I. Reactively sputtered Ti-Si-N thin films for diffusion barrier applications. II. Oxidation, diffusion and crystallization of an amorphous Zr_(60)Al_(15)Ni_(25) alloy.

Films of Ti-Si-N obtained by reactively sputtering a TiSi_2, a Ti_5Si_3, or a Ti_3Si target are either amorphous or nanocrystalline in structure. The atomic density of some films exceeds 10^23 at./cm^3. The room-temperature resistivity of the films increases with the Si and the N content. A thermal treatment in vacuum at 700 °C for 1 hour decreases the resistivity of the Ti-rich films deposited from the Ti_5Si_3 or the Ti_3Si target, but increases that of the Si-rich films deposited from the TiSi_2 target when the nitrogen content exceeds about 30 at. %.

Ti_(34)Si_(23)N_(43) deposited from the Ti_5Si_3 target is an excellent diffusion barrier between Si and Cu. This film is a mixture of nanocrystalline TiN and amorphous SiN_x. Resistivity measurement from 80 K to 1073 K reveals that this film is electrically semiconductor-like as-deposited, and that it becomes metal-like after an hour annealing at 1000 °C in vacuum. A film of about 100 nm thick, with a resistivity of 660 µΩcm, maintains the stability of Si n+p shallow junction diodes with a 400 nm Cu overlayer up to 850 °C upon 30 min vacuum annealing. When used between Si and Al, the maximum temperature of stability is 550 °C for 30 min. This film can be etched in a CF_4/O_2 plasma.

The amorphous ternary metallic alloy Zr_(60)Al_(15)Ni_(25) was oxidized in dry oxygen in the temperature range 310 °C to 410 °C. Rutherford backscattering and cross-sectional transmission electron microscopy studies suggest that during this treatment an amorphous layer of zirconium-aluminum-oxide is formed at the surface. Nickel is depleted from the oxide and enriched in the amorphous alloy below the oxide/alloy interface. The oxide layer thickness grows parabolically with the annealing duration, with a transport constant of 2.8x10^(-5) m^2/s x exp(-1.7 eV/kT). The oxidation rate is most likely controlled by the Ni diffusion in the amorphous alloy.

At later stages of the oxidation process, precipitates of nanocrystalline ZrO_2 appear in the oxide near the interface. Finally, two intermetallic phases nucleate and grow simultaneously in the alloy, one at the interface and one within the alloy.

Determination of source finiteness and depth of large earthquakes

In this thesis, a method to retrieve the source finiteness, depth of faulting, and the mechanisms of large earthquakes from long-period surface waves is developed and applied to several recent large events.

In Chapter 1, source finiteness parameters of eleven large earthquakes were determined from long-period Rayleigh waves recorded at IDA and GDSN stations. The basic data set is the seismic spectra of periods from 150 to 300 sec. Two simple models of source finiteness are studied. The first model is a point source with finite duration. In the determination of the duration or source-process times, we used Furumoto's phase method and a linear inversion method, in which we simultaneously inverted the spectra and determined the source-process time that minimizes the error in the inversion. These two methods yielded consistent results. The second model is the finite fault model. Source finiteness of large shallow earthquakes with rupture on a fault plane with a large aspect ratio was modeled with the source-finiteness function introduced by Ben-Menahem. The spectra were inverted to find the extent and direction of the rupture of the earthquake that minimize the error in the inversion. This method is applied to the 1977 Sumbawa, Indonesia, 1979 Colombia-Ecuador, 1983 Akita-Oki, Japan, 1985 Valparaiso, Chile, and 1985 Michoacan, Mexico earthquakes. The method yielded results consistent with the rupture extent inferred from the aftershock area of these earthquakes.

In Chapter 2, the depths and source mechanisms of nine large shallow earthquakes were determined. We inverted the data set of complex source spectra for a moment tensor (linear) or a double couple (nonlinear). By solving a least-squares problem, we obtained the centroid depth or the extent of the distributed source for each earthquake. The depths and source mechanisms of large shallow earthquakes determined from long-period Rayleigh waves depend on the models of source finiteness, wave propagation, and the excitation. We tested various models of the source finiteness, Q, the group velocity, and the excitation in the determination of earthquake depths.

The depth estimates obtained using the Q model of Dziewonski and Steim (1982) and the excitation functions computed for the average ocean model of Regan and Anderson (1984) are considered most reasonable. Dziewonski and Steim's Q model represents a good global average of Q determined over a period range of the Rayleigh waves used in this study. Since most of the earthquakes studied here occurred in subduction zones Regan and Anderson's average ocean model is considered most appropriate.

Our depth estimates are in general consistent with the Harvard CMT solutions. The centroid depths and their 90 % confidence intervals (numbers in the parentheses) determined by the Student's t test are: Colombia-Ecuador earthquake (12 December 1979), d = 11 km, (9, 24) km; Santa Cruz Is. earthquake (17 July 1980), d = 36 km, (18, 46) km; Samoa earthquake (1 September 1981), d = 15 km, (9, 26) km; Playa Azul, Mexico earthquake (25 October 1981), d = 41 km, (28, 49) km; El Salvador earthquake (19 June 1982), d = 49 km, (41, 55) km; New Ireland earthquake (18 March 1983), d = 75 km, (72, 79) km; Chagos Bank earthquake (30 November 1983), d = 31 km, (16, 41) km; Valparaiso, Chile earthquake (3 March 1985), d = 44 km, (15, 54) km; Michoacan, Mexico earthquake (19 September 1985), d = 24 km, (12, 34) km.

In Chapter 3, the vertical extent of faulting of the 1983 Akita-Oki, and 1977 Sumbawa, Indonesia earthquakes are determined from fundamental and overtone Rayleigh waves. Using fundamental Rayleigh waves, the depths are determined from the moment tensor inversion and fault inversion. The observed overtone Rayleigh waves are compared to the synthetic overtone seismograms to estimate the depth of faulting of these earthquakes. The depths obtained from overtone Rayleigh waves are consistent with the depths determined from fundamental Rayleigh waves for the two earthquakes. Appendix B gives the observed seismograms of fundamental and overtone Rayleigh waves for eleven large earthquakes.

Constraints on the carbon cycle and climate during the early evolution of animals

One of the greatest challenges in science lies in disentangling causality in complex, coupled systems. This is illustrated no better than in the dynamic interplay between the Earth and life. The early evolution and diversification of animals occurred within a backdrop of global change, yet reconstructing the potential role of the environment in this evolutionary transition is challenging. In the 200 million years from the end-Cryogenian to the Ordovician, enigmatic Ediacaran fauna explored body plans, animals diversified and began to biomineralize, forever changing the ocean's chemical cycles, and the biological community in shallow marine ecosystems transitioned from a microbial one to an animal one.

In the following dissertation, a multi-faceted approach combining macro- and micro-scale analyses is presented that draws on the sedimentology, geochemistry and paleontology of the rocks that span this transition to better constrain the potential environmental changes during this interval.

In Chapter 1, the potential of clumped isotope thermometry in deep time is explored by assessing the importance of burial and diagenesis on the thermometer. Eocene- to Precambrian-aged carbonates from the Sultanate of Oman were analyzed from current burial depths of 350-5850 meters. Two end-member styles of diagenesis independent of burial depth were observed.

Chapters 2, 3 and 4 explore the fallibility of the Ediacaran carbon isotope record and aspects of the sedimentology and geochemistry of the rocks preserving the largest negative carbon isotope excursion on record---the Shuram Excursion. Chapter 2 documents the importance of temperature, fluid composition and mineralogy on the delta 18-O min record and interrogates the bulk trace metal signal. Chapter 3 explores the spatial variability in delta 13-C recorded in the transgressive Johnnie Oolite and finds a north-to-south trend recording the onset of the excursion. Chapter 4 investigates the nature of seafloor precipitation during this excursion and more broadly. We document the potential importance of microbial respiratory reactions on the carbonate chemistry of the sediment-water interface through time.

Chapter 5 investigates the latest Precambrian sedimentary record in carbonates from the Sultanate of Oman, including how delta 13-C and delta 34-S CAS vary across depositional and depth gradients. A new model for the correlation of the Buah and Ara formations across Oman is presented. Isotopic results indicate delta 13-C varies with relative eustatic change and delta 34-S CAS may vary in absolute magnitude across Oman.

Chapter 6 investigates the secular rise in delta 18-Omin in the early Paleozoic by using clumped isotope geochemistry on calcitic and phosphatic fossils from the Cambrian and Ordovician. Results do not indicate extreme delta 18-O seawater depletion and instead suggest warmer equatorial temperatures across the early Paleozoic.

Measurement of the galactic cosmic ray antiproton flux from 0.25 gev to 3.11 gev with the isotope matter antimatter experiment (imax)

The intensities and relative abundances of galactic cosmic ray protons and antiprotons have been measured with the Isotope Matter Antimatter Experiment (IMAX), a balloon-borne magnet spectrometer. The IMAX payload had a successful flight from Lynn Lake, Manitoba, Canada on July 16, 1992. Particles detected by IMAX were identified by mass and charge via the Cherenkov-Rigidity and TOP-Rigidity techniques, with measured rms mass resolution ≤0.2 amu for Z=1 particles.

Cosmic ray antiprotons are of interest because they can be produced by the interactions of high energy protons and heavier nuclei with the interstellar medium as well as by more exotic sources. Previous cosmic ray antiproton experiments have reported an excess of antiprotons over that expected solely from cosmic ray interactions.

Analysis of the flight data has yielded 124405 protons and 3 antiprotons in the energy range 0.19-0.97 GeV at the instrument, 140617 protons and 8 antiprotons in the energy range 0.97-2.58 GeV, and 22524 protons and 5 antiprotons in the energy range 2.58-3.08 GeV. These measurements are a statistical improvement over previous antiproton measurements, and they demonstrate improved separation of antiprotons from the more abundant fluxes of protons, electrons, and other cosmic ray species.

When these results are corrected for instrumental and atmospheric background and losses, the ratios at the top of the atmosphere are p/p=3.21(+3.49, -1.97)x10^(-5) in the energy range 0.25-1.00 GeV, p/p=5.38(+3.48, -2.45) x10^(-5) in the energy range 1.00-2.61 GeV, and p/p=2.05(+1.79, -1.15) x10^(-4) in the energy range 2.61-3.11 GeV. The corresponding antiproton intensities, also corrected to the top of the atmosphere, are 2.3(+2.5, -1.4) x10^(-2) (m^2 s sr GeV)^(-1), 2.1(+1.4, -1.0) x10^(-2) (m^2 s sr GeV)^(-1), and 4.3(+3.7, -2.4) x10^(-2) (m^2 s sr GeV)^(-1) for the same energy ranges.

The IMAX antiproton fluxes and antiproton/proton ratios are compared with recent Standard Leaky Box Model (SLBM) calculations of the cosmic ray antiproton abundance. According to this model, cosmic ray antiprotons are secondary cosmic rays arising solely from the interaction of high energy cosmic rays with the interstellar medium. The effects of solar modulation of protons and antiprotons are also calculated, showing that the antiproton/proton ratio can vary by as much as an order of magnitude over the solar cycle. When solar modulation is taken into account, the IMAX antiproton measurements are found to be consistent with the most recent calculations of the SLBM. No evidence is found in the IMAX data for excess antiprotons arising from the decay of galactic dark matter, which had been suggested as an interpretation of earlier measurements. Furthermore, the consistency of the current results with the SLBM calculations suggests that the mean antiproton lifetime is at least as large as the cosmic ray storage time in the galaxy (~10^7 yr, based on measurements of cosmic ray ^(10)Be). Recent measurements by two other experiments are consistent with this interpretation of the IMAX antiproton results.

Rate and Microstructure Effects on the Dynamics of Carbon Nanotube Foams

Soft hierarchical materials often present unique functional properties that are sensitive to the geometry and organization of their micro- and nano-structural features across different lengthscales. Carbon Nanotube (CNT) foams are hierarchical materials with fibrous morphology that are known for their remarkable physical, chemical and electrical properties. Their complex microstructure has led them to exhibit intriguing mechanical responses at different length-scales and in different loading regimes. Even though these materials have been studied for mechanical behavior over the past few years, their response at high-rate finite deformations and the influence of their microstructure on bulk mechanical behavior and energy dissipative characteristics remain elusive.

In this dissertation, we study the response of aligned CNT foams at the high strain-rate regime of 10² - 10⁴ s^-1. We investigate their bulk dynamic response and the fundamental deformation mechanisms at different lengthscales, and correlate them to the microstructural characteristics of the foams. We develop an experimental platform, with which to study the mechanics of CNT foams in high-rate deformations, that includes direct measurements of the strain and transmitted forces, and allows for a full field visualization of the sample’s deformation through high-speed microscopy.

We synthesize various CNT foams (e.g., vertically aligned CNT (VACNT) foams, helical CNT foams, micro-architectured VACNT foams and VACNT foams with microscale heterogeneities) and show that the bulk functional properties of these materials are highly tunable either by tailoring their microstructure during synthesis or by designing micro-architectures that exploit the principles of structural mechanics. We also develop numerical models to describe the bulk dynamic response using multiscale mass-spring models and identify the mechanical properties at length scales that are smaller than the sample height.

The ability to control the geometry of microstructural features, and their local interactions, allows the creation of novel hierarchical materials with desired functional properties. The fundamental understanding provided by this work on the key structure-function relations that govern the bulk response of CNT foams can be extended to other fibrous, soft and hierarchical materials. The findings can be used to design materials with tailored properties for different engineering applications, like vibration damping, impact mitigation and packaging.

DNA-Mediated Charge Transport Devices for Protein Detection

Detection of biologically relevant targets, including small molecules, proteins, DNA, and RNA, is vital for fundamental research as well as clinical diagnostics. Sensors with biological elements provide a natural foundation for such devices because of the inherent recognition capabilities of biomolecules. Electrochemical DNA platforms are simple, sensitive, and do not require complex target labeling or expensive instrumentation. Sensitivity and specificity are added to DNA electrochemical platforms when the physical properties of DNA are harnessed. The inherent structure of DNA, with its stacked core of aromatic bases, enables DNA to act as a wire via DNA-mediated charge transport (DNA CT). DNA CT is not only robust over long molecular distances of at least 34 nm, but is also especially sensitive to anything that perturbs proper base stacking, including DNA mismatches, lesions, or DNA-binding proteins that distort the π-stack. Electrochemical sensors based on DNA CT have previously been used for single-nucleotide polymorphism detection, hybridization assays, and DNA-binding protein detection. Here, improvements to (i) the structure of DNA monolayers and (ii) the signal amplification with DNA CT platforms for improved sensitivity and detection are described.

First, improvements to the control over DNA monolayer formation are reported through the incorporation of copper-free click chemistry into DNA monolayer assembly. As opposed to conventional film formation involving the self-assembly of thiolated DNA, copper-free click chemistry enables DNA to be tethered to a pre-formed mixed alkylthiol monolayer. The total amount of DNA in the final film is directly related to the amount of azide in the underlying alkylthiol monolayer. DNA monolayers formed with this technique are significantly more homogeneous and lower density, with a larger amount of individual helices exposed to the analyte solution. With these improved monolayers, significantly more sensitive detection of the transcription factor TATA binding protein (TBP) is achieved.

Using low-density DNA monolayers, two-electrode DNA arrays were designed and fabricated to enable the placement of multiple DNA sequences onto a single underlying electrode. To pattern DNA onto the primary electrode surface of these arrays, a copper precatalyst for click chemistry was electrochemically activated at the secondary electrode. The location of the secondary electrode relative to the primary electrode enabled the patterning of up to four sequences of DNA onto a single electrode surface. As opposed to conventional electrochemical readout from the primary, DNA-modified electrode, a secondary microelectrode, coupled with electrocatalytic signal amplification, enables more sensitive detection with spatial resolution on the DNA array electrode surface. Using this two-electrode platform, arrays have been formed that facilitate differentiation between well-matched and mismatched sequences, detection of transcription factors, and sequence-selective DNA hybridization, all with the incorporation of internal controls.

For effective clinical detection, the two working electrode platform was multiplexed to contain two complementary arrays, each with fifteen electrodes. This platform, coupled with low density DNA monolayers and electrocatalysis with readout from a secondary electrode, enabled even more sensitive detection from especially small volumes (4 μL per well). This multiplexed platform has enabled the simultaneous detection of two transcription factors, TBP and CopG, with surface dissociation constants comparable to their solution dissociation constants.

With the sensitivity and selectivity obtained from the multiplexed, two working electrode array, an electrochemical signal-on assay for activity of the human methyltransferase DNMT1 was incorporated. DNMT1 is the most abundant human methyltransferase, and its aberrant methylation has been linked to the development of cancer. However, current methods to monitor methyltransferase activity are either ineffective with crude samples or are impractical to develop for clinical applications due to a reliance on radioactivity. Electrochemical detection of methyltransferase activity, in contrast, circumvents these issues. The signal-on detection assay translates methylation events into electrochemical signals via a methylation-specific restriction enzyme. Using the two working electrode platform combined with this assay, DNMT1 activity from tumor and healthy adjacent tissue lysate were evaluated. Our electrochemical measurements revealed significant differences in methyltransferase activity between tumor tissue and healthy adjacent tissue.

As differential activity was observed between colorectal tumor tissue and healthy adjacent tissue, ten tumor sets were subsequently analyzed for DNMT1 activity both electrochemically and by tritium incorporation. These results were compared to expression levels of DNMT1, measured by qPCR, and total DNMT1 protein content, measured by Western blot. The only trend detected was that hyperactivity was observed in the tumor samples as compared to the healthy adjacent tissue when measured electrochemically. These advances in DNA CT-based platforms have propelled this class of sensors from the purely academic realm into the realm of clinically relevant detection.

Mass measurements of some proton-rich nuclei

The Q values and 0^o cross sections of (He³, n) reactions forming seven proton-rich nuclei have been measured with accuracies varying from 6 to 18 keV. The Q values (in keV) are: Si²⁶ (85), S³⁰ (-573), Ar³⁴ (-759), Ti⁴² (-2865), Cr⁴⁸ (5550), Ni⁵⁶ (4513) and Zn⁶⁰ (818). At least one excited state was found for all but Ti⁴². The first four nuclei complete isotopic spin triplets; the results obtained agree well with charge-symmetry predictions. The last three, all multiples of the α particle, are important in the α and e-process theories of nucleo-synthesis in stars. The energy available for β decay of these three was found by magnetic spectrometer measurements of the (He³, p) Q values of reactions leading to V⁴⁸, Co⁵⁶, and Cu⁶⁰. Many excited states were seen: V⁴⁸ (3), Co⁵⁶ (15), Cu⁶⁰ (23). The first two states of S³⁰ are probably 0⁺ and 2⁺ from (He³, n) angular distribution measurements. Two NaI γ-ray measurements are described: the decay of Ar³⁴ (measured ^Ƭ1/2 = 1.2 ± 0.3s) and the prompt γ-ray spectrum from Fe⁵⁴(He³, nγ)Ni⁵⁶. Possible collective structure in Ni⁵⁶ and Ca⁴⁰, both doubly magic, is discussed.

The (He³, n) neutron energy and yield measurements utilized neutron-induced nuclear reactions in a silicon semiconductor detector. Cross sections for the most important detection processes, Si²⁸ (n, α) Mg²⁵ and Si²⁸ (n, p) Al²⁸, are presented for reactions leading to the first four states of both residual nuclei for neutron energies from 7.3 to 16.4 MeV. Resolution and pulse-height anomalies associated with recoil Mg²⁵ and Al²⁸ ions are discussed. The 0^o cross section for Be⁹ (α, n) C¹², used to provide calibration neutrons, has been measured with a stilbene spectrometer for n_o (5.0 ≤ E_α ≤ 12 MeV), n₁ (4.3 ≤ E_α ≤ 12.0 MeV) and n₂ (6.0 ≤ E_α ≤ 10.1 MeV). Resonances seen in the n_o yield may correspond to nine new levels in C¹³.