Title from PDF of title page. / Document formatted into pages; contains 100 pages. / Thesis (M.S.Ch.E.)--University of South Florida, 2003. / Includes bibliographical references. / Text (Electronic thesis) in PDF format. / ABSTRACT: Silicon Carbide has been a semiconductor material of interest as a high power and temperature replacement for Silicon (Si) in harsh environments due to the higher thermal conductivity and chemical stability of SiC. The cost, however, to produce this material is quite high. There are also defects in the substrate material (SiC) that penetrate into the active devices layers which are known device killers. Silicon is a material that provides a low cost substrate material for epitaxial growth and does not contain the defects that SiC substrates have. However, the large ( 22%) lattice mismatch between Si and SiC creates dislocations at the SiC/Si interface and defects in the SiC epitaxial layer. These defects result in high leakage currents in 3C-SiC/Si devices. The main focus of the this research was to reduce or eliminate these defects using novel Si substrates. / ABSTRACT: First a 3C-SiC on Si baseline process was developed under atmospheric pressure conditions consisting of 3 steps - an in-situ hydrogen etch to remove the native oxide, a carbonization step to convert the Si surface to SiC, and finally a growth step to thicken the SiC layer to the desired value. This process was then modified to establish a high-quality, low-pressure 3C-SiC CVD growth process. This LPCVD process was then used to grow 3C-SiC on numerous novel Si substrates, including porous Si, porous 3C-SiC "free-standing" substrates and SOI substrates which consisted on thin Si films bonded to poly-crystalline SiC plates. The results of these experiments are presented along with suggestions for future work so that device-grade films of 3C-SiC can be developed for various applications. / System requirements: World Wide Web browser and PDF reader. / Mode of access: World Wide Web.

Systematische Untersuchungen zur Abscheidung von Siliciumcarbid und Siliciumcarbid mit coabgeschiedenem Silicium auf Kohlenstoffsubstraten werden in dieser Arbeit vorgestellt. Die Abscheidung erfolgte mittels thermischer CVD in einer CH3SiCl3-H2-Ar-Atmosphaere. Dabei koennen neue Zusammenhaenge zwischen den Schichteigenschaften, wie chemische Zusammensetzung und Struktur, und den Beschichtungsparametern gewonnen werden. In einem zweiten Schritt kann das coabgeschiedene Silicium durch eine thermische Nitridierung in Siliciumnitrid umgewandelt werden. Bei dieser Reaktion reagiert auch die Siliciumcarbidschicht zu Siliciumnitrid. Ueber den Umweg des Titanium-Einbaus in das SiC + Si-Schichtsystem - dabei bilden sich bei der Beschichtungstemperatur Titaniumsilicide - konnte eine Mischschicht angeboten werden, die das coabgeschiedene Silicium selektiv in Siliciumnitrid umwandelt.

In der vorliegenden Arbeit werden M(II)-Formiat-Komplexe mit M=Cu, Ni, Zn beschrieben. Das themogravimetrische Verhalten dieser Komplexe wird vorgestellt. TG-MS-Untersuchungen geben erste Hinweise auf das Metallisierungsverhalten obiger Spezies. Die Charakterisierung der entsprechenden Komplexe erfolgte durch die Elementaranalyse, IR-Spektroskopie sowie in einzelnen Fällen durch die Einkristallröntgendiffraktometrie.

Vor dem Hintergrund der in der Mikroelektronik-Fertigung heute verbreiteten Kupfertechnologie werden in der vorliegenden Arbeit drei neuartige metallorganische Verbindungen, nämlich phosphitstabilisierte Kupfer(I)-Trifluoracetat-Komplexe vorgestellt und hinsichtlich ihrer Anwendbarkeit für die chemische Gasphasenabscheidung (CVD) von Kupfer untersucht. Im einzelnen handelt es ich um die Substanzen Tris(trimethylphosphit)kupfer(I)trifluoracetat (METFA), Tris(triethylphosphit)kupfer(I)trifluoracetat (ETTFA) und Tri(tris(trifluorethyl)phosphit)kupfer(I)trifluoracetat (CFTFA). Mit den Substanzen erfolgen CVD-Experimente auf TiN und Cu bei Temperaturen <400°C. Die Precursoren werden dabei mittels eines Flüssigdosiersystems mit Verdampfereinheit der Reaktionskammer zugeführt. Während METFA wegen seiner ausreichend geringen Viskosität unverdünnt verwendet werden kann, kommen für ETTFA und CFTFA jeweils Precursor-Acetonitril-Gemische zum Einsatz. Mit keinem der Neustoffe können auf TiN geschlossene Kupferschichten erzeugt werden, während dies auf Kupferunterlagen in Verbindung mit Wasserstoff als Reduktionsmittel gelingt. Die Abscheiderate beträgt hierbei 2-3nm/min; der spezifische Widerstand der Schichten bewegt sich zwischen 4μΩcm und 5μΩcm. Mit allen Substanzen werden besonders an dünnen, gesputterten Kupferschichten Agglomerationserscheinungen und Lochbildung beobachtet. Im Fall von CFTFA treten zusätzlich Schäden am darunterliegenden TiN/SiO₂-Schichtstapel auf. Vergleichende Untersuchungen mit der für die Cu-CVD etablierten Substanz (TMVS)Cu(hfac) ergeben sowohl auf Cu als auch auf TiN geschlossene Kupferschichten. Dabei liegen die Abscheideraten bei Temperaturen zwischen 180°C und 200°C im allgemeinen deutlich über 100nm/min. Ein Vergleich dieser Resultate mit den Ergebnissen für die Neustoffe legt nahe, dass den untersuchten Kupfer(I)-Trifluoracetaten keine ausreichende Tauglichkeit für Cu-CVD-Prozesse in der Mikroelektronik-Technologie bescheinigt werden kann. Die im Vergleich zu (TMVS)Cu(hfac) höhere thermische Stabilität der Precursoren und ihre Fähigkeit, mit Wasserstoff als Reaktionspartner auf Cu geschlossene Kupferschichten erzeugen zu können, deutet jedoch auf ihre eventuelle Eignung für ALD-Prozesse hin. Daher widmet sich die Arbeit in einem abschließenden Kapitel dem Thema der Atomic Layer Deposition (ALD), wobei nach einem allgemeinen Überblick besonders auf für die Mikroelektronik relevante ALD-Prozesse eingegangen wird.

Copper has become the material of choice for metallization of high-performance ultra-large scale integrated circuits. As the feature size is continuously decreasing, metal-organic chemical vapor deposition (MOCVD) appears promising for depositing the Cu seed layer required for electroplating, as well as for filling entire interconnect structures. In this work, four novel organophosphane and organophosphite Cu(I) trifluoroacetates were studied as precursors for Cu MOCVD. Details are reported on CVD results obtained with Tris(tri-n-butylphosphane)copper(I)trifluoroacetate, (ⁿBu₃P)₃CuO₂CCF₃. Solutions of this precursor with acetonitrile and isopropanol were used for deposition experiments on 100 mm Si wafers sputter-coated with Cu, Cu/TiN, and Al(2 % Si)/W. Experiments were carried out in a cold-wall reactor at a pressure of 0.7 mbar, using a liquid delivery approach for precursor dosage. On Cu seed layers, continuous films were obtained at low deposition rates (0.5 to 1 nm/min). At temperatures above 320°C, hole formation in the Cu films was observed. Deposition on TiN led to the formation of single copper particles and etching of the TiN, whereas isolating aluminum oxyfluoride was formed after deposition on Al(Si)/W. It is concluded that the formation of CF₃ radicals during decarboxylation has a negative effect on the deposition results. Furthermore, the precursor chemistry needs to be improved for a higher volatility of the complex.

Several studies have been propose to improve the adhesion of diamond films on cemented carbide tool materials, however a systematic study in identifying the role of the factors that affect the final diamond adhesion and the resulting machining performance of the tool under real manufacturing conditions is still unexplored. CVD diamond film's extraordinary qualities bring little benefit if the film fails to adhere sufficiently to the substrate. Inadequate adhesion undermines tool performance and longevity, causing unpredictable behavior under load and possibly leading to unexpected failure of the tool in the production line. This dissertation investigates the effects of different surface pretreatments on the adhesion and performance of CVD diamond coated WC-Co turning inserts for the dry machining of high silicon aluminum alloys. Different interfacial characteristics between the diamond coatings and the modified WC-Co substrate were obtained by the use of two different chemical etchings and a CrN/Cr interlayer, with the aim to produce an adherent diamond coating by increasing the interlocking effect of the diamond film, and halting the catalytic effect of the cobalt present on the cemented carbide tool. A systematic study is analyzed in terms of the initial cutting tool surface modifications, the deposition and characterization of microcrystalline diamond coatings deposited by HFCVD synthesis, the estimation of the resulting diamond adhesion by Rockwell indentations and Raman spectroscopy, and finally, the evaluation of the dry machining performance of the diamond coated tools on A390 aluminum alloys. Scanning electron microscopy (SEM), metallographic analysis, and x-ray diffraction techniques were used to characterize the morphology, cobalt content, and nature of the substrate surfaces before and after each pretreatment; optical interferometry was utilized to characterize the surface roughness. After successfully diamond depositions, the films were characterized again using SEM, Raman spectroscopy, XRD, Electron Probe Microscopy Analysis (EPMA), and optical interferometry. The experiments show that chemical etching methods exceed the effect of the CrN/Cr interlayer in increasing the diamond coating adhesion under dry cutting operations. This dissertation provided new insights about optimizing the surface characteristics of cemented carbides to produce adherent diamond coatings in the dry cutting manufacturing chain of high silicon aluminum alloys. An alternative method to measure the practical adhesion on commercial diamond coatings that can be correlated with the machining performance is proposed to be used when other methods (scratch, nanoindentation, microindentation, pin-on-disk, etc.) are not viable. This research is the first comprehensive and systematic work that links the surface/subsurface integrity of cutting tools with their ability to produce an adherent diamond coating capable to dry machine high silicon aluminum alloys.

In the modern semiconductor manufacturing processes, chemical mechanical planarization (CMP) has attained important processing step because of its ability to provide global planarization. CMP is the planarization technique which is used for the removal of excess material, as left over from the previous processing steps. In addition, CMP offers a uniform surface that is essential for subsequent processing steps, especially for the high resolution photolithography processes. In simpler notation, CMP is a process where a chemical reaction enhances in obtaining a planar surface through removal of the mechanical materials from a wafer. In this study, CMP performance of three electronic materials was investigated. Chemical vapor deposited (CVD) diamond films, as a first materials, was fabricated using hot-filament chemical vapor deposition technique (HFCVD). The synthesized microcrystalline diamond (MCD) films were characterized using Raman Spectroscopy, Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), and X-ray Diffraction (XRD). The CMP performance of the MCD and nanocrystalline diamond (NCD) synthesized in Nano Materials Research Laboratory (NMRL) were investigated by using commercial slurry procured by Logitech Inc. U.K. The post-CMP characterizations of diamond films were performed by AFM in order to investigate surface roughness. The result showed the significant reduction the surface roughness of MCD films (37 nm to 15 nm) and NCD films (18 nm to 12 nm). In addition, the CMP performance of the silicon dioxide was investigated in this research work. The novel nanodiamond-polymer based slurry was also developed by co-polymerization of N-isopropylacrylamide (NIPAM) and N,N'-methylenebisacrylamide, 3-(trimethoxysilyl) propyl methacrylate (MPS). The synthesized slurry was characterized by Transmission Electron Microscopy (TEM) for observing the dispersion of diamond particles in the polymer matrix. The investigation of silicon dioxide was carried out using conventional ceria based slurry and novel nanodiamond-polymer based slurry. The results showed excellent surface finish at the minor expense of material removal rate with nanodiamond-polymer based slurry. Also, the coefficient of friction of friction was significantly reduced by using novel nanodiamond polymer based slurry. Lastly, CMP behavior of copper wafer was examined under different polishing conditions. The polishing was carried out using the commercial slurry procured from Cabot Microelectronics Inc., U.S. The copper wafers were characterized by AFM in order to analyze surface roughness. The results showed the reduction in average surface roughness occurred from 4.7 nm to 1.7 nm. This range of average surface roughness meets the demands of modern semiconductor industries.

Background: CVD is a major cause of premature death in Nova Scotia, Canada. Objective: To determine the role of inflammation in the relationships between obesity, physical activity and IHD. Methods: Secondary analysis using exposure data from the 1995 Nova Scotia Health Survey, morbidity data from CIHI and mortality data from Statistics Canada. Results: A statistically significant association was found between abdominal obesity and IHD for women; the relationship between physical inactivity and IHD was of borderline statistical significance in men. Inflammatory markers were independently associated IHD for women. Conclusions: Abdominal obesity was a risk factor for IHD for women, whereas physical inactivity was the was the strongest predictor of IHD in men. Inflammation was found to be an independent risk factor for IHD in women but not men. There was no evidence that inflammation plays a mediating role in the obesity-IHD and physical activity-IHD relationships for women and men, respectively.

This thesis details an investigation of the suitability of commercially-available single crystal and polycrystalline diamond films made via chemical vapor deposition (CVD) that were not studied previously for use in radiotherapy dosimetry. Novel sandwich-type detectors were designed and constructed to investigate the dosimetric response of diamond films under clinical conditions. Relatively inexpensive diamond films were obtained from three manufacturers: Diamonex, Diamond Materials GmbH and Element Six. Spectrophotometry, Raman spectroscopy and bulk conductivity studies were used to characterize these films and correlate crystalline quality with detector performance. Novel detectors were designed and constructed to investigate detectors under clinical conditions, including Perspex encapsulations and PCBs to minimize fluence perturbations. The dosimetric response of these diamond detectors was examined using a 6 MV beam from a Varian Clinac 600C linear accelerator. Diamond detectors were evaluated by measuring a number of response characteristics. Polycrystalline CVD diamond films from Diamonex (100, 200, 400-μm thicknesses) were considered unsuitable for dosimetric applications due to their lack of stability, low sensitivity, high leakage currents, high priming dose and dependence on dose rate. High-quality polycrystalline diamond films from Diamond Materials (100, 200, 400-μm thicknesses) displayed characteristics that varied with film thickness. A 100-μm film featured slow response dynamics and high priming doses. Thicker films featured suitable dosimetric characteristics, e.g. negligible leakage currents, low priming doses, fast response dynamics and good sensitivity with small sensitive volumes. Element Six single crystal CVD diamond films (500-μm thicknesses) with small sensitive volumes (0.39 mm³) exhibited suitable characteristics for dosimetry. These films showed negligible leakage currents (< 1.25 pA), low priming doses (1–10 Gy), quick response dynamics, high sensitivity (47–230 nC Gy⁻¹) and were weakly dependent on dose rate and directional dependence (±1%). A relatively inexpensive single crystal CVD diamond film from Element Six that exhibited high sensitivity (230 nC Gy⁻¹ at 0.5 V μm⁻¹), amongst other favourable characteristics, was selected for further analyses. An appropriate operating voltage was determined before further clinically relevant measurements could be conducted. This included how changes in an applied electric field affected detector response, and determined whether an optimal operating voltage could be realized within the parameters of conventional instrumentation used in radiation therapy. The results of this study indicated a preference towards using 62.5 V (at ~0.13 V μm⁻¹) out of a range of 30.8–248.0 V for temporal response as required for modulated beams due to its minimal rise time (2 s) and fall time (2 s) yet sufficient sensitivity (37 nC Gy⁻¹) and weak dependence on polarity (±1.5%). Investigations were then performed on the same diamond detector to evaluate its performance under more clinically relevant conditions. Repeatability experiments revealed a temporary loss in sensitivity due to charge detrapping effects following irradiation, which was modelled to make corrections that improved short-term precision. It was shown that this detector could statistically distinguish between dose values separated by a single Monitor Unit, which corresponded to 0.77 cGy. Dose rate dependence was observed when using low, fixed doses in contrast to using stabilized currents and higher doses. Depth dose measurements using this detector compared well with ion chambers and diode dosimeters. Comparisons of initial measurements with values in the literature indicate encouraging results for fields sizes < 4 x 4 cm², but further measurements and comparisons with Monte Carlo calculations are required. Using this detector to make off-axis measurements in the edge-on orientation reduced perturbation of the beam due to its sandwich configuration and thin 150 nm Ag contacts. This diamond detector was found to be suitable for routine dosimetry with conventional radiotherapy instrumentation with a materials cost of < NZ$200.

The synthesis of highly ordered carbonaceous materials, including carbon nanofibers, has been the subject of a disparate and burgeoning literature over the past decade. Growth of carbon nanotubes via an atypical catalytic route, the decomposition of halogenated reactants as chlorobenzene (CB) over 10% (w/w) Ni/SiO2 is investigated. The C (carbon) yield and structural order are a function of reaction time and temperature. Greater degree of structural order and C yield is observed from CB relative to benzene, suggesting Cl/catalyst interaction(s) and metal site restructuring. Evaluation of the effect of H2 on C growth from CB reveals that C yield is sensitive to % (v/v) H2 with selectivity maxima at 40% (v/v) H2. Further, C yield is significantly influenced by the nature of the heteroatom substituent on the benzene ring; presence of strong electron withdrawing groups favors C yield and weak electron withdrawing or donating groups favors competing side reactions. The effect of the strong electron withdrawing group, Cl, varies with the chemical structure of the carbon source. Presence of Cl promotes C yield in the case of aromatic and straight chained (aliphatic) compounds whereas it promotes formation of benzene in the case of cyclic (aliphatic) compounds. Results are interpreted in term of substituent/ catalyst interaction and the mechanism of solid C formation. Further, effect of % (v/v) H2 on C growth characteristics varies significantly with the precursor. The C growth characteristics are strongly dependent on the nature of the support used, as demonstrated for the following supports: SiO2, Ta2O5, Al2O3, NaY, activated carbon and graphite at 10% (w/w) Ni loading. Ni/SiO2 results in maximum C yield. Variation in Ni loading significantly influences the C yield; higher loading favors greater C yield. C grown on Ni/NaY was found to be relatively more structured to C obtained on the other supports. EDX analysis of the carbon product was used to assess the possibility of Cl intercalation and it reveals presence of 0.4 at% Cl on carbon grown on Ni/Al2O3.