10.1007/s10973-006-8123-z

This work presents preparation and thermal characterization of three novel organomercurials: Hg₂(CF₃COCHCOCF₃)₂-μ₂-(CF₃COCCOCF₃)μ₂(CF₃C(OH)₂CH₂C(OH)₂CF₃) (I), Hg₂(CF₃COCHCOCF₃)₂-μ₂-(CF₃COCCOCF₃) (II) and Hg₂(CH₃COCHCOCF₃)₂-μ₂-(CH₃COCCOCF₃) (III) which means that they contain at least one direct mercury-to-carbon bond among the carbonyl groups of β-diketone molecules which are capable for chelating of metal ions. IR-spectra support the conclusion that mercury is most probably bound to the γ-carbon of fluorinated derivatives of acetylacetone and is not chelated through oxygen in any of the isolated compounds. The thermal decomposition of mercurated hexafluoro- and trifluoroacetylacetone in nitrogen occurs in a few steps. Each step was identified and studied by simultaneous DTA/TG analyzer. On the basis of dynamic heating experiments by TG applying Flynn-Wall method the activation energy for each of them was determined.     

Multiphysics Simulation Combining Large-Eddy Simulation,Wall Heat Conduction and Radiative Energy Transfer to Predict Wall Temperature Induced by a Confined Premixed Swirling Flame

A multi-physics simulation combining large-eddy simulation, conjugate heat transfer and radiative heat transfer is used to predict the wall temperature field of a confined premixed swirling flame operating under atmospheric pressure. The combustion model accounts for the effect of enthalpy defect on the flame structure whose stabilization is here sensitive to the wall heat losses. The conjugate heat transfer is accounted for by solving the heat conduction within the combustor walls and with the Hybrid-Cell Neumann-Dirichlet coupling method, enabling to dynamically adapt the coupling period. The latter coupling procedure is enhanced to determine statistics (mean, RMS, \(\ldots \)) in a permanent regime accurately and efficiently thanks to an acceleration technique which is derived and validated. The exact radiative heat transfer equation is solved with an advanced Monte Carlo method with a local control of the statistical error. The coupled simulation is carried out with or without accounting for radiation. Excellent results for the wall temperature are achieved by the fully coupled simulation which are then further analyzed in terms of radiative effects, global energy budget and fluctuations of wall heat flux and temperature.     

Modal resonant ultrasound spectroscopy for ferroelastics

Recent experimental and theoretical improvements of resonant ultrasound spectroscopy (RUS) are summarized to investigate elastic constants of phases in shape memory alloys. The proposed inversion procedure, described in this work, is particularly suitable to reliable evaluation of the temperature dependence of elastic constants of low-symmetry ferroelastic materials which may be strongly elastically anisotropic and tend to exist in twinned forms. The method is applicable even for the evaluation of single-crystal elastic constants from RUS measurements on microtwinned crystals, since it involves a homogenization algorithm based on the macroscopic deformation response of the layered structure. This potentially allows performing meaningful acoustic studies on samples with a general submicron-size layered structure.     

Comparative study of ZnO layers prepared by PLD from different targets at various oxygen pressure levels

Two series of polycrystalline zinc oxide (ZnO) layers, from Zn or ZnO targets, were grown on silicon (1 1 1) substrates by pulsed laser deposition (PLD) at ambient oxygen pressure levels, stepwise increased from 1 to 35 Pa. For ablation of targets, a pulsed Nd:YAG laser was used. The structural and morphological properties of the layers were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), and secondary ion mass spectrometry (SIMS). The SEM images of ZnO layers in SE mode show a uniform granular structure and modified surface morphology, depending on oxygen pressure. The mean grain size in height and lateral directions decreases with an increase of oxygen pressure from 1 to 5 Pa, while a subsequent rise of oxygen pressure from 5 to 35 Pa will cause an increase in the grain size. The AFM measurement revealed that the surface structures of zinc oxide layers grown from different targets were similar, and the layers formed at an ambient oxygen pressure of 5 Pa exhibited the smallest values of calculated roughness and granularity. SIMS depth profiling analyses confirmed that the ZnO composition was homogenous across the layer, up to the abrupt change of chemical composition at the interface between the ZnO layer and the Si substrate.      

Acoustic spectroscopy and electrical characterization of SiO2/Si structures with ultrathin SiO2 layers formed by nitric acid oxidation

Ultrathin silicon dioxide (SiO₂) layers formed on Si substrate with nitric acid have been investigated using both acoustic deep-level transient spectroscopy (A-DLTS) and electrical methods to characterize the interface states. The set of SiO₂/Si structures formed in different conditions (reaction time, concentrations of nitric acid (HNO₃), and SiO₂ thickness [3–9 nm]) was prepared. The leakage current density was decreased by post-oxidation annealing (POA) treatment at 250°C in pure nitrogen for 1 h and/or post-metallization annealing (PMA) treatment at 250°C in a hydrogen atmosphere for 1 h. All structures of the set, except electrical investigation, current-voltage (I - V), and capacitance — voltage (C - V) measurements, were investigated using A-DLTS to find both the interface states distribution and the role of POA and/or PMA treatment on the interface-state occurrence and distribution. The evident decreases of interface states and shift of their activation energies in the structures with PMA treatment in comparison with POA treatment were observed in most of the investigated structures. The results are analyzed and discussed.      

Pulsed laser treatment of gold and black gold thin films fabricated by thermal evaporation

The effect of pulsed laser treatment of metal, and metal blacks, was studied. Gold and black gold thin films were fabricated by thermal evaporation of gold in a vacuum and nitrogen atmosphere respectively. Black gold films were grown in a nitrogen atmosphere at pressures of 200 Pa and 300 Pa. UV pulsed laser radiation (λ = 266 nm, τ = 4 ns), with fluence ranging from 1 mJ·cm⁻² to 250 mJ·cm⁻² was used for the film treatment in a vacuum and nitrogen atmosphere. The nitrogen pressure was varied up to 100 kPa. Surface structure modifications were analyzed by optical microscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM). Energy dispersive X-ray spectroscopy (EDX) was used for chemical characterization of the samples. A significant dependence of the film optical and structural properties on laser treatment conditions (laser fluence, ambient pressure and number of applied pulses) was found. The threshold for observable damage and initiation of changes of morphology for gold and black gold surfaces was determined. Distinct modifications were observed for fluences greater than 106 mJ·cm⁻² and 3.5 mJ·cm⁻² for the gold and black gold films respectively. Absorbtivity of the black gold film is found to decrease with an increase in the number of laser pulses. Microstructural and nanostructural modifications after laser treatment of the black gold film were observed. EDX analysis revealed that no impurities were introduced into the samples during both the deposition and laser treatment.      

Wet-chemical treatment and electronic interface properties of silicon solar cell substrates

On textured n-type silicon substrates for solar cell manufacturing, the relation between light trapping behavior, structural imperfections, energetic distribution of interface state densities and interface recombination losses were investigated by applying surface sensitive techniques. The field-modulated surface photovoltage (SPV), in-situ photoluminescence (PL) measurements, total hemispherical UV-NIR-reflectance measurements and electron microscopy (SEM) were employed to yield detailed information on the influence of wet-chemical treatments on preparation induced micro-roughness and electronic properties of polished and textured silicon substrates. It was shown that isotropic as well as anisotropic etching of light trapping structures result in high surface micro-roughness and density of interface states. Removing damaged surface layers in the nm range by wet-chemical treatments, the density of these states and the related interface recombination loss can be reduced. In-situ PL measurements were applied to optimise HF-treatment times aimed at undamaged, oxide-free and hydrogen-terminated substrate surfaces as starting material for subsequent solar cell preparations.      

Low-lying spectrum of the Y-string three-quark potential using hyper-spherical coordinates

We calculate the energies of three-quark states with definite permutation symmetry (i.e. of SU(6) multiplets) in the N=0, 1, 2 shells, confined by the Y-string three-quark potential. The exact Y-string potential consists of one term, the so-called three-string term, and three angle-dependent two-string terms. Due to this technical complication we treat the problem at three increasingly accurate levels of approximation: (1) the (approximate) three-string potential expanded to first order in trigonometric functions of hyper-spherical angles; (2) the (approximate) three-string potential to all orders in the power expansion in hyper-spherical harmonics, but without taking into account the transition(s) to two-string potentials; (3) the exact minimal-length string potential to all orders in a power expansion in the hyper-spherical harmonics, and taking into account the transition(s) to two-string potentials. We show the general trend of improvement of these approximations: the exact non-perturbative corrections to the total energy are of the order of one per cent, as compared with approximation (2), yet the exact energy differences between the [20,1⁺],[70,2⁺],[56,2⁺],[70,0⁺]-plets are shifted to 2:2:0.9, from the Bowler and Tynemouth separation rule 2:2:1, which is obeyed by approximation (2) at the one per cent level. The precise value of the energy separation of the first radial excitation (“Roper”) [56^′,0⁺]-plet from the [70,1⁻]-plet depends on the approximation, but does not become negative, i.e. the “Roper” remains heavier than the odd-parity [70,1⁻]-plet in all of our approximations.     

Extreme Covariant Observables for Type I Symmetry Groups

The structure of covariant observables—normalized positive operator measures (POMs)—is studied in the case of a type I symmetry group. Such measures are completely determined by kernels which are measurable fields of positive semidefinite sesquilinear forms. We produce the minimal Kolmogorov decompositions for the kernels and determine those which correspond to the extreme covariant observables. Illustrative examples of the extremals in the case of the Abelian symmetry group are given. Dedicated to Pekka J. Lahti in honor of his sixtieth birthday     

Self-Assembly of Two Isomorphous Thiocyanate Complexes of Co(II) and Ni(II) with 3-Hydroxypicolinamide

Abstract  

The synthesis, thermal and spectral characterization, and crystal structure of isomorphous thiocyanate cobalt(II) and nickel(II) complexes with 3-hydroxypicolinamide (3-OHpia), [M(C₆H₆N₂O₂)₂(NCS)₂]·2H₂O, are reported. The metal(II) ions are chelated by two cis-oriented 3-OHpia and two thiocyanate ligands in distorted octahedral geometry. The distortion within the coordination sphere is mainly imposed by formation of the chelate rings. The compounds crystallize in monoclinic space group P2/c with two symmetrically independent molecules and a = 14.4945(2) ?, b = 8.5906(1) ?, c = 16.3865(3) ?, β = 105.987(2)°, Z = 4 (1) and a = 14.4927(5) ?, b = 8.5912(3) ?, c = 16.2712(6) ?, β = 105.740(4)°, Z = 4 (2). Commonly observed supramolecular amide synthons are not robust enough to accommodate thiocyanate ions and H₂O molecules. But instead, neutral complexes are linked through hydrogen bonds leading to two different hydrogen bonding ribbon motifs involving amide moieties and H₂O molecules [C(8)R ₂²(12) along c axis] and amide moieties and thiocyanate ions [C(8)R ₂²(16) along b axis] for symmetrically related molecules labelled as 1 [Co1 (1) and Ni1 (2)] and 2 [Co2 (1) and Ni2 (2)], respectively.