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Model Development for the Catalytic Calcination of Calcium Carbonate

Description: Lime is one of the largest manufactured chemicals in the United States. The conversion of calcium carbonate into calcium oxide is an endothermic reaction and requires approximately two to four times the theoretical quantity of energy predicted from thermodynamic analysis. With the skyrocketing costs of fossil fuels, how to decrease the energy consumption in the calcination process has become a very important problem in the lime industry. In the present study, many chemicals including lithium carbonate, sodium carbonate, potassium carbonate, lithium chloride, magnesium chloride, and calcium chloride have been proved to be the catalysts to enhance the calcination rate of calcium carbonate. By mixing these chemicals with pure calcium carbonate, these additives can increase the calcination rate of calcium carbonate at constant temperatures; also, they can complete the calcination of calcium carbonate at relatively low temperatures. As a result, the energy required for the calcination of calcium carbonate can be decreased. The present study has aimed at developing a physical model, which is called the extended shell model, to explain the results of the catalytic calcination. In this model, heat transfer and mass transfer are two main factors used to predict the calcination rate of calcium carbonate. By using the extended shell model, not only the catalytic calcination but also the inhibitive calcination of calcium carbonate have been explained.
Date: December 1987
Creator: Huang, Jin-Mo

Methods Development for Simultaneous Determination of Anions and Cations by Ion Chromatography

Description: The problem with which this research is concerned is the determination of inorganic anions and cations with single injection ion chromatography. Direct detection of the separated analyte ions occurs after the analyte ions have passed through ion-exchange resins where they are separated according to their affinity for the ion-exchange resin active sites. The techniques involve the use of essentially a non-suppressed ion chromatographic system followed by a suppressed ion chromatographic system. With this system it is possible to accomplish both qualitative and quantitative determinations.
Date: May 1987
Creator: Jones, Vonda K. (Vonda Kaye)

Direct Inject Mass Spectrometry for Illicit Chemistry Detection and Characterization

Description: The field of direct inject mass spectrometry includes a massive host of ambient ionization techniques that are especially useful for forensic analysts. Whether the sample is trace amounts of drugs or explosives or bulk amounts of synthetic drugs from a clandestine laboratory, the analysis of forensic evidence requires minimal sample preparation, evidence preservation, and high sensitivity. Direct inject mass spectrometry techniques can rarely provide all of these. Direct analyte-probed nanoextraction coupled to nanospray ionization mass spectrometry, however, is certainly capable of achieving these goals. As a multifaceted tool developed in the Verbeck laboratory, many forensic applications have since been investigated (trace drug and explosives analysis). Direct inject mass spectrometry can also be easily coupled to assays to obtain additional information about the analytes in question. By performing a parallel artificial membrane assay or a cell membrane stationary phase extraction prior to direct infusion of the sample, membrane permeability data and receptor activity data can be obtained in addition to the mass spectral data that was already being collected. This is particularly useful for characterizing illicit drugs and their analogues for a biologically relevant way to schedule new psychoactive substances.
Date: May 2016
Creator: Williams, Kristina

Calcium Silicates: Glass Content and Hydration Behavior

Description: Pure, MgO doped and B2C3 doped monocalcium, dicalcium, and tricalcium silicates were prepared with different glass contents. Characterization of the anhydrous materials was carried out using optical microscopy, infrared absorption spectroscopy, and X-ray powder diffraction. The hydration of these compounds was studied as a function of the glass contents. The hydration studies were conducted at 25°C. Water/solid ratios of 0.5, 1, 10, and 16 were used for the various experiments. The hydration behavior was monitored through calorimetry, conductometry, pH measurements, morphological developments by scanning electron microscopy, phase development by X-ray powder diffraction, and percent combined water by thermogravimetry. A highly sensitive ten cell pseudo-adiabatic microcalorimeter was designed and constructed for early hydration studies. Conductometry was found to be of great utility in monitoring the hydration of monocalcium silicate and the borate doped dicalcium silicates.
Date: August 1987
Creator: Zgambo, Thomas P. (Thomas Patrick)

The Analysis of PCDD and PCDF Emissions from the Cofiring of Densified Refuse Derived Fuel and Coal

Description: The United States leads the world in per capita production of Municipal Solid Waste (MSW), generating approximately 200 million tons per year. By 2000 A.D. the US EPA predicts a 20% rise in these numbers. Currently the major strategies of MSW disposal are (i) landfill and (ii) incineration. The amount of landfill space in the US is on a rapid decline. There are -10,000 landfill sites in the country, of which only 65-70% are still in use. The Office of Technology Assessment (OTA) predicts an 80% landfill closure rate in the next 20 years. The development of a viable energy resource from MSW, in the form of densified Refuse Derived Fuel (dRDF), provides solutions to the problems of MSW generation and fossil fuel depletions. Every 2 tons of MSW yields approximately 1 ton of dRDF. Each ton of dRDF has an energy equivalent of more than two barrels of oil. At current production rates the US is "throwing away" over 200,000,000 barrels of oil a year. In order to be considered a truly viable product dRDF must be extensively studied; in terms of it's cost of production, it's combustion properties, and it's potential for environmental pollution. In 1987 a research team from the University of North Texas, in conjunction with the US DOE and Argonne National Laboratory (ANL), cofired over 550 tons of dRDF and bdRDF with a high sulfur Kentucky coal in a boiler at ANL. This work examines the emission rates of polychlorinated dioxins (PCDDs) and furans (PCDFs) during the combustion of the dRDF, bdRDF, and coal. Even at levels of 50% by Btu content of dRDF in the fuel feedstock, emission rates of PCDDs and PCDFs were below detection limits. The dRDF is shown to be an environmentally acceptable product, which could help resolve one of the ...
Date: August 1990
Creator: Moore, Paul, 1962-

Chemical and Electronic Structure of Aromatic/Carborane Composite Films by PECVD for Neutron Detection

Description: Boron carbide-aromatic composites, formed by plasma-enhanced co-deposition of carboranes and aromatic precursors, present enhanced electron-hole separation as neutron detector. This is achieved by aromatic coordination to the carborane icosahedra and results in improved neutron detection efficiency. Photoemission (XPS) and FTIR suggest that chemical bonding between B atoms in icosahedra and aromatic contents with preservation of π system during plasma process. XPS, UPS, density functional theory (DFT) calculations, and variable angle spectroscopic ellipsometery (VASE) demonstrate that for orthocarborane/pyridine and orthocarborane/aniline films, states near the valence band maximum are aromatic in character, while states near the conduction band minimum include those of either carborane or aromatic character. Thus, excitation across the band gap results in electrons and holes on carboranes and aromatics, respectively. Further such aromatic-carborane interaction dramatically shrinks the indirect band gap from 3 eV (PECVD orthocarborane) to ~ 1.6 eV (PECVD orthocarborane/pyridine) to ~1.0 eV (PECVD orthocarborane/aniline), with little variation in such properties with aromatic/orthocarborane stoichiometry. The narrowed band gap indicate the potential for greatly enhanced charge generation relative to PECVD orthocarborane films, as confirmed by zero-bias neutron voltaic studies. The results indicate that the enhanced electron-hole separation and band gap narrowing observed for aromatic/orthocarborane films relative to PECVD orthocarborane, has significant potential for a range of applications, including neutron detection, photovoltaics, and photocatalysis. Acknowledgements: This work was supported by the Defense Threat Reduction Agency (Grant No.HDTRA1-14-1-0041). James Hilfiker is also gratefully acknowledged for stimulating discussions.
Date: December 2016
Creator: Dong, Bin

Hydraulic Activity in Synthetic and Commercial Slags

Description: Slag, by itself, shows very little hydraulic activity. However, hydration is greatly accelerated by incorporation of the slag with Portland cement. This phenomenon is due to the activating role of calcium hydroxide released from the hydration of Portland cement. This study was aimed at finding other activators that will increase hydration in both synthetic and commercial slags. The effects of chemical composition and the aggregation state of the slag on the hydration process were also investigated. For the synthetic slags, the aggregation state was altered by different quenching techniques. The chemical composition was varied by synthesizing a series of slags. The degree of hydration was studied by developing a thermogravimetric analysis technique and the glass content was determined using microscopy. Minerals were determined using powder x-ray diffraction analysis.
Date: May 1982
Creator: Saad, Bahruddin bin

Determination of Solute Descriptors for Illicit Drugs Using Gas Chromatographic Retention Data and Abraham Solvation Model

Description: In this experiment, more than one hundred volatile organic compounds were analyzed with the gas chromatograph. Six capillary columns ZB wax plus, ZB 35, TR1MS, TR5, TG5MS and TG1301MS with different polarities have been used for separation of compounds and illicit drugs. The Abraham solvation model has five solute descriptors. The solute descriptors are E, S, A, B, L (or V). Based on the six stationary phases, six equations were constructed as a training set for each of the six columns. The six equations served to calculate the solute descriptors for a set of illicit drugs. Drugs studied are nicotine (S= 0.870, A= 0.000, B= 1.073), oxycodone(S= 2.564. A= 0.286, B= 1.706), methamphetamine (S= 0.297, A= 1.570, B= 1.009), heroin (S=2.224, A= 0.000, B= 2.136) and ketamine (S= 1.005, A= 0.000, B= 1.126). The solute property of Abraham solvation model is represented as a logarithm of retention time, thus the logarithm of experimental and calculated retention times is compared.
Date: August 2015
Creator: Mitheo, Yannick K.

Study of Interactions Between Diffusion Barrier Layers and Low-k Dielectric Materials for Copper/Low-k Integration

Description: The shift to the Cu/low-k interconnect scheme requires the development of diffusion barrier/adhesion promoter materials that provide excellent performance in preventing the diffusion and intermixing of Cu into the adjacent dielectrics. The integration of Cu with low-k materials may decrease RC delays in signal propagation but pose additional problems because such materials are often porous and contain significant amounts of carbon. Therefore barrier metal diffusion into the dielectric and the formation of interfacial carbides and oxides are of significant concern. The objective of the present research is to investigate the fundamental surface interactions between diffusion barriers and various low-k dielectric materials. Two major diffusion barriers¾ tatalum (Ta) and titanium nitride (TiN) are prepared by DC magnetron sputtering and metal-organic chemical vapor deposition (MOCVD), respectively. Surface analytical techniques, such as X-ray photoelectronic spectroscopy (XPS), transmission electron microscopy (TEM), and atomic force microscopy (AFM) are employed. Ta sputter-deposited onto a Si-O-C low dielectric constant substrate forms a reaction layer composed of Ta oxide and TaC. The composition of the reaction layer varies with deposition rate (1 Å-min-1 vs. 2 Å-sec-1), but in both cases, the thickness of the TaC layer is found to be at least 30 Å on the basis of XPS spectra, which is corroborated with cross-sectional TEM data. Sputter-deposited Cu will not wet the TaC layer and displays facile agglomeration, even at 400 K. Deposition for longer time at 2 Å-sec-1 results in formation of a metallic Ta layer. Sputter deposited Cu wets (grows conformally) on the metallic Ta surface at 300 K, and resists significant agglomeration at up to ~ 600 K. Cu diffusion into the substrate is not observed up to 800 K in the UHV environment. Tetrakis(diethylamido) titanium (TDEAT) interactions with SiO2, Cu and a variety of low-k samples in the presence (~ 10-7 Torr or ...
Date: December 2003
Creator: Tong, Jinhong

Selectivity Failure in the Chemical Vapor Deposition of Tungsten

Description: Tungsten metal is used as an electrical conductor in many modern microelectronic devices. One of the primary motivations for its use is that it can be deposited in thin films by chemical vapor deposition (CVD). CVD is a process whereby a thin film is deposited on a solid substrate by the reaction of a gas-phase molecular precursor. In the case of tungsten chemical vapor deposition (W-CVD) this precursor is commonly tungsten hexafluoride (WF6) which reacts with an appropriate reductant to yield metallic tungsten. A useful characteristic of the W-CVD chemical reactions is that while they proceed rapidly on silicon or metal substrates, they are inhibited on insulating substrates, such as silicon dioxide (Si02). This selectivity may be exploited in the manufacture of microelectronic devices, resulting in the formation of horizontal contacts and vertical vias by a self-aligning process. However, reaction parameters must be rigorously controlled, and even then tungsten nuclei may form on neighboring oxide surfaces after a short incubation time. Such nuclei can easily cause a short circuit or other defect and thereby render the device inoperable. If this loss of selectivity could be controlled in the practical applications of W-CVD, thereby allowing the incorporation of this technique into production, the cost of manufacturing microchips could be lowered. This research was designed to investigate the loss of selectivity for W-CVD in an attempt to understand the processes which lead to its occurrence. The effects of passivating the oxide surface with methanol against the formation of tungsten nuclei were studied. It was found that the methanol dissociates at oxide surface defect sites and blocks such sites from becoming tungsten nucleation sites. The effect of reactant partial pressure ratio on selectivity was also studied. It was found that as the reactant partial pressures are varied there are significant changes in the ...
Date: August 1994
Creator: Cheek, Roger W. (Roger Warren)

Synthesis and study of crystalline hydrogels, guided by a phase diagram.

Description: Monodispersed nanoparticles of poly-N-isopropylacrylamide-co-allylamine (PNIPAM-co-allylamine) and PNIPAM-co-acrylic acid (AA) have been synthesized and used as building blocks for creating three-dimensional networks. The close-packed PNIPAM-co-allylamine and PNIPAM-co-AA nanoparticles were stabilized by covalently bonding neighboring particles at room temperature and at neutral pH; factors which make these networks amicable for drug loading and release. Controlled release studies have been performed on the networks using dextran markers of various molecular weights as model macromolecular drugs. Drug release was quantified under various physical conditions including a range of temperature and molecular weight. These nanoparticle networks have several advantages over the conventional bulk gels for controlling the release of biomolecules with large molecular weights. Monodispersed nanoparticles of poly-N-isopropylacrylamide-co-allylamine (PNIPAM-co-allylamine) can self-assemble into crystals with a lattice spacing on the order of the wavelength of visible light. By initiating the crystallization process near the colloidal crystal melting temperature, while subsequently bonding the PNIPAM-co-allylamine particles below the glass transition temperature, a nanostructured hydrogel has been created. The crystalline hydrogels exhibit iridescent patterns that are tunable by the change of temperature, pH value or even protein concentration. This kind of soft and wet hydrogel with periodic structures may lead to new sensors, devices, and displays operating in aqueous solutions, where most biological and biomedical systems reside. The volume-transition equilibrium and the interaction potential between neutral PINPAM particles dispersed in pure water were investigated by using static and dynamic light-scattering experiments. From the temperature-dependent size and energy parameters, the Sutherland-like potential provides a reasonable representation of the inter-particle potential for PNIPAM particles in swollen and in collapsed phases. An aqueous dispersion of PNIPAM particles can freeze at both high and low temperatures. At low temperatures, the freezing occurs at a large particle volume fraction, similar to that in a hard-sphere system; while at high temperature, the freezing occurs at ...
Date: December 2004
Creator: Huang, Gang

Brainstem Lipids' Relationship to Death

Description: Previous work relating postmortem findings with cause of death have focused on the vitreous portion of the body. This research investigated the link between phospholipids in the brainstem and cause of death. The lipids were extracted by the Folch extraction method and then separated by High Performance Thin Layer Chromatography. These techniques gave excellent separation and resolution. Results showed no link between cause of death and the type of lipids found in the brainstem after death.
Date: December 1982
Creator: Schrynemeeckers, Patrick J.

Fabrication and light scattering study of multi-responsive nanostructured hydrogels and water-soluble polymers.

Description: Monodispersed microgels composed of poly-acrylic acid (PAAc) and poly(N-isopropylacrylamide) (PNIPAM) interpenetrating networks were synthesized by 2-step method with first preparing PNIPAM microgel and then polymerizing acrylic acid that interpenetrates into the PNIPAM network. The semi-dilute aqueous solutions of the PNIPAM-PAAc IPN microgels exhibit an inverse thermo-reversible gelation. Furthermore, IPN microgels undergo the reversible volume phase transitions in response to both pH and temperature changes associated to PAAc and PNIPAM, respectively. Three applications based on this novel hydrogel system are presented: a rich phase diagram that opens a door for fundamental study of phase behavior of colloidal systems, a thermally induced viscosity change, and in situ hydrogel formation for controlled drug release. Clay-polymer hydrogel composites have been synthesized based on PNIPAM gels containing 0.25 to 4 wt% of the expandable smectic clay Na-montmorillonite layered silicates (Na-MLS). For Na-MLS concentrations ranging from 2.0 to 3.2 wt%, the composite gels have larger swelling ratio and stronger mechanical strength than those for a pure PNIPAM. The presence of Na-MLS does not affect the value of the lower critical solution temperature (LCST) of the PNIPAM. Surfactant-free hydroxypropyl cellulose (HPC) microgels have been synthesized in salt solution. In a narrow sodium chloride concentration range from 1.3 to 1.4 M, HPC chains can self-associate into colloidal particles at room temperature. The microgel particles were then obtained in situ by bonding self-associated HPC chains at 23 0C using divinyl sulfone as a cross-linker. The volume phase transition of the resultant HPC microgels has been studied as a function of temperature at various salt concentrations. A theoretical model based on Flory-Huggins free energy consideration has been used to explain the experimental results. Self-association behavior and conformation variation of long chain branched (LCB) poly (2-ethyloxazoline) (PEOx) with a CH3-(CH2)17 (C18) modified surface are investigated using light scattering techniques in various ...
Date: December 2003
Creator: Xia, Xiaohu

Hydrogen terminated silicon surfaces: Development of sensors to detect metallic contaminants and stability studies under different environments

Description: Hydrogen terminated silicon surfaces have been utilized to develop sensors for semiconductor and environmental applications. The interaction of these surfaces with different environments has also been studied in detail. The sensor assembly relevant to the semiconductor industry utilizes a silicon-based sensor to detect trace levels of metallic contaminants in hydrofluoric acid. The sensor performance with respect to two non-contaminating reference electrode systems was evaluated. In the first case, conductive diamond was used as a reference electrode. In the second case, a dual silicon electrode system was used with one of the silicon-based electrodes protected with an anion permeable membrane behaving as the quasi reference electrode. Though both systems could function well as a suitable reference system, the dual silicon electrode design showed greater compatibility for the on-line detection of metallic impurities in HF etching baths. The silicon-based sensor assembly was able to detect parts- per-trillion to parts-per-billion levels of metal ion impurities in HF. The sensor assembly developed for the environmental application makes use of a novel method for the detection of Ni2+using attenuated total reflection (ATR) technique. The nickel infrared sensor was prepared on a silicon ATR crystal uniformly coated by a 1.5 micron Nafion film embedded with dimethylglyoxime (DMG) probe molecules. The detection of Ni2+ was based on the appearance of a unique infrared absorption peak at 1572 cm-1 that corresponds to the C=N stretching mode in the nickel dimethylglyoximate, Ni(DMG)2, complex. The suitable operational pH range for the nickel infrared sensor is between 6-8. The detection limit of the nickel infrared sensor is 1 ppm in the sample solution of pH=8. ATR - FTIR spectroscopy was used to study the changes that the hydride mode underwent when subjected to different environments. The presence of trace amounts of Cu2+ in HF solutions was found to roughen the silicon ...
Date: August 2002
Creator: Ponnuswamy, Thomas Anand

Cu Electrodeposition on Ru with a Chemisorbed Iodine Surface Layer.

Description: An iodine surface layer has been prepared on Ru(poly) and Ru(0001) electrodes by exposure to iodine vapor in UHV and polarizing in a 0.1 M HClO4/0.005 M KI solution, respectively. A saturation coverage of I on a Ru(poly) electrode passivates the Ru surface against significant hydroxide, chemisorbed oxygen or oxide formation during exposure to water vapor over an electrochemical cell in a UHV-electrochemistry transfer system. Immersion of I-Ru(poly) results in greater hydroxide and chemisorbed oxygen formation than water vapor exposure, but an inhibition of surface oxide formation relative that of the unmodified Ru(poly) surface is still observed. Studies with combined electrochemical and XPS techniques show that the iodine surface adlayer remained on top of the surface after cycles of overpotential electrodeposition/dissolution of copper on both Ru(poly) and Ru(0001) electrodes. These results indicate the potential bifunctionality of iodine layer to both passivate the Ru surface in the microelectronic processing and to act as a surfactant for copper electrodeposition. The electrodeposition of Cu on Ru(0001) or polycrystalline Ru was studied using XPS with combined ultrahigh vacuum/electrochemistry methodology (UHV-EC) in 0.1 M HClO4 with Cu(ClO4)2 concentrations ranging from 0.005 M to 0.0005 M, and on polycrystalline Ru in a 0.05M H2SO4/0.005 M CuSO4/0.001 M NaCl solution. The electrochemical data show well-defined cyclic voltammograms (CV) with a Cu underpotential deposition (UPD) peak and overpotential deposition (OPD) peak. XPS spectra of Ru electrodes emersed from perchloric acid solution at cathodic potentials indicate that ClO4- anions dissociate to yield specifically adsorbed Cl and ClOx species. Subsequent Cu deposition results in the formation of a thin, insoluble Cu(II) film with Cu(I) underneath. In contrast, similar deposition on polycrystalline Ru in the sulfuric acid/Cu sulfate solution with NaCl added yields only Cu(0), indicating that the formation of Cu(II) and Cu(I) involves both Cl and perchlorate interactions with the ...
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Date: August 2005
Creator: Lei, Jipu

Interfacial Electrochemistry of Metal Nanoparticles Formation on Diamond and Copper Electroplating on Ruthenium Surface

Description: An extremely facile and novel method called spontaneous deposition, to deposit noble metal nanoparticles on a most stable form of carbon (C) i.e. diamond is presented. Nanometer sized particles of such metals as platinum (Pt), palladium (Pd), gold (Au), copper (Cu) and silver (Ag) could be deposited on boron-doped (B-doped) polycrystalline diamond films grown on silicon (Si) substrates, by simply immersing the diamond/Si sample in hydrofluoric acid (HF) solution containing ions of the corresponding metal. The electrons for the reduction of metal ions came from the Si back substrate. The diamond/Si interfacial ohmic contact was of paramount importance to the observation of the spontaneous deposition process. The metal/diamond (M/C) surfaces were investigated using Raman spectroscopy, scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and x-ray diffractometry (XRD). The morphology (i.e. size and distribution) of metal nanoparticles deposits could be controlled by adjusting the metal ion concentration, HF concentration and deposition time. XRD data indicate the presence of textured and strained crystal lattices of Pd for different Pd/C morphologies, which seem to influence the electrocatalytic oxidation of formaldehyde (HCHO). The sensitivity of electrocatalytic reactions to surface crystal structure implies that M/C could be fabricated for specific electrocatalytic applications. The research also presents electroplating of Cu on ruthenium (Ru), which a priori is a promising barrier material for Cu interconnects in the sub 0.13 μm generation integrated circuits (ICs). Cu plates on Ru with over 90% efficiency. The electrochemical nucleation and growth studies using the potentiostatic current transient method showed a predominantly progressive nucleation of Cu on Ru. This was also supported by SEM imaging, which showed that continuous thin films of Cu (ca. 400 Å) with excellent conformity could be plated over Ru without dendrite formation. Scotch tape peel tests and SEM on Cu/Ru samples both at room temperature (RT) and ...
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Date: May 2003
Creator: Arunagiri, Tiruchirapalli Natarajan

Interfacial Electrochemistry and Surface Characterization: Hydrogen Terminated Silicon, Electrolessly Deposited Palladium & Platinum on Pyrolyzed Photoresist Films and Electrodeposited Copper on Iridium

Description: Hydrogen terminated silicon surfaces play an important role in the integrated circuit (IC) industry. Ultra-pure water is extensively used for the cleaning and surface preparation of silicon surfaces. This work studies the effects of ultra-pure water on hydrogen passivated silicon surfaces in a short time frame of 120 minutes using fourier transform infrared spectroscopy – attenuated total reflection techniques. Varying conditions of ultra-pure water are used. This includes dissolved oxygen poor media after nitrogen bubbling and equilibration under nitrogen atmosphere, as well as metal contaminated solutions. Both microscopically rough and ideal monohydride terminated surfaces are examined. Hydrogen terminated silicon is also used as the sensing electrode for a potentiometric sensor for ultra-trace amounts of metal contaminants. Previous studies show the use of this potentiometric electrode sensor in hydrofluoric acid solution. This work is able to shows sensor function in ultra-pure water media without the need for further addition of hydrofluoric acid. This is considered a boon for the sensor due to the hazardous nature of hydrofluoric acid. Thin carbon films can be formed by spin coating photoresist onto silicon substrates and pyrolyzing at 1000 degrees C under reducing conditions. This work also shows that the electroless deposition of palladium and platinum may be accomplished in hydrofluoric acid solutions to attain palladium and platinum nanoparticles on a this film carbon surface for use as an electrode. Catalysis of these substrates is studied using hydrogen evolution in acidic media, cyclic voltammetry, and catalysis of formaldehyde. X-ray diffractometry (XRD) is used to ensure that there is little strain on palladium and platinum particles. Iridium is thought to be a prime candidate for investigation as a new generation copper diffusion barrier for the IC industry. Copper electrodeposition on iridium is studied to address the potential of iridium as a copper diffusion barrier. Copper electrodeposition ...
Date: December 2003
Creator: Chan, Raymond

Electrodeposition of Diamond-like Carbon Films

Description: Electrodeposition of diamond-like carbon (DLC) films was studied on different substrates using two different electrochemical methods. The first electrochemical method using a three-electrode system was studied to successfully deposit hydrogenated DLC films on Nickel, Copper and Brass substrates. The as-deposited films were characterized by scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), fourier transform infrared spectroscopy (FTIR) and cyclic voltammetry (CV). A variety of experimental parameters were shown to affect the deposition process. The second electrochemical method was developed for the first time to deposit hydrogen free DLC films on Ni substrates through a two-electrode system. The as-deposited films were characterized by Raman spectroscopy and FTIR. According to Raman spectra, a high fraction of diamond nanocrystals were found to form in the films. Several possible mechanisms were discussed for each deposition method. An electrochemical method was proposed to deposit boron-doped diamond films for future work.
Date: August 2002
Creator: Chen, Minhua

Tantalum- and ruthenium-based diffusion barriers/adhesion promoters for copper/silicon dioxide and copper/low κ integration.

Description: The TaSiO6 films, ~8Å thick, were formed by sputter deposition of Ta onto ultrathin SiO2 substrates at 300 K, followed by annealing to 600 K in 2 torr O2. X-ray photoelectron spectroscopy (XPS) measurements of the films yielded a Si(2p) binding energy at 102.1 eV and Ta(4f7/2) binding energy at 26.2 eV, indicative of Ta silicate formation. O(1s) spectra indicate that the film is substantially hydroxylated. Annealing the film to > 900 K in UHV resulted in silicate decomposition to SiO2 and Ta2O5. The Ta silicate film is stable in air at 300K. XPS data show that sputter-deposited Cu (300 K) displays conformal growth on Ta silicate surface (TaSiO6) but 3-D growth on the annealed and decomposed silicate surface. Initial Cu/silicate interaction involves Cu charge donation to Ta surface sites, with Cu(I) formation and Ta reduction. The results are similar to those previously reported for air-exposed TaSiN, and indicate that Si-modified Ta barriers should maintain Cu wettability under oxidizing conditions for Cu interconnect applications. XPS has been used to study the reaction of tert-butylimino tris(diethylamino) tantalum (TBTDET) with atomic hydrogen on SiO2 and organosilicate glass (OSG) substrates. The results on both substrates indicate that at 300K, TBTDET partially dissociates, forming Ta-O bonds with some precursor still attached. Subsequent bombardment with atomic hydrogen at 500K results in stoichiometric TaN formation, with a Ta(4f7/2) feature at binding energy 23.2 eV and N(1s) at 396.6 eV, leading to a TaN phase bonded to the substrate by Ta-O interactions. Subsequent depositions of the precursor on the reacted layer on SiO2 and OSG, followed by atomic hydrogen bombardment, result in increased TaN formation. These results indicate that TBTDET and atomic hydrogen may form the basis for a low temperature atomic layer deposition (ALD) process for the formation of ultraconformal TaNx or Ru/TaNx barriers. The interactions ...
Date: December 2004
Creator: Zhao, Xiaopeng

Electrochemical Synthesis and Characterization of Inorganic Materials from Aqueous Solutions

Description: The dissertation consists of the following three sections: 1. Hydroxyapatite (HA) coatings. In this work, we deposited HA precursor films from weak basic electrolytic solution (pH= 8-9) via an electrochemical approach; the deposits were changed into crystallite coatings of hydroxyapatite by sintering at specific temperatures (600-800 ºC). The formed coatings were mainly characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). XRD patterns show well-defined peaks of HA when sintered under vacuum conditions. FTIR measurements indicate the existence of hydroxyl groups, which were confirmed by the characteristic intensity of the stretching and bending bands at ~3575 and ~630 cm-1, respectively. The SEM shows an adhesive, crack free morphology for the double-layer coating surface of the samples sintered in a vacuum furnace. 2. Silver/polymer/clay nanocomposites. Silver nanoparticles were prepared in layered clay mineral (montmorillonite)/polymer (PVP: poly (vinyl pyrrolidone)) suspension by an electrochemical approach. The silver particles formed in the bulk suspension were stabilized by the PVP and partially exfoliated clay platelets, which acted as protective colloids to prevent coagulation of silver nanoparticles together. The synthesized silver nanoparticles/montmorillonite/PVP composite was characterized and identified by XRD, SEM, and TEM (transmission electron microscopy) measurements. 3. Ce-doped lead zirconate titanate (PZT) thin films. In this study, we fabricated cerium-doped PZT films (molar ratio of Zr/Ti:: 0.5:0.5) via cathodic electrodeposition on the indium tin oxide ( ITO) coated glass substrate. In the preparation process, the PZT films were modified by adding a small amount of cerium dopants, which led to the formation of Ce-doped PZT films after sintering at high temperatures. The fabricated PZT films on the ITO coated glass substrate may be used as electro-optic devices in the industrial application.
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Date: December 2006
Creator: Yuan, Qiuhua

Adherence/Diffusion Barrier Layers for Copper Metallization: Amorphous Carbon:Silicon Polymerized Films

Description: Semiconductor circuitry feature miniaturization continues in response to Moore 's Law pushing the limits of aluminum and forcing the transition to Cu due to its lower resistivity and electromigration. Copper diffuses into silicon dioxide under thermal and electrical stresses, requiring the use of barriers to inhibit diffusion, adding to the insulator thickness and delay time, or replacement of SiO2 with new insulator materials that can inhibit diffusion while enabling Cu wetting. This study proposes modified amorphous silicon carbon hydrogen (a-Si:C:H) films as possible diffusion barriers and replacements for SiO2 between metal levels, interlevel dielectric (ILD), or between metal lines (IMD), based upon the diffusion inhibition of previous a-Si:C:H species expected lower dielectric constants, acceptable thermal conductivity. Vinyltrimethylsilane (VTMS) precursor was condensed on a titanium substrate at 90 K and bombarded with electron beams to induce crosslinking and form polymerized a-Si:C:H films. Modifications of the films with hydroxyl and nitrogen was accomplished by dosing the condensed VTMS with water or ammonia before electron bombardment producing a-Si:C:H/OH and a-Si:C:H/N and a-Si:C:H/OH/N polymerized films in expectation of developing films that would inhibit copper diffusion and promote Cu adherence, wetting, on the film surface. X-ray Photoelectron Spectroscopy was used to characterize Cu metallization of these a-Si:C:H films. XPS revealed substantial Cu wetting of a-Si:C:H/OH and a-Si:C:H/OH/N films and some wetting of a-Si:C:H/N films, and similar Cu diffusion inhibition to 800 K by all of the a-:S:C:H films. These findings suggest the possible use of a-Si:C:H films as ILD and IMD materials, with the possibility of further tailoring a-Si:C:H films to meet future device requirements.
Date: May 2004
Creator: Pritchett, Merry

Study of Copper Electrodeposition on Ruthenium Oxide Surfaces and Bimetallic Corrosion of Copper/Ruthenium in Gallic Acid Solution

Description: Ruthenium, proposed as a new candidate of diffusion barrier, has three different kinds of oxides, which are native oxide, electrochemical reversible oxide and electrochemical irreversible oxide. Native oxide was formed by naturally exposed to air. Electrochemical reversible oxide was formed at lower anodic potential region, and irreversible oxides were formed at higher anodic potential region. In this study, we were focusing on the effect of copper electrodeposition on each type of oxides. From decreased charge of anodic stripping peaks and underpotential deposition (UPD) waves in cyclic voltammetry (CV), efficiency of Cu deposition dropped off indicating that interfacial binding strength between Cu and Ru oxides was weakened when the Ru surface was covered with irreversible oxide and native oxide. Also, Cu UPD was hindered by both O2 and H2 plasma modified Ru surfaces because the binding strength between Cu and Ru was weakened by O2 and H2 plasma treatment. Cu/Ru and Cu/Ta bimetallic corrosion was studied for understanding the corrosion behavior between diffusion barrier (Ta and Ru) and Cu interconnects under the post chemical mechanical planarization (CMP) process in semiconductor fabrication. Gallic acid is used in post CMP slurry solution and is known well as antioxidant which is supposed to oxidize itself to prevent other species from oxidizing. However, in this study under the observation of Cu microdot corrosion test, copper was corroded only in gallic acid at specific pH region of alkaline condition which is close to the pH region for post CMP solution formula. With different pH alkaline condition, gallic acid formed different oxidized products which are characterized by cyclic voltammetry and UV-Vis spectroscopy. Therefore, the specific oxidized product from particular pH region condition caused the Cu corrosion. Also, the corrosion rate of Cu microdots was influenced by substrate effect (Cu/Ru and Cu/Ta) and ambient control, which was included ...
Date: August 2007
Creator: Yu, Kyle K.

Study of Substituted Benzenesulfonate-Containing Layered Double Hydroxides and Investigation of the Hexamethylenetetramine Route of LDH Synthesis

Description: Benzenesulfonates, para-substituted with amine, chloride and methyl groups were successfully incorporated into layered double hydroxides of two different compositions, 2:1 Mg-Al LDH and 2:1 Zn-Al LDH. These parent materials were also doped with small amounts of nickel and the differences in the two systems were studied. The hexamethylenetetramine route of layered double hydroxide synthesis was investigated to verify if the mechanism is indeed homogeneous. This included attempting preparation of 2:1 Mg-Al LDH, 2:1 Zn-Al LDH and 2:1 Zn-Cr LDH with two different concentrations of hexamethylenetetramine. The analytical data of the products suggest that the homogeneous precipitation may not be the true mechanism of reaction involved in LDH synthesis by this method.
Date: May 2007
Creator: Ambadapadi, Sriram

The synthesis and study of poly(N-isopropylacrylamide)/poly(acrylic acid) interpenetrating polymer network nanoparticle hydrogels.

Description: Homogeneous hydrogels made of an interpenetrating network of poly(N-isopropylacrylamide) (PNIPAm) and poly(acrylic acid) (PAAc) are synthesized by a two-step process; first making PNIPAm hydrogels and then interpenetrating acrylic acid throughout the hydrogel through polymerization. The kinetic growth of the IPN is plotted and an equation is fitted to the data. When diluted to certain concentrations in water, the hydrogels show reversible, inverse thermal gelation at about 34°C. This shows unique application to the medical field, as the transition is just below body temperature. A drug release experiment is performed using high molecular weight dyes, and a phase diagram is created through observation of the purified, concentrated gel at varying concentrations and temperatures.
Date: August 2006
Creator: Crouch, Stephen Wallace