Dielectric Properties Investigation of Metal–Insulator–Metal (MIM) Capacitors

This study presents the construction and dielectric properties investigation of atomic-layer-deposition Al₂O₃/TiO₂/HfO₂ dielectric-film-based metal–insulator–metal (MIM) capacitors. The influence of the dielectric layer material and thickness on the performance of MIM capacitors are also systematically investigated. The morphology and surface roughness of dielectric films for different materials and thicknesses are analyzed via atomic force microscopy (AFM). Among them, the 25 nm Al₂O₃-based dielectric capacitor exhibits superior comprehensive electrical performance, including a high capacitance density of 7.89 fF·µm⁻², desirable breakdown voltage and leakage current of about 12 V and 1.4 × 10⁻¹⁰ A·cm⁻², and quadratic voltage coefficient of 303.6 ppm·V⁻². Simultaneously, the fabricated capacitor indicates desirable stability in terms of frequency and bias voltage (at 1 MHz), with the corresponding slight capacitance density variation of about 0.52 fF·µm⁻² and 0.25 fF·µm⁻². Furthermore, the mechanism of the variation in capacitance density and leakage current might be attributed to the Poole–Frenkel emission and charge-trapping effect of the high-k materials. All these results indicate potential applications in integrated passive devices.     

金催化乙炔氢氯化的密度泛函理论研究进展

乙炔氢氯化(AH)是生产氯乙烯的主要途径之一,传统上使用高毒性的汞催化剂,因此开发无汞催化剂迫在眉睫。金(Au)催化剂是最有潜力的替代催化剂之一,然而其活性Au物种、反应物的活化过程或反应过渡态结构等催化机理仍不够清晰。密度泛函理论（DFT）在研究由Au催化AH的反应机理中发挥了极其重要的作用。本文综述了DFT对金催化剂活性位点、反应物在催化剂上的吸附性质及反应机理的研究进展。重点讨论了DFT对阳离子金和金簇催化AH反应过程的模拟计算,包括Au电子状态、其它原子掺杂及金簇尺寸和形状对催化AH反应影响的模拟。结果表明DFT模拟计算在微观分子尺度上研究反应物的吸附、反应中间体及过渡态等方面发挥了关键作用,对理解Au催化AH反应机理做出了重要贡献。     

First Organic–Inorganic Hybrid Compounds Formed by Ge-V-O Clusters and Transition Metal Complexes of Aromatic Organic Ligands

Three compounds based on Ge-V-O clusters were hydrothermally synthesized and characterized by IR, UV-Vis, XRD, ESR, elemental analysis and X-ray crystal structural analysis. Both [Cd(phen)(en)]₂[Cd₂(phen)₂V₁₂O₄₀Ge₈(OH)₈(H₂O)]∙12.5H₂O (1) and [Cd(DETA)]₂[Cd(DETA)₂]_0.5[Cd₂(phen)₂V₁₂O₄₁Ge₈(OH)₇(0.5H₂O)]∙7.5H₂O (2) (1,10-phen = 1,10-phenanthroline, en = ethylenediamine, DETA = diethylenetriamine) are the first Ge-V-O cluster compounds containing aromatic organic ligands. Compound 1 is the first dimer of Ge-V-O clusters, which is linked by a double bridge of two [Cd(phen)(en)]²⁺. Compound 2 exhibits an unprecedented 1-D chain structure formed by Ge-V-O clusters and [Cd₂(DETA)₂]⁴⁺ transition metal complexes (TMCs). [Cd(en)₃]{[Cd(η₂-en)₂]₃[Cd(η₂-en)(η₂-μ₂-en)(η₂-en)Cd][Ge₆V₁₅O₄₈(H₂O)]}∙5.5H₂O (3) is a novel 3-D structure which is constructed from [Ge₆V₁₅O₄₈(H₂O)]¹²⁻ and four different types of TMCs. We also synthesized [Zn₂(enMe)₃][Zn(enMe)]₂[Zn(enMe)₂(H₂O)]₂[Ge₆V₁₅O₄₈(H₂O)]∙3H₂O (4) and [Cd(en)₂]₂{H₈[Cd(en)]₂Ge₈V₁₂O₄₈(H₂O)}∙6H₂O (5) (enMe = 1,2-propanediamine), which have been reported previously. In addition, the catalytic properties of these five compounds for styrene epoxidation have been assessed.     

自悬浮定向流法制备纳米铜微粒及其结构表征

采用自悬浮定向流法制备金属铜纳米微粒,并用TEM,XRD和AES等分析手段研究了铜纳米微粒的形貌、粒度、结构及其表面氧化层特性。结果表明,在一定的参数条件下采用自悬浮定向流法可制备出单晶纳米铜微粒,并且通过工艺参数的调控可达到对微粒粒度的控制。     

NIEDERKOORDINIERTE PHOSPHORVERBINDUNGEN, 701 1-METALLA-2,5-DIPHOSPHA PENTA-1,3-DIENE DURCH 1,4-ADDITION VON METALLCARBONYLCYCLOPENTADIENYLHYDRIDEN AN 1,4-DIPHOSPHABUTA-1,3-DIEN

Abstract

Reactions of carbonyl cyclopentadienyl hydrides from molybdenum and tungsten with 1,4-diphosphabuta-1,3-diene yield metalla-diphospha-pentadiene with a metal-phosphorus-double bond.

Metalla-diphosphapentadiene mit einer Metall-Phosphor-Doppelbindung werden durch Umsetzung von Carbonylcyclopentadienylhydriden des Molybdäns und Wolframs mit einem 1,4-Diphospha-buta-1,3-dien erhalten.     

An Experimental Study of a Flux Modulated Solid State Metathesis Reaction

A solid state metathesis (SSM) reaction was investigated with respect to the formation of rare‐earth carbodiimides, the role of the co‐produced salt (LiCl), and the eutectic flux medium (LiCl/KCl). A SSM reaction is characterized by an exothermic reaction in which a salt (often LiCl) is coproduced. When the salt melts, it can serve as a useful medium for the crystallization of a desired product. An improved crystal growth can be observed by using an eutectic flux. However, the composition of an eutectic LiCl/KCl flux is altered when LiCl is produced during the reaction. The thermal effects concerning the endothermic melting of the flux and the exothermic ingnition of the SSM reaction may compensate each other, which is not necessarily a drawback for the reaction to proceed.     

On the redox reactions of radicals with AlIII(phthalocyaninate) pendants covalently bonded to poly(ethyleneamide). Mechanistic alterations when radicals are formed inside pockets of micelle‐like polymer aggregates

The mechanisms of the redox reactions between a polymer containing Al(III) sulfonated phthalocyanine pendants, (Al^III(^?NHS(O₂)trspc)^2?)₂, and radicals have been investigated in this work. Pulse radiolysis and photochemical methods were used for these studies. Oxidizing radicals, OH^?, HCO₃^?, (CH₃)₂COHCH₂^?, and N₃^?, as well as reducing radicals, e_aq^?, CO₂^??, and (CH₃)₂C^?OH, respectively accept or donate one electron forming pendent phthalocyanine radicals, Al^III(^?NHS(O₂)trspc ^?)^{? or 3?}. The kinetics of the redox processes is consistent with a mechanism where the pendants react with radicals formed inside aggregates of five to six polymer strands. Electron donating radicals, that is, CO₂^?? and (CH₃)₂C^?OH, produce one‐electron reduced phthalocyanine pendants that, even though they were stable under anaerobic conditions, donated charge to a Pt catalyst. While the polymer was regenerated in the Pt catalyzed processes, 2‐propanol and CO₂ were respectively reduced to propane and CO. The reaction of SO₃^?? radicals with the polymer stood in contrast with the reactions of the radicals mentioned above. A first step of the mechanism, the coordination of the SO₃^?? radical to the Al(III), was subsequently followed by the formation of a SO₃^?? ‐ phthalocyanine ligand adduct. The decay of the SO₃^?? ‐ phthalocyanine ligand adduct in a ～10² ms time domain regenerates the polymer, and it was attributed to the dimerization/disproportionation of SO₃^?? radicals escaping from the aggregates of polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

SPECTROPHOTOMETRIC STUDY OF COMPLEX FORMATION BETWEEN SOME ALKALI AND ALKALINE EARTH CATIONS AND SEVERAL CONVENTIONAL (N,N), (N,O) AND (O,O) LIGANDS IN 95% ETHANOL

Abstract

The complexation of Li⁺, Na⁺, Mg²⁺ and Ca²⁺ with 1,10-phenanthroline, 2,2′-bipyridine, 1,2-phenylenediamine, 2-aminopyridine, 8-hydroxyquinoline, catechol and ethylene glycol was studied in 95% ethanol by means of a competitive spectrophotometric method using murexide as indicator. Formation constants of 1:1 conplexes were determined. In the case of all ligands used, the stability of the complexes was found to vary in the order Mg²⁺ > Ca²⁺ > Li⁺ > Na⁺. It was found that the structure influences the formation and stability of resulting complexes. Effects of various parameters on complexation are discussed.     

A new stable porous Pr-organic framework constructed by multi-iodine-substituted aromatic polycarboxylates: Synthesis,characterization, and selective adsorption of dyes

abstract

Poly[tris(dimethylformamide)(μ3-2,4,6-triiodol-1,3,5-benzene tricarboxylic acid)-praseodymium (III)] {Pr(TIBTC)(DMF)₃}_n (1) (H₃TIBTC = 2,4,6-triiodo-1,3,5-benzene tricarboxylic acid) was synthesized by the reaction of Pr(NO₃)₃·6H₂O and H₃TIBTC at 85°C in a pyrex vial. 1 was characterized by elemental analysis, IR, UV–vis, TGA, PXRD, and atomic force microscopy analytical means. Each of the central Pr ions and the three carboxyl groups from the same ligand constitute a SBU, which is then joined by a carboxyl group to form a building block. In order to further explore the functional properties of 1, we used this compound for adsorption experiments. It is found that 1 can effectively adsorb anionic dyes in aqueous solutions. In particular, there is a good adsorption efficiency for coomassie brilliant blue R-250. Therefore, 1 shows good prospects for selective adsorption of anionic dyes from wastewater solution.