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Controlled Way (controlled + way)
Selected AbstractsGrowth of ZnO crystals by vapour transport: Some ways to act on physical propertiesCRYSTAL RESEARCH AND TECHNOLOGY, Issue 8 2006R. Tena-Zaera Abstract Nowadays, the growth of ZnO by vapor transport in silica ampoules is generally made in presence of graphite. As it has been already shown, this means that the growth process is carried out in presence of a Zn excess. In order to control that and act, as a consequence, on the physical properties of crystals we have performed a systematic study of the growth process in a wide range of Zn excess compositions using well defined experimental conditions. As a preliminary characterization, optical absorption and electrical properties have been analyzed at room temperature. The results show how some physical properties of as-grown ZnO crystals can be changed in a controlled way by an adequate combination of different growth conditions such as graphite covering of inner ampoule walls, thermal difference between source material and crystallization zone and additional gas (composition and pressure). In this frame some post-growth annealing processes can be avoided reducing the time and cost of processes. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Polythiacrown Macro- and Gigantocycles with Chiral Diacetal CoresEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 12 2007Sarah Abramson Abstract We present a unique class of polythiacrown macro- and gigantocyclic[9] systems, consisting of ethylene 1,2-dithioglycol (ETG) to poly(ethylene thioglycol) (ETGn) bridges over one to six diacetal units of the cis -1,3,5,7-tetraoxadecalin (TOD) type. The latter is a dissymmetric, chiral moiety, incorporating a cavity with built-in high electron lone pair concentration, serving as the "core" of chiral macrocyclic host systems with good inclusion ability of ions and polar molecules. We describe two approaches: (i) the reactions of the 2,6-bis(bromomethyl)- cis -TOD podand (6) with ETG or higher ETGns (12n), in Cs2CO3 promoted processes, leading to the innate but uncontrolled formation of polythiacrown-TOD macrocycles having ETG/TOD ratios of 1:1 (7), 2:2 (8) and further 3:3,6:6 (111/m)10 macrocycles via open dithiol intermediates, and (ii) judicious preparation, using K2CO3, of oligomeric dibromide intermediates with ETGn:TOD ratios 1:2, 2:3 or 3:4 (14n/m), which led (with further ETGn) in a controlled way to the 2:2 (8n), or 3:3, 4:4 and 6:6 (11n/m) macro- and gigantocyclic systems. Altogether, the outcome of these processes depends on the relative concentrations of the reactants. Synthesis was accompanied by detailed (NMR and MS) spectroscopy. X-ray crystallographic analysis of a number of macrocycles, complemented by (MM & MD) computation, made possible valuable structural, stereochemical and conformational analysis. While sophisticated in their stereochemical features, these systems are readily prepared in enantiopure form and hold great promise of chemical reactivity in metal ion inclusion and molecular and chiral recognition.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Tuning and Transcription of the Supramolecular Organization of a Fluorescent Silsesquioxane Precursor into Silica-Based Materials through Direct Photochemical Hydrolysis,Polycondensation and MicropatterningADVANCED FUNCTIONAL MATERIALS, Issue 3 2009Xavier Sallenave Abstract A new fluorescent silsequioxane precursor with tuned optical properties and controlled aggregation properties is designed. The two cyclohexyl moieties introduced in the molecular structure allow the formation of very good quality films. The J-aggregated structure is transcribed into the solid by photoacid-catalyzed hydrolysis,polycondensation. Aggregation of the chromophores is reduced and highly fluorescent materials are obtained. The photoacid generator lies on the surface of the homogeneous layer of the sol,gel precursor. This phase separation presents several advantages, including UV protection of the chromophore and easy removal of the PAG. The first example of chemical amplification in the photolithography of the conjugated silsesquioxane precursor is demonstrated. As hydrolysis,polycondensation could be achieved in a controlled way by UV exposure, chemically amplified photolithography is achieved by irradiating a composite film (,110,nm thick) on silicon wafer by using a copper TEM grid as shadow mask. The pattern is produced uniformly on a miscroscopic scale of 3,mm, the photopatterned pixels remaining highly fluorescent. The sizes of the photolithographed pixels correspond to the sizes of the rectangular holes of the 300,×,75 mesh grid (hole: 63,<$>,<$>m,×,204,<$>,<$>m). [source] Synthetic Strategies for Hybrid Materials to Improve Properties for Optoelectronic Applications,ADVANCED FUNCTIONAL MATERIALS, Issue 14 2008Olga García Abstract We report, for the first time to the best of our knowledge, a systematic study to relate the laser action from BODIPY dyes, doped into monolithic hybrid matrices, with the synthetic protocols of the final materials prepared via sol-gel. To this aim, the influence of both the hydrolysis time, increased in a controlled way, and the nature of the neutralization agent (pyridine, 3-amino-propyltriethoxy-silane (APS), N -[3-(trimethoxysilyl)propyl]-ethylene diamine (TSPDA), and N1 -[3-(trimethoxysilyl)propyl]- diethylene triamine (TSPTA) on the laser action of PM567, incorporated into hybrid matrices based on copolymers of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA), with methyltriethoxysilane (TRIEOS) as inorganic precursor, was analyzed. The presence of the amine-modified silane TSPDA as neutralization agent, which is able at the same time to be anchored to the inorganic network enhancing the inorganic-organic compatibility through the matrix interphase, and utilization of hydrolysis times lower than 10 minutes, increased significantly the lasing efficiency and photostability of dye. The extension of this study to the laser behavior of BODIPY dyes embedded in other different hybrid materials based on hydrolyzed-condensed copolymers of MMA with 3-(trimethoxysilyl)propyl methacrylate (TMSPMA) in a 1/1 volumetric proportion, validates the generalization of the above conclusions, which provide guides for the optimization of the synthesis of organic-inorganic hybrid materials with optoelectronic innovative applications independently of their composition. [source] Ab initio Emulsion Polymerization by RAFT (Reversible Addition,Fragmentation Chain Transfer) through the Addition of CyclodextrinsHELVETICA CHIMICA ACTA, Issue 8 2006Bojana Apostolovic Abstract A novel process to produce homo- and copolymers by RAFT polymerization in emulsion is presented. It is known that RAFT-controlled radical polymerization can be conducted in emulsion polymerization without disturbing the radical segregation characteristic of this process, thus leading to polymerization rates identical to those encountered in the corresponding nonliving systems. However, RAFT agents are often characterized by very low water solubility and, therefore, they diffuse very slowly from the monomer droplets, where they are initially solubilized, to the reaction loci, i.e., the polymer particles. Accordingly, when used in emulsion polymerization, they are practically excluded from the reaction. In this work, we show that cyclodextrins, well-known for their ability to form water-soluble complexes with hydrophobic molecules, facilitate the transport across the H2O phase of the RAFT agent to the polymer particles. Accordingly, chains grow through the entire process in a controlled way. This leads to the production of low-polydispersity polymers with well-defined structure and end functionalities as well as to the possibility of synthesizing block copolymers by a radical mechanism. [source] Well-defined amphiphilic graft copolymer consisting of hydrophilic poly(acrylic acid) backbone and hydrophobic poly(vinyl acetate) side chainsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2009Yaogong Li Abstract A series of well-defined amphiphilic graft copolymers containing hydrophilic poly(acrylic acid) (PAA) backbone and hydrophobic poly(vinyl acetate) (PVAc) side chains were synthesized via sequential reversible addition-fragmentation chain transfer (RAFT) polymerization followed by selective hydrolysis of poly(tert -butyl acrylate) backbone. A new Br-containing acrylate monomer, tert -butyl 2-((2-bromopropanoyloxy)methyl) acrylate, was first prepared, which can be polymerized via RAFT in a controlled way to obtain a well-defined homopolymer with narrow molecular weight distribution (Mw/Mn = 1.08). This homopolymer was transformed into xanthate-functionalized macromolecular chain transfer agent by reacting with o -ethyl xanthic acid potassium salt. Grafting-from strategy was employed to synthesize PtBA- g -PVAc well-defined graft copolymers with narrow molecular weight distributions (Mw/Mn < 1.40) via RAFT of vinyl acetate using macromolecular chain transfer agent. The final PAA- g -PVAc amphiphilic graft copolymers were obtained by selective acidic hydrolysis of PtBA backbone in acidic environment without affecting the side chains. The critical micelle concentrations in aqueous media were determined by fluorescence probe technique. The micelle morphologies were found to be spheres. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6032,6043, 2009 [source] Nitroxide-mediated homo- and block copolymerization of styrene and multifunctional acryl- and methacryl derivativesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 9 2005Meizhen Yin Abstract The ability of different alkoxyamines (I1, I2, I3, I4, and I5) to initiate controlled radical polymerization of styrene was evaluated. Among them, 2-hydroxymethyl-2-[(2-methyl-1-phenyl-propyl)-(1-phenyl-ethoxy)-amino]-propane-1,3-diol (I5) gave the highest polymerization rate of styrene, and the best control over the molecular weight and the molecular weight distribution of polystyrene. Kinetic studies confirmed that with initiator I5 the polymerization of styrene proceeded in a controlled way. The controlled radical homopolymerization of multifunctional acryl- and methacryl derivatives using initiator I5 could not be realized as demonstrated by the high polydispersities (PD) obtained. However, it was possible to polymerize multifunctional acryl- and methacryl derivatives using a polystyrene macroinitiator (Pst) and, thus, novel amphiphilic block copolymers with a narrow molecular weight distribution were obtained. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1873,1882, 2005 [source] Termination Rate Coefficients for Radical Homopolymerization of Methyl Methacrylate and Styrene at Low Conversion,MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 5 2010David R. Taylor Abstract A comprehensive and systematic study of overall termination rate coefficients, kt, in low-conversion radical (homo)polymerization of methyl methacrylate and styrene is presented. Values of kt were determined by gravimetric analysis of steady-state experiments, employing 2,2,-azoisobutyronitrile as initiator. The values delivered by this simple method were found to be in qualitative and quantitative agreement with those from more modern and sophisticated techniques for measuring kt. Accordingly, correlations for bulk, low-conversion kt as a function of temperature are given for each monomer. The effects of initiator concentration, cI, and temperature on bulk kt were studied in a controlled way for both monomers. Additionally, ethyl benzene was used as solvent in order to investigate rigorously the effect of monomer concentration, cM, on styrene kt. The trends found by these systematic studies were considered in the light of what is known about the chain-length dependence of termination. Styrene's behavior was always found to be qualitatively in accord with expectation, although the variations of kt with cI and cM were not as strong as should be the case. However its activation energy, 15,kJ,·,mol,1, is shown to be almost perfectly in agreement with theory. Methyl methacrylate, on the other hand, is recalcitrant in that its overall kt does not make manifest the chain-length dependent termination that has been directly measured by other techniques. Possible reasons for these discrepancies are discussed, as are reasons for the difference in values between kt for the two monomers. On the latter topic it is concluded likely that the chain-length dependence of termination at short chain lengths is primarily responsible for styrene having kt that is higher by a factor of about 3, with there also being a contribution that arises from styrene's slower propagation. [source] Ink-Jet Printing of Luminescent Ruthenium- and Iridium-Containing Polymers for Applications in Light-Emitting DevicesMACROMOLECULAR RAPID COMMUNICATIONS, Issue 4 2005Emine Tekin Abstract Summary: Defined films of luminescent ruthenium(II) polypyridyl-poly(methyl methacrylate) (PMMA) and iridium(III) polypyridyl-polystyrene (PS) copolymers could be prepared by ink-jet printing. The copolymers were deposited on photoresist-patterned glass substrates. Films as thin as 120 nm could be printed with a roughness of 1 to 2%. In addition, the film thickness could be varied in a controlled way through the number of droplets deposited per unit area. The topography of the ink-jet printed films was analyzed utilizing an optical profilometer. The absorbance and emission spectra were measured using fast parallel UV-vis and fluorescence plate reader. Photo of the solutions of luminescent ruthenium (left) and iridium (right) containing polymers in a glass microtiter plate (top). The subsequently prepared films using ink-jet dispensing techniques are shown below. [source] Light-Induced Demixing of Hole or Electron Transporting MoietiesMACROMOLECULAR RAPID COMMUNICATIONS, Issue 20 2004Marc Behl Abstract Summary: This paper describes the synthesis of two triphenylamine monomers (hole conducting) and one triazine monomer (electron conducting) which differ in their copolymerization parameters because of their styrene and vinyl ester nature. A blend of triphenylamine monomer and poly(ethylene glycol) and mixtures of both types of monomers (triphenylamine and triazine) were illuminated through a line mask, creating laterally modulated radicals, thus leading to lateral demixing. The experiments with mixtures of triphenylamine and triazine monomers show that the concentration of p- or n-type polymers can be modulated laterally in a controlled way. AFM measurement of line pattern formed by illuminating a mixture of monomer 2 and 3 showing the height difference between illuminated and non-illuminated areas. [source] Ion implantation induced disorder in single-crystal and sputter-deposited polycrystalline CdTe characterized by ellipsometry and backscattering spectrometryPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 5 2008P. Petrik Abstract Bulk single-crystal CdTe, sputter-deposited polycrystalline CdTe films of about 2.5 micron thickness, and single-crystal Si (c-Si) have been ion implanted using 350 keV Xe at fluences ranging from 1×1013 to 16×1013 cm,2 so as to create disorder in a controlled way from fully single-crystalline to fully amorphous material. The general purpose of the investigations is to seek a parameterization of the critical point structures and establish a database for fitting the optical properties of CdTe films having different unknown grain sizes whereby the grain size will be described in terms of an effective defect density. The polycrystalline CdTe samples were magnetron sputtered onto c-Si followed by CdCl2 and Br2 -methanol treatment to improve properties in terms of grain size and surface smoothness, respectively. The fluences for use in the ion implantation of CdTe were estimated using the SRIM (Stopping and Range of Ions in Matter) software, and cross-checked by simultaneous implantation of bulk c-Si samples. The optical properties were characterized by second derivative analysis and by a generalized critical point model. Although the damage created by 350 keV Xe in the simultaneously implanted c-Si samples, as measured by both spectroscopic ellipsometry and Rutherford backscattering/ channeling spectrometry (RBS/C), agrees well with the expectations based on the SRIM simulation, the damage created in CdTe remains at a very low level even for doses several times higher than the amorphization level estimated by simulation. The character of the dechanneling of the RBS/C spectra indicates extended defects (presumably dislocation loops). This effect was similar in both single-crystal and thin film polycrystalline CdTe, although less pronounced in thin film samples. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Experiments on single levitated particles: a novel approach for investigations of electronic properties of structured II-VI-semiconductor nanoparticles in selected environmentsPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 9 2007C. Graf Abstract A novel approach for investigations of the electronic structure of II-VI semiconductor nanoparticles in selected environments is presented. CdSe/ZnS core shell nanoparticles are dispersed in a liquid non-volatile siloxane graft/block copolymer and injected in an electrodynamic trap, where a single liquid microdroplet is stably stored under ultra high vacuum conditions. In this way, it is possible to investigate quantum dots by soft X-ray spectroscopies in a liquid environment, which is not influenced by any outer surface. NEXAFS spectra of stored nanoparticles were recorded at the Zn 2p-, S 2p-, and Cd 3d-edge by measuring X-ray excited optical luminescence or the element-selective charging current of single, trapped microdroplets. The spectra are compared to those of similar CdSe/ZnS nanoparticles, which are dispersed in a controlled way in solid silica colloids as well as to those of matrix materials. An analysis of the data reveals that the electronic structure of the ZnS shell is significantly influenced by the outer functionalization and the dispersive media whereas the electronic structure of the core is shown to be independent from the surroundings. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Electrochemically Assisted Fabrication of Metal Atomic Wires and Molecular Junctions by MCBJ and STM-BJ Methods,CHEMPHYSCHEM, Issue 13 2010Dr. Jing-Hua Tian Abstract Atomic wires (point contacts) and molecular junctions are two fundamental units in the fields of nanoelectronics and devices. This Minireview introduces our recent approaches aiming to develop versatile methods to fabricate and characterize these unique metallic and molecular structures reliably. Electrochemical methods are coupled with mechanically controllable break junction (EC-MCBJ) or scanning tunneling microscopy (STM) break junction (EC-STMBJ) methods to fabricate metallic point contacts and metal/molecule/metal junctions. With the designed electrodeposition method, the metal of interest (e.g. Au, Cu, Fe or Pd) is deposited in a controlled way on the original electrode pair, on a chip for MCBJ or on the STM tip, to make the metallic contact. Then, various metal atomic wires and molecular junctions can be fabricated and characterized systematically. Herein, we measured the quantized conductance through the construction of histograms of these metal atomic point contacts and of single molecules including benzene-1,4-dithiol (BDT), ferrocene-bisvinylphenylmethyl dithiol (Fc-VPM), 4,4,-bipyridine (BPY), 1,2-di(pyridin-4-yl)ethene (BPY-EE), and 1,2-di(pyridin-4-yl)ethane (BPY-EA). Finally, we briefly discussed the future of EC-MCBJ and EC-STM for nanoelectronics and devices, for example, for the formation of heterogeneous metal-based atomic point contacts and molecular junctions. [source] Silver Coated Platinum Core,Shell Nanostructures on Etched Si Nanowires: Atomic Layer Deposition (ALD) Processing and Application in SERSCHEMPHYSCHEM, Issue 9 2010Vladimir A. Sivakov Dr. Abstract A new method to prepare plasmonically active noble metal nanostructures on large surface area silicon nanowires (SiNWs) mediated by atomic layer deposition (ALD) technology has successfully been demonstrated for applications of surface-enhanced Raman spectroscopy (SERS)-based sensing. As host material for the plasmonically active nanostructures we use dense single-crystalline SiNWs with diameters of less than 100 nm as obtained by a wet chemical etching method based on silver nitrate and hydrofluoric acid solutions. The SERS active metal nanoparticles/islands are made from silver (Ag) shells as deposited by autometallography on the core nanoislands made from platinum (Pt) that can easily be deposited by ALD in the form of nanoislands covering the SiNW surfaces in a controlled way. The density of the plasmonically inactive Pt islands as well as the thickness of noble metal Ag shell are two key factors determining the magnitude of the SERS signal enhancement and sensitivity of detection. The optimized Ag coated Pt islands on SiNWs exhibit great potential for ultrasensitive molecular sensing in terms of high SERS signal enhancement ability, good stability and reproducibility. The plasmonic activity of the core-shell Pt//Ag system that will be experimentally realized in this paper as an example was demonstrated in numerical finite element simulations as well as experimentally in Raman measurements of SERS activity of a highly diluted model dye molecule. The morphology and structure of the core-shell Pt//Ag nanoparticles on SiNW surfaces were investigated by scanning- and transmission electron microscopy. Optimized core,shell nanoparticle geometries for maximum Raman signal enhancement is discussed essentially based on the finite element modeling. 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