Island coalescence and diffusion along kinked steps on Cu(0 0 1): Evidence for a large kink Ehrlich-Schwoebel barrier

Using temperature-variable scanning tunneling microscopy, we studied the coalescence of vacancy islands on Cu(0 0 1) in ultra-high vacuum. From the temperature dependence of the relaxation of merged vacancy islands to the equilibrium shape we obtain an activation energy of the island coalescence process of 0.76 eV. From that value we deduce an activation energy for the atomic hopping coefficient of E_Γh=0.89 eV. Comparing our result with previous STM data on step fluctuations with dominant diffusion along straight step segments (E_Γh=0.68 eV; [M. Giesen, S. Dieluweit, J. Mol. Catal. A: Chem. 216 (2004) 263]) and step fluctuations with kink crossing (E_Γh=0.9 eV; [M. Giesen-Seibert, F. Schmitz, R. Jentjens, H. Ibach, Surf. Sci. 329 (1995) 47]), we conclude that there is a large extra barrier for diffusion of atoms across kinks on Cu(0 0 1) of the order of 0.23 eV. This is the first direct experimental evidence for the existence of a large kink Ehrlich-Schwoebel barrier on Cu(0 0 1).     

Investigation of crystal structure and new ellipsometric properties of hexagonal CdS epilayers

High quality hexagonal CdS epilayer was grown on GaAs (1 1 1) substrates by the hot-wall epitaxy method. The crystal structure of the grown CdS epilayers was confirmed to be the hexagonal structure by X-ray diffraction pattern and scanning electron microscopy image. The optical properties of the hexagonal CdS epilayers were investigated in a wide photon energy range between 2.0 and 8.5 eV using spectroscopic ellipsometry (SE) at room temperature. The data obtained by SE were analyzed to find the critical points of the pseudodielectric function spectra, 〈?(E)〉 = 〈?₁(E)〉 + i〈?₂(E)〉, such as E₀, E_1A, E_1B, E^0′, F₁, and two E₂ structures. In addition, the second derivative spectra, d²?(E)/dE², of the pseudodielectric function of hexagonal CdS epilayers were numerically calculated to determine the critical structures. Four structures, such as E^0′F₁, and two E₂ structures, from 6.0 eV to 8.0 eV were observed, for the first time, at 300 K by ellipsometric measurements for the hexagonal CdS epilayers.     

Fourier transform spectroscopy of the CO-stretching band of O-18 methanol

The high-resolution Fourier transform spectrum of the ν₈ CO-stretching band of CH₃¹⁸OH between 900 and 1100 cm⁻¹ has been recorded at the Canadian Light Source (CLS) synchrotron facility in Saskatoon, and the majority of the torsion-rotation structure has been analyzed. For the ν_t = 0 torsional ground state, subbands have been identified for K values from 0 to 11 for A and E torsional symmetries up to J values typically well over 30. For ν_t = 1, A and E subbands have been assigned up to K = 7, and several ν_t = 2 subbands have also been identified. Upper-state term values determined from the assigned transitions using the Ritz program have been fitted to J(J + 1) power-series expansions to obtain substate origins and sets of state-specific parameters giving a compact representation of the substate J-dependence. The ν_t = 0 subband origins have been fitted to effective molecular constants for the excited CO-stretching state and a torsional barrier of 377.49(32) cm⁻¹ is found, representing a 0.89% increase over the ground-state value. The vibrational energy for the CO-stretch state was found to be 1007.49(7) cm⁻¹. A number of subband-wide and J-localized perturbations have been seen in the spectrum, arising both from anharmonic and Coriolis interactions, and several of the interacting states have been identified.     

Investigation of energy band gap and optical properties of cubic CdS epilayers

High quality cubic CdS epilayers were grown on GaAs (1 0 0) substrates by the hot-wall epitaxy method. The crystal structure of the grown epilayers was confirmed to be the cubic structure by X-ray diffraction patterns. The optical properties of the epilayers were investigated in a wide photon energy range between 2.0 and 8.5 eV using spectroscopic ellipsometry (SE) and were studied in the transmittance spectra at a wavelength range of 400-700 nm at room temperature. The data obtained by SE were analyzed to find the critical points of the pseudodielectric function spectra, 〈?(E)〉 = 〈?₁(E)〉 + i〈?₂(E)〉, such as E₀, E₁, E₂, E^′₀, and E^′₁ structures. In addition, the optical properties related to the pseudodielectric function of CdS, such as the absorption coefficient α(E), were investigated. All the critical point structures were observed, for the first time, at 300 K by ellipsometric measurements for the cubic CdS epilayers. Also, the energy band gap was determined by the transmittance spectra of the free-standing film, and the results were compared with the E₀ structure obtained by SE measurement.     

An alternative interpretation of the optical spectra for Fe-doped KTaO3 crystals

In this paper, the excitation spectrum and luminescence at 14 569, 17 225, 18 829 and 14 659 cm^-1 for Fe³⁺ ion at the K⁺ site of KTaO₃ crystals are assigned, respectively, to the ⁶A₁(S)→⁴T₁(G), ⁴T₂(G), ⁴E₁(G)[⁴A₁(G)] and ⁴T₁(G)→⁶A₁(S) transitions rather than to the ⁶A₁(S)→⁴T₁(G), ²T₂(I), ⁴T₂(G) and ⁴T₁(G)→⁶A₁(S) transitions given in a previous paper [Bryknar et al., Radiat. Eff. Def. Solids 149(1999)51]. On the basis of this assignment, the reasonable optical spectrum parameters (in particular, the cubic field parameter Dq≈−640 cm⁻¹) are obtained. The validity of this assignment is discussed.     

Electrical and electromechanical properties of lead-potassium-yttrium-niobate ceramics—piezoelectric applications

Tungsten bronze (TB)-type oxide ceramic Pb_0.74K_0.13Y_0.13Nb₂O₆ (PKYN) has been synthesized by the standard solid state reaction method. Single phase formation, orthorhombic crystal structure was confirmed by X-ray diffraction (XRD). The substitution of Y³⁺ in Pb_0.74K_0.52Nb₂O₆ (PKN) decreased the unit cell volume and T_C=260 °C. PKYN exhibited the remnant polarization, P_r=8.5 μC/cm², and coercive field, E_c=28.71 kV/cm. Electrical spectroscopy studies were carried out over the temperature (35-595 °C) and frequency (45 Hz-5 MHz) ranges, and the charge carrier phenomenon, grain-grain boundary contribution and non-Debye-type relaxation were analyzed. The relaxation species are immobile charges in low temperature and oxygen vacancies at higher temperature. The theoretical values computed using the relations, ε′=ε_∞+sin(n(T)π/2)(a(T)/ε₀)(ω^n(T)−1); σ(ω)=σ_dc+Aωⁿ are fitted with the experimental one. The n and A parameters suggested that the charge carrier's couple with the soft mode and become mobile at T_C. The activation enthalpy, H_m=0.38 eV, has been estimated from the hopping frequency relation ω_p=ω_e exp(−H_m/k_BT). The piezoelectric constants K_t=35.4%, d₃₃=69×10⁻¹² C/N, d₃₁=−32×10⁻³ mV/N, S₁₁^E=17.8 pm²/N, etc., achieved in PKYN indicate the material is interesting for transducer applications. The activation energies from different formalisms confirmed the ionic-type conduction.     

Correlated vortex pinning in Si-nanoparticle doped MgB2

The magnetoresistivity and critical current density of well characterized Si-nanoparticle doped and undoped Cu-sheathed MgB₂ tapes have been measured at temperatures T≥28 K in magnetic fields B≤0.9 T. The irreversibility line B_irr(T) for doped tape shows a stepwise variation with a kink around 0.3 T. Such B_irr(T) variation is typical for high-temperature superconductors with columnar defects (a kink occurs near the matching field B_?) and is very different from a smooth B_irr(T) variation in undoped MgB₂ samples. The microstructure studies of nanoparticle doped MgB₂ samples show uniformly dispersed nanoprecipitates, which probably act as a correlated disorder. The observed difference between the field variations of the critical current density and pinning force density of the doped and undoped tape supports the above findings.     

Local structures and transport properties of K ions in a hollandite superstructure KxMg(8 + x)/3Sb(16 − x)/3O16

Possible local structures of K ions in the tunnel of a hollandite superstructure K_xMg_(8 + x)/3Sb_{(16 − x)/3}O₁₆ (x ≈ 1.76) were presented, and the validity of the models was confirmed by the structure refinement using single-crystal X-ray diffraction data. Additional constraint conditions were introduced in refinements so that the average structure obtained from the refinement is consistent with assumed microscopic pictures. Joint-probability density functions were calculated for specific K ions concerning the hopping process between neighboring cavities, and converted to the one-particle potentials. Three types of the energy barrier for the hopping process were seen, which were uniformly reduced applying the anharmonic atomic displacement parameters.     

Systematic study of the product((E(2_2~+)/E(2_1~+)) * B(E2)↑) through the asymmetric rotor model

A systematic study of the product((E(2_2~+)/E(2_1~+))*B(E2)↑) is carried out in the major shell space Z=50-82,N=82-126 within the framework of the asymmetric rotor model where the asymmetry parameter γ0reflects change in the nuclear structure.A systematic study of the product((E(2+)/E(2+))*B(E2)↑) with neutron number N is also discussed.The product((E(2_2~+)/E(2_1~+))*B(E2)↑) provides a direct correlation with the asymmetry parameter γ0.The effect of subshells is visible in Ba-Gd nuclei with N 82,but not in Hf-Pt nuclei with N 104.We study,for the first time,the dependency of the product((E(2_2~+)/E(2_1~+))*B(E2)↑) on the asymmetry parameterγ0.     

Isothermal reduction kinetics of nickel oxide using hydrogen: Conventional and Weibull kinetic analysis

The powder sample of nickel oxide was synthesized by sol-gel procedure. The isothermal reduction of nickel oxide using hydrogen was investigated by thermogravimetric analysis at five operating temperatures: 245, 255, 265, 275 and 300 °C. The kinetic triplet (E_a, A and f(α)) was determined using conventional and Weibull kinetic analysis. Both the kinetically procedures show that the reduction process considered can be explained with a two-step kinetic model. It is established that at lower temperatures (245 °C?T?255 °C), the reduction process considered is governed by two-parameter Šesták-Berggren autocatalytic model (first step) and at higher temperatures (T?265 °C), the reduction process is governed by Fn reaction model with different values of parameter n (second step). In this paper, the complex manner of dependence of the Weibull shape parameter (β) on temperature is established. With alterations of Weibull shape parameter from lower temperatures (β>1) to higher temperatures (β<1), it was concluded that isothermal reduction process of NiO using hydrogen can be described by a multistep reaction mechanism. These results are confirmed by the evaluated density distribution functions (ddf) of apparent activation energies (E_a), which show variations in basic characteristics at lower and higher operating temperature regions. Also, in this paper, it was shown that the shape parameter (β) of Weibull distribution function can represent the behaviour index, which indicates the kinetic pattern of the mechanism controlling the process studied.     

Optimum designs for multi-layered film structures based on the knowledge on residual stresses

Residual stresses are inevitably generated within the multi-layered film structures due to the mismatches of material properties between the adjacent layers. Using the force and moment equilibrium conditions and beam bending theory, the residual stresses in each layer can be predicted and expressed as σ_i(z) = E_i[?′ + K(z + δ)], where E_i is the elastic modulus of the layer, ?′ the strain due to the in-plane force resulting from the misfit strain, K(z + δ) characterizes the bending contribution. For a bilayer system, the expression of the residual stress in the film is relatively simple. If the each layer thickness is much less than the substrate thickness, Stoney's equation will be derived. The assumption of a constant elastic modulus throughout the system is only applicable when the film and the substrate thickness ratio is less than 0.1. Specific analyses are performed for the thermal stresses in ZrO₂/NiCoCrAlY thermal barrier coatings (TBCs) to illustrate the implementation of the analytical model. Moreover, the effects of single interlayer and graded interlayer inserted between the metallic layer and the ceramic layer on the residual stress distributions in TBCs are investigated. Additionally, the zero-deflection design is also discussed for typically duplex-layer TBC system.     

Intrinsic coercivities of molecular beam epitaxy grown single-crystal Ni films on Ag buffer layer

Single-crystal Ni films were made by the molecular beam epitaxy (MBE) method on Si(1 0 0) and Si(1 1 0) substrates, respectively, with an 100 Å thick Ag buffer layer. The growth temperature T_S was 270 °C, and the film thickness t was 500 Å. From reflection high-energy electron diffraction (RHEED) patterns, the crystalline symmetries of the two films are clear and as expected. Intrinsic coercivities, H_C(1 0 0) and H_C(1 1 0), are plotted as a function of the angle of rotation ? around the crystal axes [1 0 0] and [1 1 0], respectively. The results show that both H_C(1 0 0) and H_C(1 1 0) exhibit mixed features of the crystalline (K_C) and the induced uniaxial magnetic (K_u) anisotropies. K_u is the magneto-elastic energy, due to lattice mismatch at the Ni/Ag interface. Moreover, the crystalline anisotropy fields, H_K(1 0 0) and H_K(1 1 0), and the induced anisotropy filed, H_u, can be calculated as a function of ?, respectively. Then, each H_C curve is fitted by the equation: H_C = H_o + H_K + H_u, where H_o is the isotropic pinning field. Meanwhile, domain structures were examined by the Bitter method, using Ferrofluid 707. On the Ni(1 0 0) film, we observed the charged cross-tie walls, and on the Ni(1 1 0) film, the un-charged Bloch walls.     

Calculated influence of work function on SE escape probability and Secondary Electron Emission yield

The influence of changes of the work function, ?, or electron affinity, χ, on the escape probability, A, of Secondary Electrons, SE, is derived from their angular and energy distributions, respectively ∂δ/∂α and ∂δ/∂E_k. Based on the evaluation of the spectral distribution of inner SEs, the present approach quantifies the dominant role of potential barrier on the SE emission and its change with surface treatments or thin film deposits. For instance it is shown that a 1 eV-increase of ? for Au leads to a decrease of A, and then of SE emission yield, δ, of about 50% while a 0.4 eV-increase of χ for potassium chloride induces a decrease of a factor 4 for A and then for the SEE yield δ. These results are summarized by empirical expressions of form A/A° = (?/?°)⁻³ for Au and A/A° =(χ/χ°)^−3/2 for KCl. Applied here to an insulating sample and to a metal, the present approach may be easily transposed to any kind of material of known Fermi energy and work function, metals, or known affinity, semiconducting and insulating samples. The large SEE yield values of inorganic insulators relative to that of metals are explained by larger values of their escape probability A - KCl: A° ∼ 25% for χ° = 0.6 eV; Au: A° ∼ 4% for ?° = 3.5 eV - combined to larger SE attenuation lengths and despite a less SE generation factor. This approach underlines the significant role of A on the large deviations between SEEY data as reported in literature and a strategy combining in situ δ and ? measurements is suggested to partly compensate the corresponding dispersion of experimental results. The present approach may be transposed to other energetic projectiles such as X-rays or ions and some practical consequences related to Scanning Electron Microscopy, mechanisms of contamination and crystalline contrasts, are pointed out.     

A kinetic study of the thermal decomposition process of potassium metabisulfite: Estimation of distributed reactivity model

The thermal decomposition kinetics of potassium metabisulfite was studied by thermogravimetric (TG) and differential thermogravimetric (DTG) techniques using non-isothermal experiments. The apparent activation energy (E_a) is determined using the differential (Friedman) isoconversional method. The results of the Friedman's isoconversional analysis of the TG data suggests that the investigated decomposition process follows a single-step reaction and the observed apparent activation energy was determined as 122.4±2.1 kJ mol⁻¹. A kinetic rate equation was derived for the decomposition process of potassium metabisulfite with contracting area model, f(α)=2(1−α)^1/2, which is established using the Malek's kinetic procedure. The value of pre-exponential factor (A) is also evaluated and was found to be A=1.37×10¹² min⁻¹. By applying the Miura's procedure the distributed reactivity model (DRM) for investigated decomposition process was established. From the dependence α versus E_a, the experimental distribution curve of apparent activation energies, f(E_a), was estimated. By applying the non-linear least-squares analysis, it was found that the Gaussian distribution model (with distribution parameters E₀=121.3 kJ mol⁻¹ and σ=1.5 kJ mol⁻¹) represents the best reactivity model for describing the investigated process. Using the Miura's method, the A values were estimated at five different heating rates and the average A values are plotted against E_a. The linear relationship between the A and E_a values was established (compensation effect). Also, it was concluded that the E_a values calculated by the Friedman's method and estimated distribution curve, f(E_a), are correct even in the case when the investigated decomposition process occurs through the single-step reaction mechanism.     

Influence of Pr-doping on structural, electronic transport, magnetic properties of perovskite molybdates Sr1−xPrxMoO3 (0≤x≤0.15)

The effect of Pr-doping on structural, electronic transport, magnetic properties in perovskite molybdates Sr_1−xPr_xMoO₃ (0≤x≤0.15) has been investigated. The Pr-doping at Sr-site does not change the space group of the samples, but decreases the lattice parameter a. The magnitude of resistivity ρ increases initially (x≤0.08) and then decreases with further increasing Pr-doping level x and ρ(T) behaves as T² and T dependence in the low-temperature range blow T* and high-temperature range of 150 K<T<350 K, related to the electron-electron (e-e) and electron-phonon (e-ph) scattering, respectively. The magnetic susceptibility χ value of the sample increases with increasing x and the χ(T) curve for all samples can be well described by the model of exchange-enhanced paramagnetism. The specific heat magnitude in the low-temperature region increases with increasing Pr-doping level. The specific heat value agrees with the classical Dulong-Petit phonon specific heat, C_cl=3k_BrN_A=124.7 J/mol K in the high-temperature region and the temperature dependence of the specific heat can be well described by the formula C_p(T)/T=γ_e+β_pT² in the low-temperature range. These behaviors can be explained by the competition between the increase in the density of state (DOS) at Fermi energy level and the disorder effect due to Pr-doping.     

Calculation of the surface energy of bcc transition metals by using the second nearest-neighbor modified embedded atom method

The surface energies for 24 surfaces of all bcc transition metals Fe, Cr, Mo, W, V, Nb and Ta have been calculated by using the second nearest-neighbor modified embedded atom method. The results show that, for all bcc transition metals, the order among three low-index surface energies E_(1 1 0) < E_(1 0 0) < E_(1 1 1) is in agreement with experimental results and E_(1 1 0) is also the lowest surface energy for various surfaces. So that from surface energy minimization, the (1 1 0) texture should be favorable in the bcc films. This is also consistent with experimental results. The surface energy for the other surfaces increases linearly with increasing angle between the surfaces (h k l) and (1 1 0). Therefore, a deviation of a surface orientation from (1 1 0) can be used to estimate the relative values of the surface energy.     

A theoretical study of FeCN in the Δ electronic ground state

The three-dimensional potential energy and dipole moment surfaces for the electronic ground state ⁶Δ of FeCN have been computed at the MR-SDCI + Q + E_rel/[Roos ANO (Fe), aug-cc-pVQZ (C, N)] level of theory, where MR-SDCI means ‘multi-reference single and double excitation configuration interaction’ and ANO means ‘atomic natural orbital’. Based on these potential energy and dipole moment surfaces, the spectroscopic parameters, rovibronic energies, structural parameters, vibrational transition moments, and the wavenumbers and intensities of selected rotation-vibration transitions have been calculated. The equilibrium structure is linear with r_e(Fe-C) = 2.048 Å and r_e(C-N) = 1.168 Å, and the zero-point averaged structure is bent with 〈r(Fe-C)〉₀ = 2.082 Å, 〈r(C-N)〉₀ = 1.172 Å, and 〈∠(Fe-C-N)〉₀ = 170(5)°. At all the MR-SDCI + Q and the size-extensive multi-reference averaged quadratic coupled-cluster (MR-AQCC) levels of theory, with and without relativistic correction E_rel, that were employed in the present work, ⁶Δ FeCN is predicted to be slightly more stable than ⁶Δ FeNC. For example, the energy difference between the two isomers is approximately 150 cm⁻¹ at the highest level of theory employed, MR-AQCC + E_rel/[Roos ANO (Fe), aug-cc-pVQZ (C, N)] with zero-point energy correction. The electronic structure of ⁶Δ FeCN has also been compared with that of ⁶Δ FeNC. At present, no experimental spectroscopic data are available for ⁶Δ FeCN. It is hoped that the present work will stimulate experimental investigations of this molecule.     

Ellipsometric investigation of optical constant and energy band gap of Zn1−xMnxSe/GaAs (1 0 0) epilayers

Zn_1−xMn_xSe/GaAs (1 0 0) epilayers were grown using a hot-wall epitaxy method. The spectroscopic ellipsometry was used to determine the optical dielectric constant. The obtained pseudodielectric function spectra revealed the distinct structures at energies of E₀, E₀ + Δ₀, E₁, E₁ + Δ₁, E₂ and  + Δ₀ critical points (CPs) at lower Mn composition range. These critical points were determined by analytical line-shapes fitted to numerically calculated derivatives of their pseudodielectric functions. The peak characteristics were changed with the change in Mn composition. The spectral dependence of pseudodielectric function 〈?〉 was used to obtain the fundamental energy gaps E₀ including a unique relation with Mn composition. Also, the shifting and broadening of the CPs were observed with increasing Mn composition.     

Analysis of confinement potential fluctuation and band-gap renormalization effects on excitonic transition in GaAs/AlGaAs multiquantum wells grown on (1 0 0) and (3 1 1)A GaAs surfaces

The competition between confinement potential fluctuations and band-gap renormalization (BGR) in GaAs/Al_xGa_1−xAs$\mathrm{GaAs}/{\mathrm{Al}}_x{\mathrm{Ga}}_{1-x}\mathrm{As}$ quantum wells grown on [1 0 0] and [3 1 1]A GaAs substrates is evaluated. The results clearly demonstrate the coexistence of the band-tail states filling related to potential fluctuations and the band-gap renormalization caused by an increase in the density of photogenerated carriers during the photoluminescence (PL) experiments. Both phenomena have strong influence on temperature dependence of the PL-peak energy (E_PL(T))$(E_{\mathit{PL}}(T))$. As the photon density increases, the E_PL can shift to either higher or lower energies, depending on the sample temperature. The temperature at which the displacement changes from a blueshift to a redshift is governed by the magnitude of the potential fluctuations and by the variation of BGR with excitation density. A simple band-tail model with a Gaussian-like distribution of the density of state was used to describe the competition between the band-tail filling and the BGR effects on E_PL(T).     

Conversion coefficients and E0 transitions in102, 104, 106Pd

In in-beam (p, p′) experiments, electron and γ-spectra were measured in the electron energy range of 500-1840 keV for¹⁰²Pd and¹⁰⁴Pd, and 600–1580 keV for¹⁰⁶Pd. The conversion coefficients of all transitions in this range were obtained with accuracies of about 20%, in some favourable cases 10%. Special attention was given to 0⁺′-0⁺ transitions from the two-phonon triplets to the ground states with the following results for the branching ratios 0⁺′-0⁺ (ground state) to 0⁺′-2⁺ (one-phonon state):¹⁰²Pd:T _k (E0)/T _γ (E2)<(2.1±3.6)·10^{?7 104}Pd:T _k (E0)/T _γ (E2)=(6.0±1.4)·10^{?5 106}Pd:T _k (E0)/T _γ (E2)=(6.0±2.0)·10^?4