Evaluation of the initial growth of electroless deposited Co(W,P) diffusion barrier thin film for Cu metallization

The formation mechanism of electroless deposited Co(W,P) films is investigated. Co(W,P) films, containing 88-90 at% of Co and 10-12 at% of W and P, are deposited directly onto p-type Si(100) substrate via Pd wet activation. Co(W,P) initially nucleates around Pd activation sites and this is followed by a strong lateral growth. Uniform Co(W,P) thin films can be obtained after 2 min deposition. Fast immersion measurement shows that the mixed potential of Co(W,P) is −0.78 V versus Ag/AgCl electrode. XRD examination shows that the Pd layer has a domination of (111) texture and the principle microstructure of the as-deposited Co(W,P) film is the hcp phase of nano-sized ε-Co. The inelastic mean free path of diffused Cu in Co(W,P) is determined to be 7.37 Å which is significantly smaller than that (9.9 Å) in pure Co, indicating that Co(W,P) is a very effective barrier layer.     

Sequential intermediates in the base-catalyzed conversion of bis(pi-conjugated propargyl) sulfones to 1,3-dihydrobenzo- and naphtho[c]thiophene-2,2-dioxides

[reaction: see text] In a recent article, we reported on the base-catalyzed rearrangements of dipropargyl selenides, -sulfides, -sulfoxides, and -sulfones that eventually lead to polycyclic aromatic products. In the present work, we report on the first isolation and characterization of the thiophene dioxide intermediates 5b,c from a mild tandem isomerization/cyclization/aromatization of bis(pi-conjugated propargyl) sulfones. Monoallene 2b,c and diallene 3b intermediates were also identified by NMR. A kinetic study of the rearrangement of 1a-c revealed that the unusual facile tandem process is highly dependent on the nature of gamma-substitution.     

Structural analysis of electrolyte solutions for rechargeable Mg batteries by stereoscopic means and DFT calculations

We present a rigorous analysis of unique, wide electrochemical window solutions for rechargeable magnesium batteries, based on aromatic ligands containing organometallic complexes. These solutions are comprised of the transmetalation reaction products of Ph(x)MgCl(2-x) and Ph(y)AlCl(3-y) in different proportions, in THF. In principle, these reactions involve the exchange of ligands between the magnesium and the aluminum based compounds, forming ionic species and neutral molecules, such as Mg(2)Cl(3)(+)·6THF, MgCl(2)·4THF, and Ph(y)AlCl(4-y)(-) (y = 0-4). The identification of the equilibrium species in the solutions is carried out by a combination of Raman spectroscopy, multinuclear NMR, and single-crystal XRD analyses. The association of the spectroscopic results with explicit identifiable species is supported by spectral analyses of specially synthesized reference compounds and DFT quantum-mechanical calculations. The correlation between the identified solution equilibrium species and the electrochemical anodic stability window is investigated. This study advances both development of new nonaqueous solution chemistry and possible development of high-energy density rechargeable Mg batteries.     

Finding the maximum,merging, and sorting in a parallel computation model

A model for synchronized parallel computation is described in which all p processors have access to a common memory. This model is used to solve the problems of finding the maximum, merging, and sorting by p processors. The main results are: 1. Finding the maximum of n elements (1 < p ≤ n) within a depth of $\text{O(}\text{n}\text{p}\text{+}\text{log log}\text{p)}$; (optimal for $\text{p ≤}\text{n}\text{log log}\text{n}$). 2. Merging two sorted lists of length m and n (m ≤ n) within a depth of $\text{O(}\text{n}\text{p}\text{+}\text{log}\text{n)}$ for p ≤ n (optimal for $\text{p ≤}\text{n}\text{log}\text{n}$), $\text{O(}\text{log}\text{m}\text{log}\text{p}\text{n}\text{)}$ for $\text{p ≥ n(= O(k)}\text{if}\text{p = m}{}^{\mathrm{<mtext>1</mtext><mtext>k</mtext>}}\text{n, k > 1)}$. 3. Sorting n elements within a depth of $\text{O(}\text{n}\text{p}\text{log}\text{n}\text{+}\text{log}\text{n}\text{log}\text{p)}$ for p ≤ n, (optimal for $\text{p ≤}\text{n}\text{log}\text{n}$). $\text{O(}\text{log}{}^2\text{n}\text{log}\text{p}\text{n}\text{) +}\text{log}\text{n)}$ for $\text{p ≥ n (= O(k}\text{log}\text{n)}\text{if}\text{p = n}{}^{\mathrm{<mtext>1+</mtext><mtext>1</mtext><mtext>k</mtext>}}\text{, k > 1)}$. The depth of O(klogn) for $\text{p = n}{}^{\mathrm{<mtext>1+</mtext><mtext>1</mtext><mtext>k</mtext>}}$ processors was also achieved by Hirschberg (Comm. ACM21, No. 8 1978, 657–661) and Preparata IEEE Trans ComputersC-27 (July 1978), 669–673). Our algorithm is substantially simpler. All the elementary operations including allocation of processors to their jobs are taken into account in deriving the depth complexity and not only comparisons.     

Fast canonization of circular strings

A circular string A = (a₁,…,a_n) is a string that has n equivalent linear representations A_i = a_i,…,a_n,a₁,…,a_i?1 for i = 1,…,n. The a_i's are assumed to be well ordered. We say that A_i < A_j if the word a_i…a_na₁…a_i?1 precedes the word a_j…a_na₁…a_j?1 in the lexicographic order, A_i ? A_j if either A_i < A_j or A_i = A_j. A_i0 is a minimal representation of A if A_i0 ? A_i for all 1 ≤ i ≤ n. The index i₀ is called a minimal starting point (m.s.p.). In this paper we discuss the problem of finding m.s.p. of a given circular string. Our algorithm finds, in fact, all the m.s.p.'s of a given circular string A of length n by using at most $\text{n + ?}\text{d}\text{2}\text{?}$ comparisons. The number d denotes the difference between two successive m.s.p.'s (see Lemma 1.1) and is equal to n if A has a unique m.s.p. Our algorithm improves the result of 3n comparisons given by K. S. Booth. Only constant auxiliary storage is used.     

Growth of Au/Ag nanowires in thin surfactant solution films: an electron microscopy study

The surfactant templated gold-silver nanowire growth process in a thin solution film was probed by cryo-transmission electron microscopy (cryo-TEM). The increasing surfactant concentration upon film drying appears to induce phase transformations in the film and form a liquid crystalline template for the nanowires growth. High-resolution transmission electron microscopy (HRTEM) and electron holography revealed that the nanowires were polycrystalline with some preferred crystallite orientations and had a roughly cylindrical cross-section. Further improvement of the technique may lead to highly ordered metal nanowire arrays within the surfactant matrix similar to the closely related mesoporous materials.     

The reactivity of quaternary ammonium- versus potassium-fluorides supported on metal oxides: paving the way to an instantaneous detoxification of chemical warfare agents

The reactions of the chemical warfare agents (CWAs) 2,2'-dichloroethyl sulfide (HD), O-ethyl S-2-(diisopropylamino)-ethyl methylphosphonothioate (VX) and isopropyl methylphosphonofluoridate (GB) with various metal oxide-supported quaternary ammonium fluorides (QAF) and/or potassium fluoride (KF) reagents are described. These active sorbents, which were prepared by a modified procedure, include alumina, silica and titania, enriched with "available" (not bound to the surface) fluoride ions. Alumina-based fluoride reagents were found to be more active than their silica or titania counterparts. QAF/Al(2)O(3) reagents, compared to KF/Al(2)O(3), exhibit an exceptional reactivity toward HD, as demonstrated both in reaction rates and product identity. For example, with TBAF, t(1/2) is 15 min for the formation of the elimination product divinyl sulfide (DVS), while with KF, t(1/2) is 10 h for the formation of the hydrolysis product thiodiglycol (TDG). On the other hand, both sorbents reacted similarly against the nerve agents GB or VX. In order to increase the "available" fluoride content on the solid surface, the mixed active sorbent TBAF/KF/Al(2)O(3) (20/20/60) was developed. On this powder, all three CWAs were degraded instantaneously at the low loading of 1 wt% (t(1/2) < 2 min) and rapidly at the higher loadings of 5-10 wt% (t(1/2) of minutes scale). We assume that the relatively large amount of inorganic fluoride (KF) acts synergistically as a reservoir for the more reactive organic fluorides (TBAF). Moreover, the alumina surface hydroxyl groups may also operate as a water reservoir for the hydrolysis of VX or GB. Therefore, TBAF/KF/Al(2)O(3) might be considered as a promising destructive sorbent for CWAs.     

Determining the relationship between tree-stem respiration and CO2 efflux by δO2/Ar measurements

Respiration in forest tree stems is an important component of the global carbon cycle. This respiration is traditionally estimated by measurements of the CO(2) efflux from the stem. However, recent studies have suggested that movement of CO(2) in the transpiration stream causes large errors in the respiration estimated by the CO(2) efflux. Here we demonstrate a new approach for determining the ratio of respiration to CO(2) efflux, which is based on specially designed chambers, and combined CO(2) and O(2) measurements. The high accuracy O(2) measurement is performed by mass spectrometric measurement of the O(2)/Ar ratio. Testing the method gave repeatable results which point that in some conditions up to 40% of the respired CO(2) can be carried away from the site of respiration.