on the self-implanted Si samples, both as-implanted and after annealing between 200 and 700 °C for time intervals ranging from 15 to 120 min. No change in the S parameter was noted after the thermal treatment up to 500 °C. However, the divacancies (V₂) created as a consequence of the implantation were found to start agglomerating at 600 °C, forming vacancy clusters in two distinct layers below the surface; the first layer is up to 0.5 μm and the second layer is up to 2 μm. The S-W plots of the data suggest that clusters of the size of hexavacancies (V₆) could be formed in both layers after annealing for up to an hour at 600 °C or half an hour at 650 °C. After annealing for longer times, it is expected that vacancies are a mixture of V₆ and V₂, with V₆ most probably dominating in the first layer. Further annealing for longer times or higher temperatures breaks up the vacancy clusters or anneals them away.     

Ionic conductivity of NTE materials c- Zr1−xErxW2O8−x/2

It is found that the c- Zr_1−xEr_xW₂O_8−x/2 solid solutions which are well known to have isotropic NTE properties clearly exhibit oxygen-ionic conductance and their ionic conductivities are measured to be about 10⁻⁴ S cm⁻¹ at 673 K, which is comparable to that of ceria-based solid electrolytes.     

Anomalous electrical conductivity of the potassium deficient linear chain platinum compound: K1.75Pt(CN)4·1.5H2O

Four probe single crystal dc conductivity, σ, has been measured for K_1.75Pt (CN)₄·1.5H₂O for temperature 360K > T > 30K on crystals prepared via electrochemical growth, with σ (295K)

25–50 Ω^?1cm^?1. An anomalous behavior in σ (T) is reported with σ (T) nearly constant for T > 300K and 160K > T > 80K, and rapidly decreasing σ (T) observed for 300K > T > 160K and T < 80K. The data for 200K < T < 308K are analyzed in terms of a three-dimensional second order phase transition occurring at T_c = 308K. These results contrast sharply with those of the well studied K₂Pt(CN)₄X_0.3·3H₂0 (X=Cl,Br).     

Microfabrication and magnetoelectric properties of amorphous magnetic-tunnel-junctions with Co–Fe–B/Al–O/Co–Fe–B hardcore structure

Both single-barrier magnetic tunnel junctions (SBMTJs) and double-barrier magnetic tunnel junctions (DBMTJs) with an amorphous hardcore structure of Co₆₀Fe₂₀B₂₀/Al–O/Co₆₀Fe₂₀B₂₀ were microfabricated. A high TMR ratio of 102.2% at 4.2 K was observed in the SBMTJs after annealing at 265 °C for 1 h. High TMR ratio of 56.2%, low junction resistance-area product RS of 4.6 kΩ μm², small coercivity H_C=25 Oe, and relatively large bias-voltage-at-half-maximum TMR with the value V_1/2 greater than 500 mV at room temperature (RT) had been achieved in such Co–Fe–B SBMTJs. Whereas, high TMR ratio of 60% at RT and 89% at 30 K, low junction resistance-area product RS of 7.8 kΩ μm² at RT and 8.3 kΩ μm² at 30 K, low coercivity H_C=8.5 Oe at RT and H_C=14 Oe at 30 K, and relatively large bias-voltage-at-half-maximum TMR with the value V_1/2 greater than 1150 mV at RT had been achieved in the Co–Fe–B DBMTJs. Temperature dependence of the TMR ratio, resistance, and coercivity from 4.2 K to RT, and applied voltage dependence of the TMR ratio and resistance at RT for such amorphous MTJs were also investigated.     

Investigation on spectral features of tungsten ions in PbO-Bi2O3-As2O3 glass matrix

Lead bismuth arsenate glasses mixed with different concentrations of WO₃ (ranging from 0 to 6.0 mol%) were synthesized. Differential thermal analysis (DTA), optical absorption, ESR and IR spectral studies have been carried out. The results of DTA have indicated that there is a gradual decrease in the resistance of the glass against devitrification with increase in the concentration of WO₃ upto 4.0 mol%.The optical absorption spectra of these glasses exhibited a relatively broad band peaking at about 880 nm identified due to d_xy→d_x²_−y² transition of W⁵⁺ ions; this band is observed to be more intense in the spectrum of glass containing 4.0 mol% of WO₃. Further, two prominent kinks attributed to ³P₀→¹S₀, ¹D₂ transitions of Bi³⁺ ions have also been located in the absorption spectra. The ESR spectra of these glasses recorded at room temperature exhibited an asymmetric signal at g_⊥∼1.71 and g_ll∼1.61. The intensity of the signal is observed to be maximal for the spectrum of the glass W₄. The quantitative analysis of optical absorption and ESR spectral studies have indicated that there is a maximum reduction of tungsten ions from W⁶⁺ state to W⁵⁺ state in the glass containing 4.0 mol% of WO₃. The IR spectral studies have indicated that there is a increasing degree of disorder in the glass network with increase in the concentration of WO₃ upto 4.0 mol%.