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  Partner: UNT Libraries
 Decade: 2000-2009
 Degree Discipline: Analytical Chemistry
 Collection: UNT Theses and Dissertations
Hydrogen terminated silicon surfaces: Development of sensors to detect metallic contaminants and stability studies under different environments

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

Date: August 2002
Creator: Ponnuswamy, Thomas Anand
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 ...
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Interfacial Electrochemistry and Surface Characterization: Hydrogen Terminated Silicon, Electrolessly Deposited Palladium & Platinum on Pyrolyzed Photoresist Films and Electrodeposited Copper on Iridium

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

Date: December 2003
Creator: Chan, Raymond
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 ...
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Interfacial Electrochemistry of Metal Nanoparticles Formation on Diamond and Copper Electroplating on Ruthenium Surface

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

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Date: May 2003
Creator: Arunagiri, Tiruchirapalli Natarajan
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 ...
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Interfacial Study of Copper Electrodeposition with the Electrochemical Quartz Crystal Microbalance (EQCM)

Interfacial Study of Copper Electrodeposition with the Electrochemical Quartz Crystal Microbalance (EQCM)

Date: May 2005
Creator: Ojeda Mota, Oscar Ulises
Description: The electrochemical quartz crystal microbalance (EQCM) has been proven an effective mean of monitoring up to nano-scale mass changes related to electrode potential variations at its surface. The principles of operation are based on the converse piezoelectric response of quartz crystals to mass variations on the crystal surface. In this work, principles and operations of the EQCM and piezo-electrodes are discussed. A conductive oxide, ruthenium oxide (RuO2) is a promising material to be used as a diffusion barrier for metal interconnects. Characterization of copper underpotential deposition (UPD) on ruthenium and RuO2 electrodes by means of electrochemical methods and other spectroscopic methods is presented. Copper electrodeposition in platinum and ruthenium substrates is investigated at pH values higher than zero. In pH=5 solutions, the rise in local pH caused by the reduction of oxygen leads to the formation of a precipitate, characterized as posnjakite or basic copper sulfate by means of X-ray electron spectroscopy and X-ray diffraction. The mechanism of formation is studied by means of the EQCM, presenting this technique as a powerful in-situ sensing device.
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Metal Oxide Reactions in Complex Environments: High Electric Fields and Pressures above Ultrahigh Vacuum

Metal Oxide Reactions in Complex Environments: High Electric Fields and Pressures above Ultrahigh Vacuum

Date: August 2005
Creator: Qin, Feili
Description: Metal oxide reactions at metal oxide surfaces or at metal-metal oxide interfaces are of exceptional significance in areas such as catalysis, micro- and nanoelectronics, chemical sensors, and catalysis. Such reactions are frequently complicated by the presence of high electric fields and/or H2O-containing environments. The focus of this research was to understand (1) the iron oxide growth mechanism on Fe(111) at 300 K and 500 K together with the effect of high electric fields on these iron oxide films, and (2) the growth of alumina films on two faces of Ni3Al single crystal and the interaction of the resulting films with water vapor under non-UHV conditions. These studies were conducted with AES, LEED, and STM. XPS was also employed in the second study. Oxidation of Fe(111) at 300 K resulted in the formation of Fe2O3 and Fe3O4. The substrate is uniformly covered with an oxide film with relatively small oxide islands, i.e. 5-15 nm in width. At 500 K, Fe3O4 is the predominant oxide phase formed, and the growth of oxide is not uniform, but occurs as large islands (100 - 300 nm in width) interspersed with patches of uncovered substrate. Under the stress of STM induced high electric fields, dielectric ...
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Passivation effects of surface iodine layer on tantalum for the electroless copper deposition.

Passivation effects of surface iodine layer on tantalum for the electroless copper deposition.

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Date: May 2004
Creator: Liu, Jian
Description: The ability to passivate metallic surfaces under non-UHV conditions is not only of fundamental interests, but also of growing practical importance in catalysis and microelectronics. In this work, the passivation effect of a surface iodine layer on air-exposed Ta for the copper electroless deposition was investigated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Although the passivation effect was seriously weakened by the prolonged air exposure, iodine passivates the Ta substrate under brief air exposure conditions so that enhanced copper wetting and adhesion are observed on I-passivated Ta relative to the untreated surface.
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Process Evaluation and Characterization of Tungsten Nitride as a Diffusion Barrier for Copper Interconnect Technology

Process Evaluation and Characterization of Tungsten Nitride as a Diffusion Barrier for Copper Interconnect Technology

Date: August 2005
Creator: Ekstrom, Bradley Mitsuharu
Description: The integration of copper (Cu) and dielectric materials has been outlined in the International Technology Roadmap for Semiconductors (ITRS) as a critical goal for future microelectronic devices. A necessity toward achieving this goal is the development of diffusion barriers that resolve the Cu and dielectric incompatibility. The focus of this research examines the potential use of tungsten nitride as a diffusion barrier by characterizing the interfacial properties with Cu and evaluating its process capability for industrial use. Tungsten nitride (β-W2N) development has been carried out using a plasma enhanced chemical vapor deposition (PECVD) technique that utilizes tungsten hexafluoride (WF6), nitrogen (N2), hydrogen (H2), and argon (Ar). Two design of experiments (DOE) were performed to optimize the process with respect to film stoichiometry, resistivity and uniformity across a 200 mm diameter Si wafer. Auger depth profiling showed a 2:1 W:N ratio. X-ray diffraction (XRD) showed a broad peak centered on the β-W2N phase. Film resistivity was 270 mohm-cm and film uniformity < 3 %. The step coverage (film thickness variance) across a structured etched dielectric (SiO2, 0.35 mm, 3:1 aspect ratio) was > 44 %. Secondary ion mass spectroscopy (SIMS) measurements showed good barrier performance for W2N between Cu and SiO2 ...
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Reactivity of Oxide Surfaces and Metal-Oxide Interfaces: Effects of Water Vapor Pressure on Ultrathin Aluminum Oxide Films, and Studies of Platinum Growth Modes on Ultrathin Oxide Films and Their Effects on Adhesion

Reactivity of Oxide Surfaces and Metal-Oxide Interfaces: Effects of Water Vapor Pressure on Ultrathin Aluminum Oxide Films, and Studies of Platinum Growth Modes on Ultrathin Oxide Films and Their Effects on Adhesion

Date: May 2004
Creator: Garza, Michelle
Description: The reactivity of oxide surfaces and metal-oxide interfaces play an important role in many technological applications such as corrosion, heterogeneous catalysis, and microelectronics. The focus of this research was (1) understanding the effects of water vapor exposure of ultrathin aluminum oxide films under non-ultrahigh vacuum conditions (>10-9 Torr) and (2) characterization of Pt growth modes on ultrathin Ta silicate and silicon dioxide films and the effects of growth modes on adhesion of a Cu overlayer. These studies were conducted with X-ray photoelectron spectroscopy (XPS). Ni3Al(110) was oxidized (10-6 Torr O2, 800K) followed by annealing (1100K). The data indicate that the annealed oxide film is composed of NiO, Al2O3 and an intermediate phase denoted here as "AlOx". Upon exposure of the oxide film at ambient temperature to increasing water vapor pressure (10-6 - 5 Torr), a shift in both the O(1s) and Al(2p)oxide peak maxima to lower binding energies is observed. In contrast, exposure of Al2O3/Al(polycrystalline) to water vapor under the same conditions results in a high binding energy shoulder in the O(1s) spectra which indicates hydroxylation. Spectral decomposition provides further insight into the difference in reactivity between the two oxide films. The corresponding trends of the O(1s)/Ni0(2p3/2) and Al(2p)/Ni0(2p3/2) spectral ...
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The Revival of Electrochemistry: Electrochemical Deposition of Metals in Semiconductor Related Research

The Revival of Electrochemistry: Electrochemical Deposition of Metals in Semiconductor Related Research

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Date: August 2005
Creator: Wang, Chen
Description: Adherent Cu films were electrodeposited onto polycrystalline W foils from purged solutions of 0.05 M CuSO4 in H2SO4 supporting electrolyte and 0.025 M CuCO3∙Cu(OH)2 in 0.32 M H3BO3 and corresponding HBF4 supporting electrolyte, both at pH = 1. Films were deposited under constant potential conditions at voltages between -0.6 V and -0.2 V versus Ag/AgCl. All films produced by pulses of 10 s duration were visible to the eye, copper colored, and survived a crude test called "the Scotch tape test", which involves sticking the scotch tape on the sample, then peeling off the tape and observing if the copper film peels off or not. Characterization by scanning electron microscopy (SEM)/energy dispersive X-ray (EDX) and X-ray photon spectroscopy (XPS) confirmed the presence of metallic Cu, with apparent dendritic growth. No sulfur impurity was observable by XPS or EDX. Kinetics measurements indicated that the Cu nucleation process in the sulfuric bath is slower than in the borate bath. In both baths, nucleation kinetics does not correspond to either instantaneous or progressive nucleation. Films deposited from 0.05 M CuSO4/H2SO4 solution at pH > 1 at -0.2 V exhibited poor adhesion and decreased Cu reduction current. In both borate and sulfate baths, small ...
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Study of Copper Electrodeposition on Ruthenium Oxide Surfaces and Bimetallic Corrosion of Copper/Ruthenium in Gallic Acid Solution

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

Date: August 2007
Creator: Yu, Kyle K.
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 ...
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Study of Interactions Between Diffusion Barrier Layers and Low-k Dielectric Materials for Copper/Low-k Integration

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

Date: December 2003
Creator: Tong, Jinhong
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 ...
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Study of Ruthenium and Ruthenium Oxide's Electrochemical Properties and Application as a Copper Diffusion Barrier

Study of Ruthenium and Ruthenium Oxide's Electrochemical Properties and Application as a Copper Diffusion Barrier

Date: August 2005
Creator: Zhang, Yibin
Description: As a very promising material of copper diffusion barrier for next generation microelectronics, Ru has already obtained a considerable attention recently. In this dissertation, we investigated ruthenium and ruthenium oxide electrochemical properties and the application as a copper diffusion barrier. Cu under potential deposition (UPD) on the RuOx formed electrochemically was first observed. Strong binding interaction, manifesting by the observed Cu UPD process, exists between Cu and Ru as well as its conductive ruthenium oxide. Since UPD can be conformally formed on the electrode surface, which enable Ru and RuOx has a potential application in the next generation anode. The [Cl-] and pH dependent experiment were conducted, both of them will affect UPD Cu on Ru oxide. We also found the Cu deposition is thermodynamically favored on RuOx formed electrochemically. We have studied the Ru thin film (5nm) as a copper diffusion barrier. It can successfully block Cu diffusion annealed at 300 oC for 10min under vacuum, and fail at 450 oC. We think the silicidation process at the interface between Ru and Si. PVD Cu/Ru/Si and ECP Cu/Ru/Si were compared each other during copper diffusion study. It was observed that ECP Cu is easy to diffuse through Ru barrier. ...
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Study of Substituted Benzenesulfonate-Containing Layered Double Hydroxides and Investigation of the Hexamethylenetetramine Route of LDH Synthesis

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

Date: May 2007
Creator: Ambadapadi, Sriram
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.
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Synthesis and study of crystalline hydrogels, guided by a phase diagram.

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

Date: December 2004
Creator: Huang, Gang
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 ...
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The synthesis and study of poly(N-isopropylacrylamide)/poly(acrylic acid) interpenetrating polymer network nanoparticle hydrogels.

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

Date: August 2006
Creator: Crouch, Stephen Wallace
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.
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Tantalum- and ruthenium-based diffusion barriers/adhesion promoters for copper/silicon dioxide and copper/low κ integration.

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

Date: December 2004
Creator: Zhao, Xiaopeng
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 ...
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Thermodynamics of the Abraham General Solvation Model: Solubility and Partition Aspects

Thermodynamics of the Abraham General Solvation Model: Solubility and Partition Aspects

Date: August 2006
Creator: Stovall, Dawn Michele
Description: Experimental mole fraction solubilities of several carboxylic acids (2-methoxybenzoic acid, 4-methoxybenzoic acid, 4-nitrobenzoic acid, 4-chloro-3-nitrobenzoic acid, 2-chloro-5-nitrobenzoic acid,2-methylbenzoic acid and ibuprofen) and 9-fluorenone, thianthrene and xanthene were measured in a wide range of solvents of varying polarity and hydrogen-bonding characteristics. Results of these measurements were used to calculate gas-to-organic solvent and water-to-organic solvent solubility ratios, which were then substituted into known Abraham process partitioning correlations. The molecular solute descriptors that were obtained as the result of these computations described the measured solubility data to within an average absolute deviation of 0.2 log units. The calculated solute descriptors also enable one to estimate many chemically, biologically and pharmaceutically important properties for the ten solutes studied using published mathematical correlations.
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