Phase transformations and vacancy formation energies of transition metals by positron annihilation

The technique of the coincidence count rate at the peak of the angular correlation curve (CCR) in positron annihilation has been applied to the investigation of vacancy formation energies in thermal equilibrium in nickel, cobalt, and iron. The monovacancy formation energyE ^1v/F has been determined to (1.55±0.05) eV and (1.34±0.07) eV for nickel and cobalt, and (1.60±0.10) eV for α-iron, and (1.40±0.15) eV for γ-iron, respectively. The structural phase transformations in cobalt (693 K) and iron (1183 K, 1663 K) are exhibited by discontinuities of the CCR. In the case of cobalt the CCR follows exactly the change of the thermal expansion at the transition temperature. The temperature dependence of the CCR in the prevacancy region is found to be proportional to the thermal expansion for all metals investigated.     

Injection and thermodepolarization currents in GaSe <Co> single crystals

The current-voltage characteristics (CVC) at different temperatures, the temperature dependence of electric conductivity [σ(T)] and the currents of thermostimulated depolarization (TSD) have been studied in GaSe <0.05 at.% Co> on a combined basis.The location depth (E_t=0.57eV) and the concentration of traps (N_t=2.7x10¹²cm^?3) have been determined from the temperature dependence of the trapping factor. In the course of TSD investigations, levels with location depths of 0.28±0.02 and 0.57±0.03 eV have been revealed. It is noted that traps with the energy of 0.57±0.03 eV are found both with TSD measurements and on the basis of the temperature dependence of the electric conductivity and the trapping factor.It has been established that the hole centres above the valence band are responsible for the CVC, σ(T) and TSD. The location depths, concentrations and trapping cross-sections of these centres have been determined.     

μ+SR study of vacancies in thermal equilibrium in ferromagnets

Muon spin precession frequencies and transverse relaxation rates have been measured on demagnetized iron, cobalt, and FeCo alloys (3 at%–50 at% Co) between room temperature and the Curie temperatureT _c. The increase of the relaxation rate in iron between 930 K and 1010 K could be quantitatively attributed to the trapping of positive muons by vacancies in thermal equilibrium, resulting in an enthalpy of monovacancy formation ofH _1V ^F =(1.7±0.1) eV. the smallest vacancy concentrations detected are = 10⁻⁸.     

Ionic conductivity and dielectric measurements in single crystal βAgI

Ionic conductivity measurements have been made on pure, copper-doped and cadmium-doped single crystals. Dielectric measurements in the frequency range 30Hz–100Hz showed that there was no anomalously to be (0.64 ± 0.02) eV and migration energies for silver ion intersitials and vacancies in the c direction to be (0.41 ± 0.02) eV and (0.50 ± 0.02) eV respectively. ESR measurements have shown that copper exists as Cu⁺ in these crystals. Dielectric measurements in the frequency range (OHz–100KHz showed that there was no anomalously high value for ? as reported earlier.     

The scattering of hydrogen,deuterium, and the rare gases from silver (111) single crystals

The scattering of hydrogen, deuterium, and the rare gases from the (111) face of silver has been studied at ultrahigh vacuum. The surfaces were prepared by argon ion bombardment and high temperature annealing. Incident angles between 20° and 65° and surface temperatures between room temperature and 573°K have been investigated. The scattering data exhibit quasi-elastic scattering (He, H₂, D₂), inelastic scattering (Ne, Ar, Kr), and trapping dominated scattering (Xe). Identification of these scattering regimes correlates with D/kT_g and is consistent with similar data from Pt(111) and W(110). The separate effects of microscopic surface roughness and thermal roughening have been identified and thermal attenuation in the elastic regime correlated with dynamical interactions rather than thermal roughening. Trapping and rotational coupling are discussed. Comparison of the data with scattering from epitaxial (111) silver indicates that the epitaxial surfaces are significantly more disordered than the single crystal surfaces.     

Determination of the vacancy formation energy for different sublattices of ordered β-CuZn alloy by positron annihilation method

The temperature dependence of positron annihilation has been investigated for samples of the ordered β-CuZn alloy with different crystallographic orientations. The results obtained have been interpreted on the basis of the extended trapping model. Analysis of the temperature dependence of the peak coincidence count gives the values of the free energy of formation for vacant sites, left by Cu- and Zn atoms equal 0.58±0.02 eV and 0.77±0.04 eV, respectively. The dependence of the vacancy formation energy on the long-range order parameter has not been observed.     

用正电子湮没寿命谱研究凝聚态甲烷的温度关系

在30—150K温度范围内,测量了高纯凝聚态甲烷中的正电子寿命谱随温度的变化。在固态甲烷中,正电子素(简称Ps)在自由体积中形成,形成率为²7%。正-正电子素(其符号为o-Ps)的寿命随温度变化的特征可用o-Ps在热激活空位型缺陷中的捕获来说明,且由Ps捕获模型和实验测得的o-Ps寿命求得缺陷激活能E_a=0.10±0.02eV。在液态甲烷中,Ps形成率高达36%,且o-Ps寿命长达5—7ns,这表明液态甲烷中形成了Ps气泡态。我们用经验公式估算了这种气泡的尺寸及其微观表面张力。 关键词：     

Diffusion of sodium in rubidium chloride

The diffusion of Na²²Cl in RbCl was measured in the temperature range 377–707°C by the tracer-sectioning technique. The activation energy is 2.06± 0.02 and 0.59 ± 0.01 eV in the intrinsic and extrinsic regions, respectively. The temperature dependence of the correlation factor, as deduced from isotope-effect measurements, is 0.19 eV in the intrinsic region and -0.05 eV in the extrinsic region. When a theoretical value for the Na^+- vacancy binding energy is used, values of ½h_f =1.22, eV and h_m= 0.55 eV are obtained where h_f is the energy of formation, and h_m the energy of motion, of a cation vacancy. These values are not in agreement with the calculation by Tosi and Doyama.     

Lattice site occupation and precipitate dissolution of implanted and irradiated Al(Rh) and Al(Ir)

Abstract

The apparent substitutional fraction, f_s , of Rh and Ir implanted into Al single crystals at 293 K with peak concentrations of 0.17±0.01 at.% is 0.57 ± 0.02 and 0.47±0.02, respectively. Upon annealing to 593 K f_s decreases and the critical angles of the impurities narrow due to partially coherent precipitate formation. Irradiation with 300 keV Ar ions at 77 K with deposited energy densities up to 20 dpa leads to precipitate dissolution accompanied by an increase of f_s up to 0.70±0.02 for Al(Rh) and 0.82±0.02 for Al(Ir). The relatively high f_s values do not decrease during annealing from 77 K to 293 K, indicating that vacancy trapping is not a dominant process. Precipitate formation seems therefore to limit the maximum obtainable f_s values during implantation at 293 K for these systems.     

Self-diffusion of oxygen in superstoichiomertric uranium dioxide in the range of the superion phase transition

The self-diffusion of oxygen in the superion transition range (1300–3000 K) of superstoichiometric uranium dioxide UO_{2 + x} is studied by the method of molecular dynamics using the pair interaction potential recovered from data for the thermal expansion of the UO₂ lattice. It is shown that three portions can be distinguished in the temperature dependence of the coefficient of oxygen self-diffusion in UO_{2 + x} , lnD = f(1/T), for all the compositions studied (x = 0, 0.008, and 0.030). These portions, each being described by the Arrhenius relationship, correspond to the crystalline, transition, and superion states of UO_{2 + x} . At low temperatures (1300–1820 K), the activation energies of oxygen diffusion for the above compositions are, respectively, 2.66 ± 0.44, 1.33 ± 0.10, and 1.00 ± 0.09 eV. At the beginning of the transition region, these activation energies rise to 3.40 ± 0.11, 2.24 ± 0.10, and 1.66 ± 0.60 eV. In the superion state, the activation energy of oxygen diffusion for all the compositions is the same, 1.25 ± 0.15 eV, within the error limit. As the oxygen content in UO_{2 + x} grows, the phase transition temperature decreases considerably and may reach 1600 K at x = 0.2. Comparison with experimental data for the low-temperature oxygen diffusion coefficient and with the data of UO₂ simulation using graphic processors shows good agreement of the results. By comparing the concentration dependences of the oxygen diffusion coefficient that are obtained by magnetic dynamics simulation with experimental data, it is shown that quantitative calculation of these dependences in the case of UO_{2 + x} can be carried out only for compositions with x < 0.03 if the given type of potential is used.     

Positron lifetimes and annihilation lineshape in Cd and au from 4.2 K to the melting points

By means of an integrated source-specimen technique the temperature dependence of positron lifetimes and annihilation lineshapes has been measured, on the same specimens of gold and cadmium from 4.2K to the melting points, and also in electronirradiated and quenched gold. The anomalous temperature dependence of positron annihilation at intermediate temperatures (200 to 350 K in Cd, 270 to 750 K in Au) discovered by Lichtenberger, Schulte, and MacKenzie is confirmed. The data are incompatible with the idea that the intermediate temperature dependence is due to thermal expansion. They are well explained by an extension of the trapping model which includes the formation of metastable self-trapped positrons. From lineshape measurements after electron irradiation at 180 K and after quenching it is deduced that the trapping rate of positrons at vacancy-type defects in Au is temperature independent below room temperature.     

Optical properties and ultrafast electron dynamics in gold–silver alloy and core–shell nanoparticles

Silver and gold are the two most popular metals used for many nanoparticle applications, such as surface enhanced Raman scattering or surface enhanced fluorescence, in which the local field enhancement associated with the excitation of the localized surface-plasmon–polariton resonance (SPR) is exploited. Therefore, tunability of the SPR over a wide energy range is required. For this purpose we have investigated core–shell nanoparticles composed of gold and silver with different shell thicknesses as well as the impact of alloying on these nanoparticles due to a tempering process. The nanoparticles were prepared by subsequent deposition of Au and Ag atoms or vice versa on quartz substrates followed by diffusion and nucleation. Their linear extinction spectra were measured as a function of shell thickness and annealing temperature. It turned out that different gold shell thicknesses on silver cores allow a tuning of the SPR position from 2.79 to 2.05 eV, but interestingly without a significant change on the extinction amplitude. Heating of core–shell nanoparticles up to only 540 K leads to the formation of alloy nanoparticles, accompanied by a back shift of the SPR to 2.60 eV. Calculations performed in quasi-static approximation describe the experimental results quite well and prove the structural assignments of the samples. In additional experiments, we applied the well-established persistent spectral hole burning technique to the alloy nanoparticles in order to determine the ultrafast dephasing time T ₂. We obtained a dephasing time of T ₂=(8.1±1.6) fs, in good agreement with the dephasing time of T _2,∞=8.9 fs, which is already included in the dielectric function of the bulk.     

Temperature effect on nitrogen-induced absorption of oxygen in the Herzberg continuum

The effect of temperature on the total absorption of O₂ induced by collisions with N₂ has been measured at various temperatures in the Herzberg continuum using a one meter normal incidence grating monochromator. It is observed that absorption increases as the temperature decreases which is ascribed to changes in the rate of formation of the dimers O₂-O₂ and O₂-N₂. The interaction constants for these dimers are determined as functions of temperature and are then utilized to calculate the heat of dissociations of O₂-O₂ and O₂-N₂. Their respective values are found to be 0.0146±0.001 and 0.0425±0.002 eV. Also, the interaction constants for these dimers measured at 200±1°K are utilized to investigate their effect on the absorption of solar radiation in the stratosphere.     

Processes involved in the formation of silver clusters on silicon surface

We analyze scanning electron microscopy measurements for structures formed in the deposition of solid silver clusters onto a silicon(100) substrate and consider theoretical models of cluster evolution onto a surface as a result of diffusion and formation of aggregates of merged clusters. Scanning electron microscopy (SEM) data are presented in addition to energy dispersive X-ray spectrometry (EDX) measurements of the these films. Solid silver clusters are produced by a DC magnetron sputtering source with a quadrupole filter for selection of cluster sizes (4.1 and 5.6 nm or 1900 and 5000 atoms per cluster in this experiment); the energy of cluster deposition is 0.7 eV/atom. Rapid thermal annealing of the grown films allows analysis of their behavior at high temperatures. The results exhibit formation of cluster aggregates via the diffusion of deposited solid clusters along the surface; an aggregate consists of up to hundreds of individual clusters. This process is essentially described by the diffusion-limited aggregation (DLA) model, and thus a grown porous film consists of cluster aggregates joined by bridges. Subsequent annealing of this film leads to its melting at temperatures lower than to the melting point of bulk silver. Analysis of evaporation of this film at higher temperatures gives a binding energy in bulk silver of ɛ₀= (2.74 ± 0.03) eV/atom. The text was submitted by the authors in English.     

The trapping of K and Na atoms by a clean W(110) surface trajectory calculations

The fraction of K and Na atoms initially trapped by the W(110) surface has been measured as a function of the incident energy (0.5–15 eV) and as a function of the incident angle. The trapping probability equals one at low incident energies (E_i ? 0.5 eV) and decreases with increasing energy. The measurements show an increase of trapping with increasing angle of incidence θ_i (measured from the surface normal). Simultaneously the desorption energies Q_i were determined from the temperature dependence of the measured mean residence time on the W(110) surface. We obtained for K: Q_i = 2.05 ± 0.02 eV, and for Na: Q_i = 2.60 ± 0.04 eV.The trapping phenomenon at a solid surface was approximated in a theoretical way by calculating the in-plane trajectory of a projectile scattered from a diatomic surface-molecule. The important feature which showed up was the conversion of tangential to normal momentum of the projectile, and thus the inapplicability of cube models. As a function of the angle of incidence two regimes can be distinguished: at the smaller angles the scattering is governed by simultaneous interaction of the projectile with two neighbouring surface atoms, and at the higher angles of incidence the single particle interaction contributes most to the momentum transfer.     

A study of copper adsorption on (100) tungsten by high field microscopy

An increase in the work function of a copper layer approximately three monolayers deep on tungsten (100) can be thermally induced at temperatures above 540 K. Helium ion microscopy reveals a consequent but small increase in structural perfection of the tungsten substrate surface, which is akin to the rearrangement of gold, but the change in work function of the copper layer appears not to depend upon the rearrangement. Detailed investigation of changes in work function at (100) using a probe-hole field emission microscope shows that copper in the first monolayer increases φ₁₀₀ by 0.42 eV at monolayer coverage, probably by formation of an array of dipoles of moment μ₀ = (1.6 ± 0.5) × 10^?30 C m with polarizability α = 3.80 ± 1.8 ų. A large apparent increase in φ₁₀₀ of 1.6 eV takes place when a thicker copper layer is spread so that it surrounds and approaches (100), and this is ascribed to a reduction in the field enhancement factor β produced by the surrounding copper. Comparison of the present findings with those of Bauer et al. reveals substantial agreement on the behaviour of the first monolayer and two major differences in the behaviour of thicker layers: (i) an increase in φ₁₀₀ from 4.25 to 7.1 eV which we observe above 540 K, and (ii) absence of any evidence for breakup of third and higher layers to form crystallites. It is tentatively suggested that (i) results from band-structure changes accompanying structural reorganisation within the adsorbed layer, which take place under experimental conditions not used by Bauer et al., and that (ii) is due to the absence of steps in the probed area of (100) which can act as nucleating centres for crystallite formation on a macroscopic (100) surface.     

Effects of temperature and impurities on electron radiation damage in the high voltage microscope

This paper describes the results of irradiation of specimens of copper and copper containing up to 2 at % beryllium in the high-voltage electron microscope. The results of irradiation at temperatures ranging from 20–500 K are described and discussed in the light of recently proposed theories of defect nucleation. Although the results are difficult to interpret because of the many diverse factors which influence the nucleation and growth of the damage it was found that the values for the volume density of defects were in general agreement with the predictions, if the effects of the foil surfaces were taken into account.

The corrected densities were used to derive values for the activation energy for motion of an interstitial in copper, E_m , and the binding energy between an interstitial and a beryllium atom, E_b . The results obtained were 0.12±0.03 eV for E_m and 0.29±0.07 eV for E_b .     

Measurement of the lattice parameter of sodium by neutron-back-scattering

We report high precision results (δa/a ≈ 3 x 10^-6) of the lattice parameter of high purity sodium (99.99%) in the temperature region from 32°C up to the melting point. Data of the crystal quality are also given: the half width of the angular mosaic spread amounts to about 4'. Preliminary results on vacancy formation energy and entropy, using literature data of volume expansion, are 0.35 ± 0.02 eV and (3.7 ± 0.5) k_B resp. for a single vacancy.     

Thermal depolarisation current study of electron irradiated fluorinated ethylene propylene

Thermally stimulated current (TSC) studies have been reported in the co-polymer of tetrafluoro ethylene and hexafluoropropylene films. Depolarisation current peaks are obtained atα ₁,α ₂ andβ relaxation temperatures of the polymer and the detrapping process is explained on the basis of its molecular motion. A cross-over electron energy of 18 keV is observed where the nature of TSC spectra undergoes a remarkable change. This is explained in relation to the surface states in FEP. Five groups of trapping levels, 0.25±0.08, 0.57±0.10, 1.07±0.1, 1.3±0.25 and 2.3±0.4 eV are obtained.     

Devaluation of the gold standard in x-ray photoelectron spectroscopy

The value of vapor-deposited gold as a standard in x-ray photo-electron spectroscopy has been studied. During the deposition gold may react with the sample giving consequent shifts and/or broadening of the Au 4f peaks. Shifts to higher binding energies have been observed with KCN and NACl and to lower energies with Na₂S₂O₃ and copper phthalocyanine. The An 4f peaks have been investigated over the temperature range ?50 to 200°C. At higher temperatures peaks due to metallic gold are observed. Anomalous effects have been observed in the XPS spectrum of gold plated copper phthalocyanine in the binding energy range 650–950 eV.