Insights into the influence of solvent polarity on the crystallization of poly(ethylene oxide) spin-coated thin films via in situ grazing incidence wide-angle X-ray scattering

Controlling polymer thin-film morphology and crystallinity is crucial for a wide range of applications, particularly in thin-film organic electronic devices. In this work, the crystallization behavior of a model polymer, poly(ethylene oxide) (PEO), during spin-coating is studied. PEO films were spun-cast from solvents possessing different polarities (chloroform, THF, and methanol) and probed via in situ grazing incidence wide-angle X-ray scattering. The crystallization behavior was found to follow the solvent polarity order (where chloroform < THF < methanol) rather than the solubility order (where THF > chloroform > methanol). When spun-cast from nonpolar chloroform, crystallization largely followed Avrami kinetics, resulting in the formation of morphologies comprising large spherulites. PEO solutions cast from more polar solvents (THF and methanol) do not form well-defined highly crystalline morphologies and are largely amorphous with the presence of small crystalline regions. The difference in morphological development of PEO spun-cast from polar solvents is attributed to clustering phenomena that inhibit polymer crystallization. This work highlights the importance of considering individual components of polymer solubility, rather than simple total solubility, when designing processing routes for the generation of morphologies with optimum crystallinities or morphologies.

In vivo characterization of myocardial tissue post myocardial infarction using combined fluorescence and diffuse reflectance spectroscopy

Accurately assessing the extent of myocardial tissue injury induced by Myocardial infarction (MI) is critical to the planning and optimization of MI patient management. With this in mind, this study investigated the feasibility of using combined fluorescence and diffuse reflectance spectroscopy to characterize a myocardial infarct at the different stages of its development. An animal study was conducted using twenty male Sprague-Dawley rats with MI. In vivo fluorescence spectra at 337 nm excitation and diffuse reflectance between 400 nm and 900 nm were measured from the heart using a portable fiber-optic spectroscopic system. Spectral acquisition was performed on (1) the normal heart region; (2) the region immediately surrounding the infarct; and (3) the infarcted region—one, two, three and four weeks into MI development. The spectral data were divided into six subgroups according to the histopathological features associated with various degrees/severities of myocardial tissue injury as well as various stages of myocardial tissue remodeling, post infarction. Various data processing and analysis techniques were employed to recognize the representative spectral features corresponding to various histopathological features associated with myocardial infarction. The identified spectral features were utilized in discriminant analysis to further evaluate their effectiveness in classifying tissue injuries induced by MI. In this study, it was observed that MI induced significant alterations (p < 0.05) in the diffuse reflectance spectra, especially between 450 nm and 600 nm, from myocardial tissue within the infarcted and surrounding regions. In addition, MI induced a significant elevation in fluorescence intensities at 400 and 460 nm from the myocardial tissue from the same regions. The extent of these spectral alterations was related to the duration of the infarction. Using the spectral features identified, an effective tissue injury classification algorithm was developed which produced a satisfactory overall classification result (87.8%). The findings of this research support the concept that optical spectroscopy represents a useful tool to non-invasively determine the in vivo pathophysiological features of a myocardial infarct and its surrounding tissue, thereby providing valuable real-time feedback to surgeons during various surgical interventions for MI.

Synthesis and electron emission properties of aligned carbon nanotube arrays

Carbon nanotubes (CNTs) have become one of the most interesting allotropes of carbon due to their intriguing mechanical, electrical, thermal and optical properties. The synthesis and electron emission properties of CNT arrays have been investigated in this work. Vertically aligned CNTs of different densities were synthesized on copper substrate with catalyst dots patterned by nanosphere lithography. The CNTs synthesized with catalyst dots patterned by spheres of 500 nm diameter exhibited the best electron emission properties with the lowest turn-on/threshold electric fields and the highest field enhancement factor. Furthermore, CNTs were treated with NH3 plasma for various durations and the optimum enhancement was obtained for a plasma treatment of 1.0 min. CNT point emitters were also synthesized on a flat-tip or a sharp-tip to understand the effect of emitter geometry on the electron emission. The experimental results show that electron emission can be enhanced by decreasing the screening effect of the electric field by neighboring CNTs. In another part of the dissertation, vertically aligned CNTs were synthesized on stainless steel (SS) substrates with and without chemical etching or catalyst deposition. The density and length of CNTs were determined by synthesis time. For a prolonged growth time, the catalyst activity terminated and the plasma started etching CNTs destructively. CNTs with uniform diameter and length were synthesized on SS substrates subjected to chemical etching for a period of 40 minutes before the growth. The direct contact of CNTs with stainless steel allowed for the better field emission performance of CNTs synthesized on pristine SS as compared to the CNTs synthesized on Ni/Cr coated SS. Finally, fabrication of large arrays of free-standing vertically aligned CNT/SnO2 core-shell structures was explored by using a simple wet-chemical route. The structure of the SnO2 nanoparticles was studied by X-ray diffraction and electron microscopy. Transmission electron microscopy reveals that a uniform layer of SnO2 is conformally coated on every tapered CNT. The strong adhesion of CNTs with SS guaranteed the formation of the core-shell structures of CNTs with SnO2 or other metal oxides, which are expected to have applications in chemical sensors and lithium ion batteries.

In Vivo Characterization of Myocardial Tissue Post Myocardial Infarction Using Combined Fluorescence and Diffuse Reflectance Spectroscopy

Accurately assessing the extent of myocardial tissue injury induced by Myocardial infarction (MI) is critical to the planning and optimization of MI patient management. With this in mind, this study investigated the feasibility of using combined fluorescence and diffuse reflectance spectroscopy to characterize a myocardial infarct at the different stages of its development. An animal study was conducted using twenty male Sprague-Dawley rats with MI. In vivo fluorescence spectra at 337 nm excitation and diffuse reflectance between 400 nm and 900 nm were measured from the heart using a portable fiber-optic spectroscopic system. Spectral acquisition was performed on - (1) the normal heart region; (2) the region immediately surrounding the infarct; and (3) the infarcted region - one, two, three and four weeks into MI development. The spectral data were divided into six subgroups according to the histopathological features associated with various degrees / severities of myocardial tissue injury as well as various stages of myocardial tissue remodeling, post infarction. Various data processing and analysis techniques were employed to recognize the representative spectral features corresponding to various histopathological features associated with myocardial infarction. The identified spectral features were utilized in discriminant analysis to further evaluate their effectiveness in classifying tissue injuries induced by MI. In this study, it was observed that MI induced significant alterations (p < 0.05) in the diffuse reflectance spectra, especially between 450 nm and 600 nm, from myocardial tissue within the infarcted and surrounding regions. In addition, MI induced a significant elevation in fluorescence intensities at 400 and 460 nm from the myocardial tissue from the same regions. The extent of these spectral alterations was related to the duration of the infarction. Using the spectral features identified, an effective tissue injury classification algorithm was developed which produced a satisfactory overall classification result (87.8%). The findings of this research support the concept that optical spectroscopy represents a useful tool to non-invasively determine the in vivo pathophysiological features of a myocardial infarct and its surrounding tissue, thereby providing valuable real-time feedback to surgeons during various surgical interventions for MI.

Improving the identification of high-z Herschel sources with position priors and optical/NIR and FIR/mm photometric redshifts

We present preliminary results about the detection of high redshift (U)LIRGs in the Bullet cluster field by the PACS and SPIRE instruments within the Herschel Lensing Survey (HLS) Program. We describe in detail a photometric procedure designed to recover robust fluxes and deblend faint Herschel sources near the confusion noise. The method is based on the use of the positions of Spitzer/MIPS 24 μm sources as priors. Our catalogs are able to reliably (5σ) recover galaxies with fluxes above 6 and 10 mJy in the PACS 100 and 160 μm channels, respectively, and 12 to 18 mJy in the SPIRE bands. We also obtain spectral energy distributions covering the optical through the far-infrared/millimeter spectral ranges of all the Herschel detected sources, and analyze them to obtain independent estimations of the photometric redshift based on either stellar population or dust emission models. We exemplify the potential of the combined use of Spitzer position priors plus independent optical and IR photometric redshifts to robustly assign optical/NIR counterparts to the sources detected by Herschel and other (sub-)mm instruments.

Atomic vapor deposition of bismuth titanate thin films

c-axis oriented ferroelectric bismuth titanate (Bi4Ti 3O12) thin films were grown on (001) strontium titanate (SrTiO3) substrates by an atomic vapor deposition technique. The ferroelectric properties of the thin films are greatly affected by the presence of various kinds of defects. Detailed x-ray diffraction data and transmission electron microscopy analysis demonstrated the presence of out-of-phase boundaries (OPBs). It is found that the OPB density changes appreciably with the amount of titanium injected during growth of the thin films. Piezo-responses of the thin films were measured by piezo-force microscopy. It is found that the in-plane piezoresponse is stronger than the out-of-plane response, due to the strong c-axis orientation of the films.

Piezoresponse force microscopy investigations of Aurivillius phase thin films

The sol-gel synthesis and characterization of n≥3n≥3 Aurivillius phase thin filmsdeposited on Pt/Ti/SiO2–SiPt/Ti/SiO2–Si substrates is described. The number of perovskite layers, nn, was increased by inserting BiFeO3BiFeO3 into three layered Aurivillius phase Bi4Ti3O12Bi4Ti3O12 to form compounds such as Bi5FeTi3O15Bi5FeTi3O15 (n=4)(n=4). 30% of the Fe3+Fe3+ ions in Bi5FeTi3O15Bi5FeTi3O15 were substituted with Mn3+Mn3+ ions to form the structureBi5Ti3Fe0.7Mn0.3O15Bi5Ti3Fe0.7Mn0.3O15. The electromechanical responses of the materials were investigated using piezoresponse force microscopy and the results are discussed in relation to the crystallinity of the films as measured by x-ray diffraction.

Magnetic field-induced ferroelectric switching in multiferroic aurivillius phase thin films at room temperature

Single-phase multiferroic materials are of considerable interest for future memory and sensing applications. Thin films of Aurivillius phase Bi 7Ti3Fe3O21 and Bi6Ti 2.8Fe1.52Mn0.68O18 (possessing six and five perovskite units per half-cell, respectively) have been prepared by chemical solution deposition on c-plane sapphire. Superconducting quantum interference device magnetometry reveal Bi7Ti3Fe 3O21 to be antiferromagnetic (TN = 190 K) and weakly ferromagnetic below 35 K, however, Bi6Ti2.8Fe 1.52Mn0.68O18 gives a distinct room-temperature in-plane ferromagnetic signature (Ms = 0.74 emu/g, μ0Hc =7 mT). Microstructural analysis, coupled with the use of a statistical analysis of the data, allows us to conclude that ferromagnetism does not originate from second phase inclusions, with a confidence level of 99.5%. Piezoresponse force microscopy (PFM) demonstrates room-temperature ferroelectricity in both films, whereas PFM observations on Bi6Ti2.8Fe1.52Mn0.68O18 show Aurivillius grains undergo ferroelectric domain polarization switching induced by an applied magnetic field. Here, we show for the first time that Bi6Ti2.8Fe1.52Mn0.68O18 thin films are both ferroelectric and ferromagnetic and, demonstrate magnetic field-induced switching of ferroelectric polarization in individual Aurivillius phase grains at room temperature.

Heterogeneously grown tunable group-IV laser on silicon

Tunable tensile-strained germanium (epsilon-Ge) thin films on GaAs and heterogeneously integrated on silicon (Si) have been demonstrated using graded III-V buffer architectures grown by molecular beam epitaxy (MBE). epsilon-Ge epilayers with tunable strain from 0% to 1.95% on GaAs and 0% to 1.11% on Si were realized utilizing MBE. The detailed structural, morphological, band alignment and optical properties of these highly tensile-strained Ge materials were characterized to establish a pathway for wavelength-tunable laser emission from 1.55 μm to 2.1 μm. High-resolution X-ray analysis confirmed pseudomorphic epsilon-Ge epitaxy in which the amount of strain varied linearly as a function of indium alloy composition in the InxGa1-xAs buffer. Cross-sectional transmission electron microscopic analysis demonstrated a sharp heterointerface between the epsilon-Ge and the InxGa1-xAs layer and confirmed the strain state of the epsilon-Ge epilayer. Lowtemperature micro-photoluminescence measurements confirmed both direct and indirect bandgap radiative recombination between the Γ and L valleys of Ge to the light-hole valence band, with L-lh bandgaps of 0.68 eV and 0.65 eV demonstrated for the 0.82% and 1.11% epsilon-Ge on Si, respectively. The highly epsilon-Ge exhibited a direct bandgap, and wavelength-tunable emission was observed for all samples on both GaAs and Si. Successful heterogeneous integration of tunable epsilon-Ge quantum wells on Si paves the way for the implementation of monolithic heterogeneous devices on Si.

Competing anisotropies in exchange biased nano-structured thin films

The magnetic anisotropies of a patterned, exchange biased Fe50Mn50/Ni80Fe20 system are studied using ferromagnetic resonance, supplemented by Brillouin light scattering experiments and Kerr magnetometry. The exchange biased bi-layer is partially etched into an antidot geometry so that the system approximates a Ni80 Fe20 layer in contact with antidot structured Fe50 Mn50 . Brillouin light scattering measurements of the spin wave frequency dependence on the wave vector reveal a magnonic band gap as expected for a periodic modulation of the magnetic properties. Analysis of the ferromagnetic resonance spectra reveals 8-fold and 4-fold contributions to the magnetic anisotropy. Additionally, the antidot patterning decreases the magnitude of the exchange bias and modifies strongly its angular dependence. Softening of all resonance modes is most pronounced for the applied magnetic field aligned within 10◦ of the antidot axis, in the direction of the bias. Given the degree to which one can tailor the ground state, the resulting asymmetry at low frequencies could make this an interesting candidate for applications such as selective/directional microwave filtering and multi-state magnetic logic.

Multiferroic Iron Oxide Thin Films at Room Temperature

Multiferroic behaviour at room temperature is demonstrated in ε-Fe2O3. The simple composition of this new ferromagnetic ferroelectric oxide and the discovery of a robust path for its thin film growth by using suitable seed layers may boost the exploitation of ε-Fe2O3 in novel devices.

Spray Pyrolysed Tin Chalcogenide Thin Films: Optimization of optoelectronic properties of SnS for possible photovoltaic application as an absorber layer

In the early 19th century, industrial revolution was fuelled mainly by the development of machine based manufacturing and the increased use of coal. Later on, the focal point shifted to oil, thanks to the mass-production technology, ease of transport/storage and also the (less) environmental issues in comparison with the coal!! By the dawn of 21st century, due to the depletion of oil reserves and pollution resulting from heavy usage of oil the demand for clean energy was on the rising edge. This ever growing demand has propelled research on photovoltaics which has emerged successful and is currently being looked up to as the only solace for meeting our present day energy requirements. The proven PV technology on commercial scale is based on silicon but the recent boom in the demand for photovoltaic modules has in turn created a shortage in supply of silicon. Also the technology is still not accessible to common man. This has onset the research and development work on moderately efficient, eco-friendly and low cost photovoltaic devices (solar cells). Thin film photovoltaic modules have made a breakthrough entry in the PV market on these grounds. Thin films have the potential to revolutionize the present cost structure of solar cells by eliminating the use of the expensive silicon wafers that alone accounts for above 50% of total module manufacturing cost.

Insight into Biological Small-Molecule Activation from Enzymes, Model Complexes, and X-ray Spectroscopy

Thesis (Ph.D.)--University of Washington, 2016-08