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Adhesion/Diffusion Barrier Layers for Copper Integration: Carbon-Silicon Polymer Films and Tantalum Substrates

Description: The Semiconductor Industry Association (SIA) has identified the integration of copper (Cu) with low-dielectric-constant (low-k) materials as a critical goal for future interconnect architectures. A fundamental understanding of the chemical interaction of Cu with various substrates, including diffusion barriers and adhesion promoters, is essential to achieve this goal. The objective of this research is to develop novel organic polymers as Cu/low-k interfacial layers and to investigate popular barrier candidates, such as clean and modified tantalum (Ta) substrates. Carbon-silicon (C-Si) polymeric films have been formed by electron beam bombardment or ultraviolet (UV) radiation of molecularly adsorbed vinyl silane precursors on metal substrates under ultra-high vacuum (UHV) conditions. Temperature programmed desorption (TPD) studies show that polymerization is via the vinyl groups, while Auger electron spectroscopy (AES) results show that the polymerized films have compositions similar to the precursors. Films derived from vinyltrimethyl silane (VTMS) are adherent and stable on Ta substrates until 1100 K. Diffusion of deposited Cu overlayers is not observed below 800 K, with dewetting occurred only above 400 K. Hexafluorobenzene moieties can also be incorporated into the growing film with good thermal stability. Studies on the Ta substrates demonstrate that even sub-monolayer coverages of oxygen or carbide on polycrystalline Ta significantly degrade the strength of Cu/Ta chemical interactions, and affect the kinetics of Cu diffusion into bulk Ta. On clean Ta, monolayer coverages of Cu will de-wet only above 600 K. A partial monolayer of adsorbed oxygen (3L O2 at 300 K) results in a lowering of the de-wetting temperature to 500 K, while saturation oxygen coverage (10 L O2, 300 K) results in de-wetting at 300 K. Carbide formation also lowers the de-wetting temperature to 300 K. Diffusion of Cu into the Ta substrate at 1100 K occurs only after a 5-minute induction period. This induction period increases ...
Date: December 1999
Creator: Chen, Li

Analysis of Acid Gas Emissions in the Combustion of the Binder Enhanced d-RDF by Ion Chromatography

Description: Waste-to-energy has become an attractive alternative to landfills. One concern in this development is the release of pollutants in the combustion process. The binder enhanced d-RDF pellets satisfy the requirements of environmental acceptance, chemical/biological stability, and being storeable. The acid gas emissions of combusting d-RDF pellets with sulfur-rich coal were analyzed by ion chromatography and decreased when d-RDF pellets were utilized. The results imply the possibility of using d-RDF pellets to substitute for sulfur-rich coal as fuel, and also substantiate the effectiveness of a binder, calcium hydroxide, in decreasing emissions of SOx. In order to perform the analysis of the combustion sample, sampling and sample pretreatment methods prior to the IC analysis and the first derivative detection mode in IC are investigated as well. At least two trapping reagents are necessary for collecting acid gases: one for hydrogen halides, and the other for NOx and SOx. Factors affecting the absorption of acid gases are studied, and the strength of an oxidizing agent is the main factor affecting the collection of NOx and SOx. The absorption preference series of acid gases are determined and the absorption models of acid gases in trapping reagents are derived from the analytical results. To prevent the back-flushing of trapping reagents between impingers when leak-checking, a design for the sampling train is suggested, which can be adopted in sample collections. Several reducing agents are studied for pretreating the sample collected in alkali-permanganate media. Besides the recommendation of the hydrogen peroxide solution in EPA method, methanol and formic acid are worth considering as alternate reducing agents in the pretreatment of alkaline-permanganate media prior to IC analysis. The first derivative conductivity detection mode is developed and used in IC system. It is efficient for the detection and quantification of overlapping peaks as well as being applicable for non-overlapping ...
Date: August 1988
Creator: Jen, Jen-Fon

Biological Inhibitors

Description: Four isosteric series of plant growth-regulating compounds were prepared. Using an Avena sativa coleptile assay system, derivatives in series I and IV inhibited segment elongation to a greater degree than did comparable derivatives in series II and III.
Date: December 1971
Creator: Sargent, Dale Roger

Bonding Studies in Group IV Substituted n,n-dimethylanilines

Description: The purpose of the present work is to study the effects of the trimethylsilyl and trimethylgermyl substituents on the N,N-dimethylamino ring system. Both ground and excited state interactions were studied and their magnitudes determined. The experimental data were then used in conjunction with molecular orbital calculations to differentiate among, and determine the importance of, d-p bonding, hyperconjugation or polarization of the trimethylsilyl group on the ground and excited state bonding.
Date: December 1971
Creator: Drews, Michael James

Characterization of Low Barrier Hydrogen Bonds in Enzyme Catalysis: an Ab Initio and DFT Investigation

Description: Hartree-Fock, Moller-Plesset, and density functional theory calculations have been carried out using 6-31+G(d), 6-31+G(d,p) and 6-31++G(d,p) basis sets to study the properties of low-barrier or short-strong hydrogen bonds (SSHB) and their potential role in enzyme-catalyzed reactions that involve proton abstraction from a weak carbon-acid by a weak base. Formic acid/formate anion, enol/enolate and other complexes have been chosen to simulate a SSHB system. These complexes have been calculated to form very short, very short hydrogen bonds with a very low barrier for proton transfer from the donor to the acceptor. Two important environmental factors including small amount of solvent molecules that could possibly exist at the active site of an enzyme and the polarity around the active site were simulated to study their energetic and geometrical influences to a SSHB. It was found that microsolvation that improves the matching of pK as of the hydrogen bond donor and acceptor involved in the SSHB will always increase the interaction of the hydrogen bond; microsolvation that disrupts the matching of pKas, on the other hand, will lead to a weaker SSHB. Polarity surrounding the SSHB, simulated by SCRF-SCIPCM model, can significantly reduce the strength and stability of a SSHB. The residual strength of a SSHB is about 10--11 kcal/mol that is still significantly stable compared with a traditional weak hydrogen bond that is only about 3--5 kcal/mol in any cases. These results indicate that SSHB can exist under polar environment. Possible reaction intermediates and transition states for the reaction catalyzed by ketosteroid isomerase were simulated to study the stabilizing effect of a SSHB on intermediates and transition states. It was found that at least one SSHB is formed in each of the simulated intermediate-catalyst complexes, strongly supporting the LBHB mechanism proposed by Cleland and Kreevoy. Computational results on the activation energy for ...
Date: August 1999
Creator: Pan, Yongping

Chemical Equilibria in Binary Solvents

Description: Dissertation research involves development of Mobile Order Theory thermodynamic models to mathematically describe and predict the solubility, spectral properties, protonation equilibrium constants and two-phase partitioning behavior of solutes dissolved in binary solvent mixtures of analytical importance. Information gained provide a better understanding of solute-solvent and solvent-solvent interactions at the molecular level, which will facilitate the development of better chemical separation methods based upon both gas-liquid and high-performance liquid chromatography, and better analysis methods based upon complexiometric and spectroscopic methods. Dissertation research emphasizes chemical equilibria in systems containing alcohol cosolvents with the understanding that knowledge gained will be transferable to more environmentally friendly aqueous-organic solvent mixtures.
Date: August 1997
Creator: McHale, Mary E. R.

Chromatographic and Spectroscopic Studies on Aquatic Fulvic Acid

Description: High Performance Liquid Chromatography (HPLC) was used to investigate the utility of this technique for the analytical and preparative separation of components of aquatic fulvic acids (FA). Three modes of HPLC namely adsorption, anion exchange and reversed phase were evaluated. Aquatic fulvic acids were either extracted from surface water and sediment samples collected from the Southwest of the U.S., or were provided in a high purity form from the USGS. On the adsorption mode, a major fraction of aquatic fulvic acid was isolated on a semipreparative scale and subjected to Carbon-13 NMR and FAB Mass Spectroscopy. Results indicated that (1) The analyzed fraction of fulvic acid contains more aliphatic than aromatic moieties; (2) Methoxy, carboxylic acids, and esters are well-defined moieties of the macromolecule; (3) Phenolic components of the macromolecules were not detected in the Carbon-13 NMR spectrum possibly because of the presence of stable free radicals. Results of the anion exchange mode have shown that at least three types of acidic functionalities in aquatic fulvic acid can be separated. Results also indicated that aquatic fulvic acid can be progressively fractionated by using subsequent modes of HPLC. Results of reversed phase mode have shown that (1) The fractionation of aquatic fulvic acid by RP-HPLC is essentially controlled by the polarity and/or pH of the carrier solvent system; (2) Under different RP-HPLC conditions aquatic fulvic acid from several locations are fractionated into the same major components; (3) Fulvic acid extracted from water and sediment from the same site are more similar than those extracted from different sites; (4) Cationic and anionic ion pair reagents indicated the presence of amphoteric compounds within the polymeric structure of fulvic acid. Each mode of HPLC provided a characteristic profile of fulvic acid. The results of this research provided basic information on the behavior of aquatic ...
Date: August 1986
Creator: Chang, David Juan-Yuan

Combined Electrochemistry and Spectroscopy of Complexes and Supramolecules containing Bipyridyl and Other Azabiphenyl Building Blocks

Description: A group of azabiphenyl complexes and supramolecules, and their reduced and oxidized forms when possible, were characterized by cyclic voltammetry and electronic absorption spectroscopy. The oxidized and reduced species, if sufficiently stable, were further generated electrochemically inside a specially designed quartz cell with optically transparent electrode, so that the spectra of the electrochemically generated species could be taken in situ. Assignments were proposed for both parent and product electronic spectra. Species investigated included a range of Ru(II) and Pt(II) complexes, as well as catenanes and their comparents. Using the localized electronic model, the electrochemical reduction can be in most cases assigned as azabiphenyl-based, and the oxidation as transition metal-based. This is consistent with the fact that the azabiphenyl compounds have a low lying π* orbital. The electronic absorption spectra of the compounds under study are mainly composed of π —> π* bands with, in some cases, charge transfer bands also.
Date: August 1995
Creator: Yang, Lei

Computational Studies of C–H/C–C Manipulation Utilizing Transition Metal Complexes

Description: Density Functional Theory (DFT) is an effective tool for studying diverse metal systems. Presented herein are studies of a variety of metal systems, which can be applied to accomplish transformations that are currently difficult/impossible to achieve. The specific topics studied utilizing DFT include: 1) C–H bond activation via an Earth-abundant transition metal complex, 2) C–H bond deprotonation via an alkali metal superbase, 3) and amination/aziridination reactions utilizing a CuI reagent. Using DFT, the transformation to methanol (CH3OH) from methane (CH4) was examined. The transition metal systems studied for this transformation included a model FeII complex. This first-row transition metal is an economical, Earth-abundant metal. The ligand set for this transformation includes a carbonyl ligand in one set of complexes as well as a phosphite ligand in another. The 3d Fe metal shows the ability to convert alkyls/aryls to their oxidized counterpart in an energetically favorable manner. Also, “superbasic” alkali metal amides were investigated to perform C—H bond cleavage. Toluene was the substrate of interest with Cs chosen to be the metal of interest because of the highly electropositive nature of this alkali metal. These highly electrophilic Cs metal systems allow for very favorable C—H bond scission with a toluene substrate. Finally, the amination and aziridination of C–H and C=C bonds, respectively, by a CuI reagent was studied. The mechanism was investigated using DFT calculations. Presently, these mechanisms involving the use of coinage metals are debated. Our DFT simulations shed some insight into how these transformations occur and ultimately how they can be manipulated.
Date: May 2015
Creator: Pardue, Daniel B.

Computational Studies of Selected Ruthenium Catalysis Reactions.

Description: Computational techniques were employed to investigate pathways that would improve the properties and characteristics of transition metal (i.e., ruthenium) catalysts, and to explore their mechanisms. The studied catalytic pathways are particularly relevant to catalytic hydroarylation of olefins. These processes involved the +2 to +3 oxidation of ruthenium and its effect on ruthenium-carbon bond strengths, carbon-hydrogen bond activation by 1,2-addition/reductive elimination pathways appropriate to catalytic hydrogen/deuterium exchange, and the possible intermediacy of highly coordinatively unsaturated (e.g., 14-electron) ruthenium complexes in catalysis. The calculations indicate a significant decrease in the Ru-CH3 homolytic bond dissociation enthalpy for the oxidation of TpRu(CO)(NCMe)(Me) to its RuIII cation through both reactant destabilization and product stabilization. This oxidation can thus lead to the olefin polymerization observed by Gunnoe and coworkers, since weak RuIII-C bonds would afford quick access to alkyl radical species. Calculations support the experimental proposal of a mechanism for catalytic hydrogen/deuterium exchange by a RuII-OH catalyst. Furthermore, calculational investigations reveal a probable pathway for the activation of C-H bonds that involves phosphine loss, 1,2-addition to the Ru-OH bond and then reversal of these steps with deuterium to incorporate it into the substrate. The presented results offer the indication for the net addition of aromatic C-H bonds across a RuII-OH bond in a process that although thermodynamically unfavorable is kinetically accessible. Calculations support experimental proposals as to the possibility of binding of weakly coordinating ligands such as dinitrogen, methylene chloride and fluorobenzene to the "14-electron" complex [(PCP)Ru(CO)]+ in preference to the formation of agostic Ru-H-C interactions. Reactions of [(PCP)Ru(CO)(1-ClCH2Cl)][BAr'4] with N2CHPh or phenylacetylene yielded conversions that are exothermic to both terminal carbenes and vinylidenes, respectively, and then bridging isomers of these by C-C bond formation resulting from insertion into the Ru-Cipso bond of the phenyl ring of PCP. The QM/MM and DFT calculations on full complexes ...
Date: December 2007
Creator: Barakat, Khaldoon A.

Computational Study of Small Molecule Activation via Low-Coordinate Late First-Row Transition Metal Complexes

Description: Methane and dinitrogen are abundant precursors to numerous valuable chemicals such as methanol and ammonia, respectively. However, given the robustness of these substrates, catalytically circumventing the high temperatures and pressures required for such transformations has been a challenging task for chemists. In this work, computational studies of various transition metal catalysts for methane C-H activation and N2 activation have been carried out. For methane C-H activation, catalysts of the form LnM=E are studied, where Ln is the supporting ligand (dihydrophosphinoethane or β-diketiminate), E the activating ligand (O, NCH3, NCF3) at which C-H activation takes place, and M the late transition metal (Fe,Co,Ni,Cu). A hydrogen atom abstraction (HAA) / radical rebound (RR) mechanism is assumed for methane functionalization (CH4 à CH3EH). Since the best energetics are found for (β-diket)Ni=O and (β-diket)Cu=O catalysts, with or without CF3 substituents around the supporting ligand periphery, complete methane-to-methanol cycles were studied for such systems, for which N2O was used as oxygen atom transfer (OAT) reagent. Both monometallic and bimetallic OAT pathways are addressed. Monometallic Fe-N2 complexes of various supporting ligands (LnFe-N2) are studied at the beginning of the N2 activation chapter, where the effect of ligand on N2 activation in end-on vs. side-on N2 isomers is discussed. For (β-diket)Fe-N2 complexes, the additional influence of diketiminate donor atom (N(H) vs. S) is briefly addressed. The remainder of the chapter expands upon the treatment of β-diketiminate complexes. First, the activation and relative stabilities of side-bound and end-bound N2 isomers in monometallic ((β-diket)M-N2) and bimetallic ((β-diket)M-N2-M(β-diket)) first row transition metal complexes are addressed. Second, the thermodynamics of H/H+/H- addition to (β-diket)Fe-bound N2, followed by subsequent H additions up to release of ammonia, is discussed, for which two mechanisms (distal and alternating) are considered. Finally, the chapter concludes with partial distal and alternating mechanisms for H addition to N2 ...
Date: May 2010
Creator: Pierpont, Aaron

Computer Simulations of Dilute Polymer Solutions: Chain Overlaps and Entanglements

Description: Chain conformations and the presence of chain overlaps and entanglements in dilute polymer solutions have been analyzed. The fundamental problem of existence of chain overlaps in dilute solutions is related to the drag reduction phenomenon (DR). Even though DR occurs in solutions with the concentration of only few parts per million (ppm), some theories suggest that entanglements may play an important role in DR mechanism. Brownian dynamics technique have been used to perform simulations of dilute polymer solutions at rest and under shear flow. A measure of interchain contacts and two different measures of entanglements have been devised to evaluate the structure of polymer chains in solution. Simulation results have shown that overlaps and entanglements do exist in static dilute solutions as well as in solutions under shear flow. The effect of solution concentration, shear rate and molecular mass have been examined. In agreement with the solvation theory of DR mechanism, simulation results have demonstrated the importance of polymer + polymer interactions in dilute solutions.
Date: August 1996
Creator: Drewniak, Marta

The Development of Predictive Models for the Acid Degradation of Chrysotile Asbestos

Description: The purpose of this study was to determine the factors affecting the acid degradation of chrysotile asbestos (Mg_3Si_2O_5(OH_4)) . Millions of tons of asbestos have found use in this country as insulative or ablative material. More than 95 percent of the asbestos in use is of the chrysotile variety. The remaining 5 percent is composed of various types of fibrous amphiboles. The inhalation of asbestos can lead to several diseases in humans. Asbestosis, lung cancer and mesothelioma are the most common afflictions associated with asbestos inhalation, and they may occur up to 40 years after the initial exposure. It has previously been reported that if more than 50 percent of the magnesium is removed from a chrysotile sample its carcinogenicity is reduced to nil. Several inorganic acids were studied to determine their ability to leach magnesium from chrysotile. It was found that the ability to leach magnesium was dependent upon the acidic anion in addition to the concentration of the acid. The ordering of the efficiency of the acids in their ability to remove magnesium from chrysotile was found to be HCl > H_2SO_4 > H_3PO_4 > HNO_3. Predictive equations were developed to allow the calculation of the amount of magnesium removed under various acid concentrations as a function of time and acid species. The effects of temperature and dissolved spectator cations upon the degradation process were also examined. There was no major effect on the amount of magnesium removed as a function of spectator cation concentration. An infrared method was also developed to allow the determination of the percent degradation of a chrysotile sample directly. The shifts in the positions of three silicate stretching peaks (1068 cm^-1, 948 cm^-1 and 715 cm^-1) and one magnesium oxygen stretching peak (415 cm"1) as a function of the percent magnesium removed were ...
Date: May 1993
Creator: Ingram, Kevin D. (Kevin Dean)

Diffusion Barriers/Adhesion Promoters. Surface and Interfacial Studies of Copper and Copper-Aluminum Alloys

Description: The focus of this research is to study the interaction between copper and the diffusion barrier/adhesion promoter. The behavior of copper sputter-deposited onto sputter-cleaned tantalum nitride is investigated. The data show that copper growth on tantalum nitride proceeds with the formation of 3-D islands, indicating poor adhesion characteristics between copper and Ta0.4N. Post-annealing experiments indicate that copper will diffuse into Ta0.4N at 800 K. Although the data suggests that Ta0.4N is effective in preventing copper diffusion, copper's inability to wet Ta0.4N will render this barrier ineffective. The interaction of copper with oxidized tantalum silicon nitride (O/TaSiN) is characterized. The data indicate that initial copper depositions result in the formation a conformal ionic layer followed by Cu(0) formation in subsequent depositions. Post-deposition annealing experiments performed indicate that although diffusion does not occur for temperatures less than 800 K, copper "de-wetting" occurs for temperatures above 500 K. These results indicate that in conditions where the substrate has been oxidized facile de-wetting of copper may occur. The behavior of a sputter-deposited Cu0.6Al0.4 film with SiO2 (Cu0.6Al0.4/SiO2) is investigated. The data indicate that aluminum segregates to the SiO2 interface and becomes oxidized. For copper coverages less than ~ 0.31 ML (based on a Cu/O atomic ratio), only Cu(I) formation is observed. At higher coverages, Cu(0) is observed. These data are in contrast with the observed behavior of copper metal deposited onto SiO2 (Cu/SiO2). The data for Cu/SiO2 show that copper does not wet SiO2 and forms 3-D nuclei. Furthermore, post-annealing experiments performed on Cu0.6Al0.4/SiO2 show that neither de-wetting nor diffusion of copper occurs for temperatures up to 800 K, while Cu diffusion into SiO2 occurs ~ 600 K. These data indicate that aluminum alloyed with copper at the SiO2 interface serves as an effective adhesion promoter and thermal diffusion barrier.
Date: August 2000
Creator: Shepherd, Krupanand Solomon

Diphosphine Ligand Activation Studies with Organotransition-Metal Compounds

Description: Thermolysis of CoRu(CO)7(m -PPh2) (1) in refluxing 1,2-dichloroethane in the presence of the diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) furnishes the new mixed-metal complexes CoRu(CO)4(μ -P-P)(μ -PPh2) [where P-P = bma (3); bpcd (6)], along with trace amounts of the known complex CoRu(CO)6(PPh3)(μ -PPh2) (4). The requisite pentacarbonyl intermediates CoRu(CO)5(μ -P-P)(μ -PPh2) [where P-P = bma (2); bpcd (5)] have been prepared by separate routes and studied for their conversion to CoRu(CO)4(μ -P-P)(μ -PPh2). The complexes 2/3 and 5/6 have been isolated and fully characterized in solution by IR and NMR spectroscopy. The kinetics for the conversion of 2→3 and of 5→6 were measured by IR spectroscopy in chlorobenzene solvent. On the basis of the first-order rate constants, CO inhibition, and the activation parameters, a mechanism involving dissociative CO loss as the rate-limiting step is proposed. The solid-state structure of CoRu(CO)4(μ -bma)(μ -PPh2) (3) reveals that the two PPh2 groups are bound to the ruthenium center while the maleic anhydride π bond is coordinated to the cobalt atom. Thermolysis of the cluster Ru3(CO)12 with the bis(phosphine)hydrazine ligand (MeO)2PN(Me)N(Me)P(OMe)2 (dmpdmh) in toluene at 75°C furnishes the known clusters Ru4(CO)12[μ -N(Me)N(Me)] (9) and Ru3(CO)11[P(OMe)3] (10), in addition to the new cluster Ru3(CO)10(dmpdmh) (8) and the phosphite-tethered cluster Ru3(CO)9[μ -P(OMe)3] (11). The simple substitution product Ru3(CO)10(dmpdmh), a logical intermediate to clusters 9-11, was synthesized by treating Ru3(CO)12 and dmpdmh with Me3NO in CH2Cl2 at room temperature, and independent thermolysis reactions using cluster 8 were shown to yield clusters 9-11. The tetrahedrane cluster FeCo2(CO)9(μ3-S) reacts with the redox-active ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) to give the disubstituted cluster FeCo2(CO)7(bpcd)(μ3-S) as the sole product. This diphosphine-substituted cluster contains a cobalt-bound, chelating bpcd ligand. The solid-state structure has been unequivocally established by X-ray diffraction analysis. Cyclic voltammetric studies on FeCo2(CO)7(bpcd)(μ3-S) reveal the presence of two quasireversible ...
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Date: December 2000
Creator: Wang, Jiancheng

Discontinuous Thermal Expansions and Phase Transformations in Crystals at Higher Temperatures

Description: The purpose of this investigation is to make more detailed studies of transformations. Fourteen compounds have been examined by high temperature X-ray diffraction for this purpose. The investigations have been carried out in such a way as to reveal: 1. the existence of transformations, 2. the influence of polarizability on thermal expansion, 3. the anisotropy of expansion, and 4. the discontinuity of thermal expansion.
Date: 1967
Creator: Hsu, Yuan Tsun