The low-energy electron spectrum from the EC-decay of 57Co: 0 eV up to 15 keV

The low-energy electron spectrum from the ⁵⁷Co decay has been examined in the region from 0 up to 15 keV at instrumental resolution ranging from 2 to 15 eV. Two electrostatic spectrometers and radioactive sources prepared by vacuum evaporation of ⁵⁷Co onto Al foils were utilized. Relative intensities of the main spectrum components have been obtained as follows: (TSE+LLX+Shake-off)/LMM/KLL/KLM/KMM/K−14.4/L−14.4/MN−14.4=116±12/51±4/59.7±1.8/15.2±0.4/1.15±0.07/49.6±1.5/5.05±0.15/0.79±0.02 where TSE means “true secondary electrons”. Absolute and relative energies of the LMM, KLL, KLM, and KMM Auger transitions in Fe have also been determined, as well as their relative intensities with the exception of the LMM lines, the shapes of which were strongly distorted due to the inelastic electron scattering and probably also chemical effects. From the measured conversion electron lines of the 14.4 keV M1 transition in ⁵⁷Fe, a transition energy of 14412.8±0.8 eV and the E2 admixture less than 8×10⁻⁶ were derived. Relative intensities of both the KL_2,3(M_4,5N₁) Auger line group and the M_4,5N₁−14.4 conversion line were found to be lower by about 30% for the “oxide” state of decaying ⁵⁷Co atoms than for the “metallic” state. Pronounced broadenings of narrow spectrum lines have been observed as a consequence of the oxidation of the ⁵⁷Co sources in the laboratory atmosphere. Natural widths for most of the KLL, KLM, and KMM Auger lines and those of the K, L₁, L₂, L₃, M₁, M₂, M₃ and N₁ atomic levels in ⁵⁷Fe were also determined.     

On the rate constants of OH + HO2 and HO2 + HO2: A comprehensive study of H2O2 thermal decomposition using multi-species laser absorption

Hydrogen peroxide (H₂O₂) and hydroperoxy (HO₂) reactions present in the H₂O₂ thermal decomposition system are important in combustion kinetics. H₂O₂ thermal decomposition has been studied behind reflected shock waves using H₂O and OH diagnostics in previous studies (Hong et al. (2009) [9] and Hong et al. (2010) [6,8]) to determine the rate constants of two major reactions: H₂O₂ + M → 2OH + M (k₁) and OH + H₂O₂ → H₂O + HO₂ (k₂). With the addition of a third diagnostic for HO₂ at 227 nm, the H₂O₂ thermal decomposition system can be comprehensively characterized for the first time. Specifically, the rate constants of two remaining major reactions in the system, OH + HO₂ → H₂O + O₂ (k₃) and HO₂ + HO₂ → H₂O₂ + O₂ (k₄) can be determined with high-fidelity.No strong temperature dependency was found between 1072 and 1283 K for the rate constant of OH + HO₂ → H₂O + O₂, which can be expressed by the combination of two Arrhenius forms: k₃ = 7.0 × 10¹² exp(550/T) + 4.5 × 10¹⁴ exp(?5500/T) [cm³ mol^?1 s^?1]. The rate constants of reaction HO₂ + HO₂ → H₂O₂ + O₂ determined agree very well with those reported by Kappel et al. (2002) [5]; the recommendation therefore remains unchanged: k₄ = 1.0 × 10¹⁴ exp(?5556/T) + 1.9 × 10¹¹⁺exp(709/T) [cm³ mol^?1 s^?1]. All the tests were performed near 1.7 atm.     

Methylene bromide chemistry and photochemistry on rutile TiO2(110)

The chemistry and photochemistry of methylene bromide (CD₂Br₂) on the rutile TiO₂(110) surface was probed using temperature programmed desorption (TPD). CD₂Br₂ desorbed in three desorption states at 145, 160 and 250 K tentatively assigned to desorption from the multilayer, from an η¹-CD₂Br₂ species and a bridging η²-CD₂Br₂ species, respectively. The latter two TPD states presumably involve binding of CD₂Br₂ molecules to the surface through Br coordination at five-coordinate Ti⁴⁺ surface sites. The 160 and 250 K TPD states saturated at coverages of 1.0 and 0.33 ML, respectively, where 1 ML is equivalent to the surface Ti⁴⁺ site density (5.2 × 10¹⁴ cm^? 2). No thermal decomposition of CD₂Br₂ was observed on either the clean surface or with preadsorbed O₂. UV irradiation of CD₂Br₂ on TiO₂(110) resulted in predominately photodesorption, with trace amounts of photodecomposition evidenced in TPD. The rate of CD₂Br₂ photodesorption from TiO₂(110) occurred with a low cross section (~ 2 × 10^? 21 cm²) similar to that expected from direct optical excitation of CD₂Br₂. This observation suggests that charge carriers generated in TiO₂(110) were no more effective in activating adsorbed CD₂Br₂ molecules than would be expected through direct molecular excitation. These findings suggest that photocatalytic destruction of halocarbons such as CD₂Br₂ on TiO₂ may preferentially occur though indirect processes (such as OH radical attack) as opposed to direct electron transfer processes involving charge carriers generated in TiO₂ by bandgap excitation.     

Electronic charge transfer between Au nano-particles and TiO2-terminated SrTiO3(0 0 1) substrate

The interaction between Au nano-particles and oxide supports is recently discussed in terms of the catalytic activities. This paper reports the electronic charge transfer between Au nano-particles and TiO₂-terminated SrTiO₃(0 0 1) substrate, which is compared with that for stoichiometric(S)-, pseudo-stoichiometric(S¹)- and reduced(R)-TiO₂(1 1 0) supports. We observed the photoelectron spectra of Au 4f, O 2s, Ti 3p, and Sr 4p lines and also measured the work functions for Au/oxides supports using synchrotron-radiation light. As the results, all the O 2s, Ti 3p, and Sr 4p lines for Au/SrTiO₃(0 0 1) show lower binding energy shifts in a quite same manner and abrupt increase in the work function is seen in an initial stage. This clearly evidences an electronic charge transfer from the substrate to Au probably due to a much larger work function of Au than SrTiO₃(0 0 1), which leads to an upward band bending (0.3 eV) just like a Schottky contact. Electronic charge transfers also take place at Au/S- and Au/S¹-TiO₂(1 1 0) and Au/R-TiO₂(1 1 0) interfaces, where electrons are transferred from Au to S- and S¹-TiO₂ and from R-TiO₂ to Au, as predicted by ab initio calculations.     

Influence of rapid thermal annealing on electrical and structural properties of double metal structure Au/Ni/n-InP (1 1 1) diodes

The effect of rapid thermal annealing on the electrical and structural properties of Ni/Au Schottky contacts on n-InP have been investigated by current–voltage (I–V), capacitance–voltage (C–V), auger electron spectroscopy (AES) and X-ray diffraction (XRD) techniques. The Au/Ni/n-InP Schottky contacts are rapid thermally annealed in the temperature range of 200–500 °C for a duration of 1 min. The Schottky barrier height of as-deposited Ni/Au Schottky contact has been found to be 0.50 eV (I–V) and 0.86 eV (C–V), respectively. It has been found that the Schottky barrier height decreased with increasing annealing temperature as compared to as-deposited sample. The barrier height values obtained are 0.43 eV (I–V), 0.72 eV (C–V) for the samples annealed at 200 °C, 0.45 eV (I–V) and 0.73 eV (C–V) for those at 400 °C. Further increase in annealing temperature to 500 °C the barrier height slightly increased to 0.46 eV (I–V) and 0.78 eV (C–V) compared to the values obtained for the samples annealed at 200 °C and 400 °C. AES and XRD studies showed the formation of indium phases at the Ni/Au and InP interface and may be the reason for the increase in barrier height. The AFM results showed that there is no significant degradation in the surface morphology (rms roughness of 1.56 nm) of the contact even after annealing at 500 °C.     

Improved electrical parameters of vacuum annealed Ni/4H-SiC (0 0 0 1) Schottky barrier diode

The reported work has been focused on the improvement of electrical parameters of Schottky diode using vacuum annealing at mild temperature in Ar gas ambient. Nickel Schottky barrier diodes were fabricated on 50 μm epitaxial layer of n-type 4H-SiC (0 0 0 1) substrate. The values of leakage current, Schottky barrier height (?_B), ideality factor (η) and density of interface states (N_SS) were obtained from experimentally measured current–voltage (I–V) and capacitance–voltage (C–V) characteristics before and after vacuum annealing treatment. The data revealed that ?_B, η and reverse leakage current for the as-processed diodes are 1.25 eV, 1.6 and 1.2 nA (at ?100 V), respectively, while for vacuum annealed diodes these parameters are 1.36 eV, 1.3 and 900 pA (at same reverse voltage). Improved characteristics have been resulted under the influence of vacuum annealing because of lesser number of minority carrier generation due to incessant reduction of number of available discrete energy levels in the bandgap of 4H-SiC substrate and lesser number of interface states density at Ni/4H-SiC (0 0 0 1) interface.     

Deep level transient spectroscopy (DLTS) study of defects introduced in antimony doped Ge by 2 MeV proton irradiation

Deep level transient spectroscopy (DLTS) and Laplace-DLTS have been used to investigate the defects created in Sb doped Ge after irradiation with 2 MeV protons having a fluence of 1×10¹³ protons/cm². The results show that proton irradiation resulted in primary hole traps at E_V +0.15 and E_V +0.30 eV and electron traps at E_C ?0.38, E_C ?0.32, E_C ?0.31, E_C ?0.22, E_C ?0.20, E_C ?0.17, E_C ?0.15 and E_C ?0.04 eV. Defects observed in this study are compared with those introduced in similar samples after MeV electron irradiation reported earlier. E_C ?0.31, E_C ?0.17 and E_C ?0.04, and E_V +0.15 eV were not observed previously in similar samples after high energy irradiation. Results from this study suggest that although similar defects are introduced by electron and proton irradiation, traps introduced by the latter are dose dependent.     

Monochromatic soft X-ray-induced reactions of CCl2F2 adsorbed on Si(111)-7 × 7 near the Si(2p) edge

Continuous-time photoelectron spectroscopy (PES) and continuous-time core-level photon-stimulated desorption (PSD) spectroscopy were used to study the monochromatic soft X-ray-induced reactions of CCl₂F₂ molecules adsorbed on Si(111)-7 × 7 at 30 K (CCl₂F₂ dose = 2.0 × 10¹⁴ molecules/cm², ~ 0.75 monolayer) near the Si(2p) core level. Evolution of adsorbed CCl₂F₂ molecules was monitored by using continuous-time photoelectron spectroscopy at two photon energies of 98 and 120 eV to deduce the photolysis cross section as a function of energy. It was found that the photolysis cross sections for 98 and 120 eV photons are _~1.4 × 10^? 18 and ~ 8.0 × 10^? 18 cm², respectively. Sequential F⁺ PSD spectra obtained by using continuous-time core-level photon-stimulated desorption spectroscopy in the photon energy range of 98–110 eV show the variation of their shapes with photon exposure and depict the formation of surface SiF species. The dissociation of CCl₂F₂ molecules adsorbed on Si(111)-7 × 7, irradiated by monochromatic soft X-ray in the photon energy range of 98–110 eV, is mainly due to dissociative electron attachment and indirect dipolar dissociation induced by photoelectrons emitted from the silicon surface.     

Interaction of NO with the O-rich RuO2(1 1 0) surface at 300 K

The interaction of NO with the O-rich RuO₂(1 1 0) surface, exposing coordinatively unsaturated O-bridge, O-cus, and Ru-cus atoms, was studied at 300 K by thermal desorption spectroscopy (TDS) and high-resolution electron energy-loss spectroscopy (HREELS). The conclusions are validated by isotope substitution experiments with ¹⁸O. During exposure to NO an O···N–O surface group (NO₂-cus) is formed with O-cus. Additionally, a smaller number of empty Ru-cus sites are filled by NO-cus. If one warms the sample to 400 K, NO₂-cus does not desorb but decomposes into O and NO again, the latter being either released into gas phase or adsorbed as NO-cus. With O-bridge such a surface group is not stable at 300 K. Our experiments further prove that O-cus is more reactive than O-bridge.     

Band overlap via chemical pressure control in double perovskite (Sr2−xCax)FeMoO6 (0 ⩽ x ⩽ 2.0) with TMR effect

The chemical pressure control in (Sr_2−xCa_x)FeMoO₆ (0 ⩽ x ⩽ 2.0) with double perovskite structure has been investigated systematically. We have performed first-principles total energy and electronic structure calculations for x = 0 and x = 2.0. The increasing Ca content in (Sr_2−xCa_x)FeMoO₆ samples increases the magnetic moment close to the theoretical value due to reduction of Fe/Mo anti-site disorder. An increasing Ca content results in increasing (Fe²⁺ + Mo⁶⁺)/(Fe³⁺ + Mo⁵⁺) band overlap rather than bandwidth changes. This is explained from simple ionic size arguments and is supported by X-ray absorption near edge structure (XANES) spectra and band structure calculations.     

Electronic structure and fundamental absorption edges of KPb2Br5, K0.5Rb0.5Pb2Br5, and RbPb2Br5 single crystals

X-ray photoelectron core-level and valence-band spectra for pristine and Ar⁺-ion irradiated (001) surfaces of KPb₂Br₅, K_0.5Rb_0.5Pb₂Br₅, and RbPb₂Br₅ single crystals grown by the Bridgman method have been measured and fundamental absorption edges of the ternary bromides have been recorded in the polarized light at 300 K and 80 K. The present X-ray photoelectron spectroscopy (XPS) results reveal high chemical stability of (001) surfaces of K_xRb_1?xPb₂Br₅ (x=0, 0.5, and 1.0) single crystals. Substitution of potassium for rubidium in K_xRb_1?xPb₂Br₅ does not cause any changes of binding energy values and shapes of the XPS constituent element core-level spectra. Measurements of the fundamental absorption edges indicate that band gap energy, E_g, increases by about 0.14 and 0.19 eV when temperature decreases from 300 K to 80 K in KPb₂Br₅ and RbPb₂Br₅, respectively. Furthermore, there is no dependence of the E_g value for KPb₂Br₅ upon the light polarization, whilst the band gap energy value for RbPb₂Br₅ is bigger by 0.03–0.05 eV in the case of E6c compared to those in the cases of E6a and E6b.     

Saturable absorber at 940 nm using single wall carbon nanotubes deposited by vertical evaporation technique

The vertical evaporation technique allows us to fabricate aligned single wall carbon saturable absorbers. The nonlinear parameters of the absorber at the wavelength of 940 nm were measured. The measured bi-exponential lifetimes of the absorber are 330 fs and 850 fs, respectively. The saturation intensity and modulation depth were found to be 2000 μJ/cm² and 10% for SWCNT absorber at the direction of alignment, in comparison to 950 μJ/cm² and 7% for the SWCNT solution.     

Oxygen diffusion studies on (Y2O3)2(Sc2O3)9(ZrO2)89

The oxygen tracer diffusion coefficient (D?) has been measured for 9 mol% scandia 2 mol% yttria co-doped zirconia solid solution, (Y₂O₃)₂(Sc₂O₃)₉(ZrO₂)₈₉, using isotopic exchange and line scanning by Secondary Ion Mass Spectrometry, as a function of temperature. The values of the tracer diffusion coefficient are in the range of 10^? 8–10^? 7 cm² s^? 1 and the Arrhenius activation energy was calculated to be 0.9 eV; both valid in the temperature range of 600–900 °C. Electrical conductivity measurements were carried out using 2-probe and 4-probe AC impedance spectroscopy, and a 4-point DC method at various temperatures. There is a good agreement between the measured tracer diffusion coefficients (D?, Ea = 0.9 eV) and the diffusion coefficients calculated from the DC total conductivity data (D_σ, Ea = 1.0 eV), the latter calculated using the Nernst–Einstein relationship.     

Synthesis and characterization of layered Li1−x(Ni0.5Co0.5)1−yFeyO2(0 ≤ (1 − x) ≤ 1 and 0 ≤ y ≤ 0.2) cathodes

Layered Li(Ni_0.5Co_0.5)_1−yFe_yO₂ cathodes with 0 ≤ y ≤ 0.2 have been synthesized by firing the coprecipitated hydroxides of the transition metals and lithium hydroxide at 700 °C and characterized as cathode materials for lithium ion batteries to various cutoff charge voltages (up to 4.5 V). While the y = 0.05 sample shows an improvement in capacity, cyclability, and rate capability, those with y = 0.1 and 0.2 exhibit a decline in electrochemical performance compared to the y = 0 sample. Structural characterization of the chemically delithiated Li_1−x(Ni_0.5Co_0.5)_1−yFe_yO₂ samples indicates that the initial O3 structure is maintained down to a lithium content (1 − x) ≈ 0.3. For (1 − x) < 0.3, while a P3 type phase is formed for the y = 0 sample, an O1 type phase is formed for the y = 0.05, 0.1 and 0.2 samples. Monitoring the average oxidation state of the transition metal ions with lithium contents (1 − x) reveals that the system is chemically more stable down to a lower lithium content (1 − x) ≈ 0.3 compared to the Li_1−xCoO₂ system. The improved structural and chemical stabilities appear to lead to better cyclability to higher cutoff charge voltages compared to that found before with the LiCoO₂ system.     

Anionic conductors Ln2/3[Bi12O14](MoO4)5 with Ln = La,Nd, Gd,Ho, Yb. Synthesis–spark plasma sintering–structure–electric properties

A new series of columnar phases Ln_2/3□_1/3[Bi₁₂O₁₄](MoO₄)₅ (□ vacancy) with Ln = La, Nd, Gd, Ho and Yb have been synthesized and structurally characterized. They feature the same formula as the molybdate phase Bi_2/3□_1/3[Bi₁₂O₁₄](MoO₄)₅ and crystallize in the monoclinic system, space group P2/c. These phases are isostructural with the prototype structure Bi[Bi₁₂O₁₄](MoO₄)₄(VO₄). Pellets of this rare-earth series obtained by spark plasma sintering and measured by impedance spectroscopy show a good anionic conductivity with a parabolic evolution whose maximum is raised by the Gd species at a determined value σ = 6.6 × 10^− 3 S cm^− 1 at 980 K.     

Electrical and structural investigations of perovskite structure reactively sputter deposited coatings

Sr(Zr_0.84Y_0.16)_0.91O_3 ? δ (SZY) and Ba(Zr_0.84Y_0.16)_0.96O_3 ? δ (BZY) protonic conductor coatings were co-sputter deposited from metallic targets in argon–oxygen reactive gas mixtures. The chemical and structural features were investigated by energy dispersive X-ray spectroscopy and X-ray diffraction, and their morphology was assessed by scanning electron microscopy of the surface and of brittle fracture cross sections. The electrical properties of the coating were determined by complex impedance spectroscopy as a function of temperature in air. Relationships are established between the electrical properties and the morphology of the coatings. The SZY as deposited coatings is amorphous and crystallises under the convenient perovskite structure after annealing treatment at 873 K under air. The BZY as deposited coatings is crystallised at 523 K in situ under perovskite structure and a further annealing treatment increases the grain size. Conductivities and activation energies of crystallised coatings were 3.1 · 10^? 5 S cm^? 1/2 · 10^? 5 S cm^? 1 and 0.65 eV/0.71 eV after stabilization at 773 K for strontium and barium zirconate, respectively.     

Ferroelectric phase transition and optical performance of PLZnNZT transparent ceramics

Lead-based Pb_0.97La_0.02(Zn_1/3Nb_2/3)_0.3(Zr_0.53Ti_0.47)_0.7O₃ (PLZnNZT) transparent ceramics with the addition of 2 wt% excess PbO were prepared by hot-pressing sintering method. The hot-pressing sintered PLZnNZT ceramics exhibit dense and large-grained microstructure, and perovskite structure with distorted cubic-like symmetry. The ceramics exhibit normal ferroelectric-like dielectric behavior with slightly diffused ferroelectric phase transition characteristic. The PLZnNZT ceramics exhibit fully developed, symmetric and saturated P–E hysteresis loop and large piezoelectric constant d₃₃, being 468 pC/N. The ceramics with 120 μm thickness exhibit maximum transmittance of 53% at 850 nm when Fresnel losses was not included, almost totally transparent in the mid IR region (2500–5600 nm), and low-lying optical band gap energy E_g of 3.23 eV. Three diffused Raman bands centering around 240 cm⁻¹, 560 cm⁻¹ and 750 cm⁻¹ are observed by micro-Raman spectroscopy, which can be attributed to F2g [BO₆] bending vibration, A1g [BO₆] stretching vibration and “soft mode” mixed by the bending and stretching vibrations, respectively, confirming the normal ferroelectric-like characteristic.     

Metastable helium atom scattering from Ni(1 1 0) surface

The survival probability (SP) of metastable helium atoms (He¹) during scattering from the clean, alkalated and oxygen-adsorbed Ni(1 1 0) surfaces has been examined in the kinetic energy range of 50–400 meV. The measurements were carried out using a time-of-flight technique and a pulsed-discharge type metastable helium atom source. The SP is nearly constant for a kinetic energy (E_kin) of 50–100 meV and decreases exponentially with the increase in E_kin at 100–400 meV. It has been shown that the SP at E_kin=100–400 meV depends on the repulsive part of the He¹-surface interaction potential.     

Structure and conductivity investigations of alkaline earth substituted uranium oxide,U1 − xMxO2 ± δ (M = Mg,Ca, Sr) for solid oxide fuel cell applications

Alkaline earth substituted UO₂ (U_1 − xM_xO_2 ± δ; M = Mg, Ca, Sr; 0.1 ≤ x ≤ 0.525) with fluorite structure was synthesized in reducing atmosphere. Structure and conductivity properties of U_1 − xM_xO_2 ± δ fluorites were investigated for possible application in solid oxide fuel cells (SOFC). At room temperature and ambient atmosphere the materials are stable; however they decompose at an oxygen partial pressure p_O2 > 10^− 4 atm and temperatures higher than 600 °C. The total conductivity measured for the best conducting U_1 − xM_xO_2 ± δ material with M = Ca and x = 0.177 is as high as 3 S/cm at p_O2 < 10^− 4 atm at 600 °C. The relatively low ionic transference number (t_i∼0.02) is disadvantageous for potential use as electrolyte material for SOFC applications. The high conductivity and possible depolarization effects suggest potential use as anode materials in SOFC.     

First-principles study of small palladium clusters on NiAl(1 1 0) alloy surface

Theoretical calculations focused on the geometry, stability, electronic and magnetic properties of small palladium clusters Pd_n (n=1–5) adsorbed on the NiAl(1 1 0) alloy surface were carried out within the framework of density functional theory (DFT). In agreement with the experimental observations, both Ni-bridge and Al-bridge sites are preferential for the adsorption of single palladium atom, with an adsorption energy difference of 0.04 eV. Among the possible structures considered for Pd_n (n=1–5) clusters adsorbed on NiAl(1 1 0) surface, Pd atoms tend to form one-dimensional (1D) chain structure at low coverage (from Pd₁ to Pd₃) and two-dimensional (2D) structures are more stable than three-dimensional (3D) structures for Pd₄ and Pd₅. Furthermore, metal-substrate bonding prevails over metal–metal bonding for Pd cluster adsorbed on NiAl(1 1 0) surface. The density of states for Pd atoms of Pd/NiAl(1 1 0) system are strongly affected by their chemical environment. The magnetic feature emerged upon the adsorption of Pd clusters on NiAl(1 1 0) surface was due to the charge transfer between Pd atoms and the substrate. These findings may shade light on the understanding of the growth of Pd metal clusters on alloy surface and the construction of nanoscale devices.