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Metal Complexes for Organic Optoelectronic ApplicationsJanuary 2017 (has links)
abstract: Organic optoelectronic devices have drawn extensive attention by over the past two decades. Two major applications for Organic optoelectronic devices are efficient organic photovoltaic devices(OPV) and organic light emitting diodes (OLED). Organic Solar cell has been proven to be compatible with the low cost, large area bulk processing technology and processed high absorption efficiencies compared to inorganic solar cells. Organic light emitting diodes are a promising approach for display and solid state lighting applications. To improve the efficiency, stability, and materials variety for organic optoelectronic devices, several emissive materials, absorber-type materials, and charge transporting materials were developed and employed in various device settings. Optical, electrical, and photophysical studies of the organic materials and their corresponding devices were thoroughly carried out. In this thesis, Chapter 1 provides an introduction to the background knowledge of OPV and OLED research fields presented. Chapter 2 discusses new porphyrin derivatives- azatetrabenzylporphyrins for OPV and near infrared OLED applications. A modified synthetic method is utilized to increase the reaction yield of the azatetrabenzylporphyrin materials and their photophysical properties, electrochemical properties are studied. OPV devices are also fabricated using Zinc azatetrabenzylporphyrin as donor materials. Pt(II) azatetrabenzylporphyrin were also synthesized and used in near infra-red OLED to achieve an emission over 800 nm with reasonable external quantum efficiencies. Chapter 3, discusses the synthesis, characterization, and device evaluation of a series of tetradentate platinum and palladium complexesfor single doped white OLED applications and RGB white OLED applications. Devices employing some of the developed emitters demonstrated impressively high external quantum efficiencies within the range of 22%-27% for various emitter concentrations. And the palladium complex, i.e. Pd3O3, enables the fabrication of stable devices achieving nearly 1000h. at 1000cd/m2 without any outcoupling enhancement while simultaneously achieving peak external quantum efficiencies of 19.9%. Chapter 4 discusses tetradentate platinum and palladium complexes as deep blue emissive materials for display and lighting applications. The platinum complex PtNON, achieved a peak external quantum efficiency of 24.4 % and CIE coordinates of (0.18, 0.31) in a device structure designed for charge confinement and the palladium complexes Pd2O2 exhibited peak external quantum efficiency of up to 19.2%. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2017
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From Materials to Devices: (I) Ultrathin Flexible Implantable Bio-probes with Biodegradable Sacrificial Layers (II) Carrier Spin Injection and Transport in DiamondJanuary 2018 (has links)
abstract: My research has been focusing on the innovations of material and structure designs, and the development of fabrication processes of novel nanoelectronics devices.
My first project addresses the long-existing challenge of implantable neural probes, where high rigidity and high flexibility for the probe need to be satisfied at the same time. Two types of probes that can be used out of the box have been demonstrated, including (1) a compact probe that spontaneously forms three-dimensional bend-up devices only after implantation, and (2) an ultra-flexible probe as thin as 2 µm attached to a small silicon shaft that can be accurately delivered into the tissue and then get fully released in situ without altering its shape and position as the support is fully retracted. This work provides a general strategy to prepare ultra-small and flexible implantable probes that allow high insertion accuracy and minimal surgical damages with best biocompatibility.
My second project focuses on the injection and characterization of carrier spins in single crystal diamond based nanoscale devices. The conventional diamond-based quantum information process that exploits nitrogen vacancy centers faces a major barrier of large scale communication. Electron/hole spin in diamond devices, on the other hand, could also be a good candidate for quantum computing due to the very small spin-orbit coupling and great coherent transport length of spin. To date, there has been no demonstration of carrier spin transport in diamond. In this work, I try to answer this fundamental question of how to inject and characterize electron spins in Boron doped diamond. Nanoscale diamond devices have been fabricated to investigate this question, including Hall bar device for material characterization, and lateral spin valve for injecting spin-polarized current into a mesoscopic diamond bar and detecting induced pure spin current. The preliminary results show signatures of spin transport in heavily doped diamond films.
Looking into the future, the knowledge we obtained in these two projects, including the strategy to integrate thin-film nanoelectronics devices on a flexible bio-probe configuration, and how to build spintronic devices with diamond structures, could be unified in the exploration of spin-based sensors in biological systems. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2018
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Recycling Valuable Materials from Crystalline-Si Solar ModulesJanuary 2018 (has links)
abstract: A major obstacle to sustainable solar technologies is end-of-life solar modules. In this thesis, a recycling process is proposed for crystalline-Si solar modules. It is a three-step process to break down Si modules and recover various materials. Over 95% of a module by weight can be recovered with this process. Two new technologies are demonstrated to enable the proposed recycling process. One is sequential electrowinning which allows multiple metals to be recovered one by one from Si modules, Ag, Pb, Sn and Cu. The other is sheet resistance monitoring by the 4-point probe which maximizes the amount of solar-grade Si recovered from Si modules with high throughput. The purity of the recovered metals is above 99% and the recovery rate can achieve between 70~80%. The recovered Si meets the specifications for solar-grade Si and at least 91% of Si from c-Si solar cells can be recovered. The recovered Si and metals are new feedstocks to the solar industry and generate over $12/module in revenue. This revenue enables a profitable recycling business for Si modules without any government support. The chemicals for recycling are carefully selected to minimize their environmental impact and also the cost. A network for collecting end-of-life solar modules is proposed based on the current distribution network for solar modules to contain the collection cost. As a result, the proposed recycling process for c-Si modules is technically, environmentally and financially sustainable. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2018
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Study of Doped Magnetic SystemsJanuary 2018 (has links)
abstract: Doping and alloying agents are commonly used to engineer the properties of magnetic materials. This study investigates the effects of doping manganese in thin films of Ni80Fe20 (permalloy) and Ni65Fe15Co20 magnetic systems for low power memory technologies, including those that operate at low temperature.
Elemental manganese is anti-ferromagnetic with a Neel temperature of 100 K. When used as a dopant in a magnetic material, it is found to often align its moment in an antiferromagnetic direction. Thus, the addition of manganese might be expected to reduce the overall saturation magnetization (MS) of the magnetic system. In this study, we show that the use of manganese dopants in Ni80Fe20 (permalloy) and Ni65Fe15Co20 thin films can reduce their saturation magnetization and still retain excellent switching properties.
Magnetic properties and transport properties were determined using Vibrating Sample Magnetometer. A 19% decrease in the MS of (Ni80Fe20)1-xMnx thin films and a 36% decrease for (Ni65Fe15Co20)1-xMnx thin films for dopant levels of x = 30%. The impact of depositing a ruthenium (Ru) under-layer for (Ni65Fe15Co20)1-xMnx system was also studied.
The structural (lattice parameters and phases), surface (roughness and topography) and electrical properties (resistivity and mean free path) of the Mn-doped Ni65Fe15Co20 films were determined with X-Ray Diffraction, Atomic Force Microscopy and Four-Point probe technique respectively.
The properties were analyzed and Ni65Fe15Co20 system with Ru- under-layer with 20 at. % Mn content was found to exhibit the following low-field switching properties at 10 K; MS~700 emu.cm-3, easy axis coercivity ~10 Oe and hard axis coercivity ~5 Oe, easy axis squareness ~0.9 and anisotropy field ~12 Oe, that are deemed useful for low-power memory applications that could be used at cryogenic temperatures.
To determine the transport properties thought these magnetic layers for use in superconductor/ferromagnetic memory structures, a study of the oxidation conditions of Al films was performed in order to produce a reliable aluminum oxide tunnel barrier on top of these films. The production of N-I-F-S (Normal metal-Insulator-Ferromagnet-Superconductor) tunnel junctions will allow for the investigation of the tunneling density of states as a function of ferromagnetic layer thickness, allowing for the determination of important transport parameters relevant to magnetic barrier Josephson junction devices. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2018
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Interface Electronic State Characterization of Dielectrics on Diamond and C-BNJanuary 2018 (has links)
abstract: Diamond and cubic boron nitride (c-BN) are ultra wide band gap semiconductors (Eg>3.4 eV) and share similar properties in various aspects, including being isoelectronic, a 1% lattice mismatch, large band gap, high thermal conductivity. Particularly, the negative electron affinity (NEA) of diamond and c-BN is an unusual property that has led to effects such as p-type surface conductivity, low temperature thermionic emission, and photon enhanced thermionic emission. In this dissertation, the interface chemistry and electronic structure of dielectrics on diamond and c-BN are investigated with X-ray and ultraviolet photoemission spectroscopy (XPS and UPS). The first study established that the surface conductive states could be established for thin Al2O3 on diamond using a post deposition H-plasma process. At each step of the atomic layer deposition (ALD) and plasma processing, the band alignment was characterized by in situ photoemission and related to interface charges. An interface layer between the diamond and dielectric layer was proposed to explain the surface conductivity. The second study further investigated the improvement of the hole mobility of surface conductive diamond. A thin layer of Al2O3 was employed as an interfacial layer between surface conductive hydrogen-terminated (H-terminated) diamond and MoO3 to increase the distance between the hole accumulation layer in diamond and negatively charged states in acceptor layer. With an interfacial layer, the ionic scattering, which was considered to limit the hole mobility, was reduced. By combining two oxides (Al2O3 and MoO3), the hole mobility and concentration were modulated by altering the thickness of the Al2O3 interfacial layer. The third study focused on the electronic structure of vanadium-oxide-terminated c-BN surfaces. The vanadium-oxide-termination was formed on c-BN by combining vanadium deposition using molecular beam deposition (MBD) and oxygen plasma treatment. After thermal annealing, a thermally stable NEA was achieved on c-BN. A model was proposed based on the deduced interface charge distribution to explain the establishment of an NEA. / Dissertation/Thesis / Doctoral Dissertation Physics 2018
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Transmission Electron Microscopy Study of the Two-Dimensional Electron Gas at SrTiO3-Based Oxide InterfacesJanuary 2018 (has links)
abstract: The two-dimensional electron gas (2DEG) at SrTiO3-based oxide interfaces has been extensively studied recently for its high carrier density, high electron mobility, superconducting, ferromagnetic, ferrroelectric and magnetoresistance properties, with possible application for all-oxide devices. Understanding the mechanisms behind the 2DEG formation and factors affecting its properties is the primary objective of this dissertation.
Advanced electron microscopy techniques, including aberration-corrected electron microscopy and electron energy-loss spectroscopy (EELS) with energy-loss near-edge structure (ELNES) analysis, were used to characterize the interfaces. Image and spectrum data-processing algorithms, including subpixel atomic position measurement, and novel outlier detection by oversampling, subspace division based EELS background removal and bias-free endmember extraction algorithms for hyperspectral unmixing and mapping were heavily used. Results were compared with density functional theory (DFT) calculations for theoretical explanation.
For the γ-Al2O3/SrTiO3 system, negative-Cs imaging confirmed the formation of crystalline γ-Al2O3. ELNES hyperspectral unmixing combined with DFT calculations revealed that oxygen vacancies, rather than polar discontinuity, were the key to the 2DEG formation. The critical thickness can be explained by shift of the Fermi level due to Ti out diffusion from the substrate to the film.
At the LaTiO3/SrTiO3 interface, aberration-corrected imaging showed crystallinity deterioration in LaTiO3 films a few unit cells away from the interface. ELNES showed that oxygen annealing did not alter the crystallinity but converted Ti3+ near the interface into Ti4+, which explained disappearance of the conductivity.
At the EuO/SrTiO3 interface, both high-resolution imaging and ELNES confirmed EuO formation. ELNES hyperspectral unmixing showed a Ti3+ layer confined to within several unit cells of the interface on the SrTiO3 side, confirming the presence of oxygen vacancies.
At the BaTiO3/SrTiO3 interface, spontaneous polarization and local lattice parameters were measured directly in each unit cell column and compared with oxidation state mapping using ELNES with unit-cell resolution. The unusually large polarization near the interface and the polarization gradient were explained by oxygen vacancies and the piezoelectric effect due to epitaxial strain and strain gradient from relaxation. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2018
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Selenate and Chromate Removal with Titanium Dioxide based PhotocatalystsJanuary 2018 (has links)
abstract: As selenium and chromium are toxic even at low levels, it is very necessary to remove them from drinking water with proper ways. In this work, titanium dioxide based photocatalysts were mainly investigated in detail for their photoreduction ability towards selenate and chromate in aqueous environment. Firstly, photoreduction ability of layered double hydroxide (LDH) nanosheets with commercial TiO2 particle hybrid materials was investigated towards selenate or chromate. The results showed that commercial LDH/TiO2 (P90) composite, homemade LDH nanosheets/TiO2 (P90) composite and also in situ LDH/TiO2 (P25) composite all did not indicate significant improvement on photoreduction performance towards selenate or chromate. Secondly, TiO2 nanosheets material was synthesized with TiS2 as precursor via hydrothermal treatment. Morphology of TiO2 nanosheets were characterized by SEM, AFM and TEM. Photodegradation of MB (methylene blue) with TiO2 nanosheets was performed. In the future, first approach is to synthesize visible-light driven LDH photocatalyst NiFe-LDH nanosheets with TiO2 nanosheets hybrid material for selenate removal. Second approach is to use anion intercalation/insertion via electrochemical process to remove anions in drinking water. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2018
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Electrochemical Stability of Nanoscale ElectrodesJanuary 2012 (has links)
abstract: The electrochemical behavior of nanoscale solids has become an important topic to applications, such as catalysis, sensing, and nano–electronic devices. The electrochemical behavior of elemental metal and alloy particles was studied in this work both theoretically and experimentally. A systematic thermodynamic derivation for the size–dependent Pourbaix Diagram for elemental metal particles is presented. The stability of Pt particles was studied by in situ electrochemical scanning tunneling microscopy (ECSTM). It is shown that small Pt particles dissolve at a lower potential than the corresponding bulk material. For the alloy particles, two size ranges of AuAg particles, ∼4 nm and ∼45 nm in diameter, were synthesized by co–reduction of the salts of Au and Ag from an aqueous phase. The alloy particles were dealloyed at a series of potential by chronoamperometry in acid, and the resulting morphology and composition were characterized by electron microscopy, energy dispersive X–ray spectroscopy (EDX). In the case of the smaller particles, only surface dealloying occurred yielding a core–shell structure. A porous structure was observed for the larger particles when the potential was larger than a critical value that was within 50 mV of the thermodynamic prediction. / Dissertation/Thesis / Ph.D. Engineering 2012
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Electrochemical and Photoelectrochemical Properties of the Copper Hydroxyphosphate Mineral LibetheniteJanuary 2013 (has links)
abstract: There has been much interest in photoelectrochemical conversion of solar energy in recent years due to its potential for low-–cost, sustainable and renewable production of fuels. Despite the huge potential, there are still a number of technical barriers due to the many constraints needed in order to drive photoelectrochemical reactions such as overall water splitting and the identification of efficient and effective semiconductor materials. To this end, the search for novel semiconductors that can act as light absorbers is still needed. The copper hydroxyphosphate mineral libethenite (CHP), which has a chemical formula of Cu2(OH)PO4, has been recently shown to be active for photocatalytic degradation of methylene blue under UV-–irradiation, indicating that photo-excited electrons and holes can effectively be generated and separated in this material. However, CHP has not been well studied and many of its fundamental electrochemical and photoelectrochemical properties are still unknown. In this work, the synthesis of different morphologies of CHP using hydrothermal synthesis and precipitation methods were explored. Additionally, a preliminary investigation of the relevant fundamental characteristics such as the bandgap, flatband potential, band diagram, electrochemical and photoelectrochemical properties for CHP was performed. Better understanding of the properties of this material may lead to the development of improved catalysts and photocatalysts from natural sources. / Dissertation/Thesis / M.S. Materials Science and Engineering 2013
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Atom Dynamics of Amorphous Materials by X-Ray Photon Correlation Spectroscopy (XPCS) & Neutron SpectroscopySarker, Suchismita 14 December 2017 (has links)
<p> The mitigation of greenhouse gas emissions on the environment led to the development of non-polluting hydrogen fuel cell use in automobiles. Syngas produced from coal gasification is converted to H<sub>2</sub> and CO2 gasses by the water shift reaction. Metallic membranes are used to separate H<sub> 2</sub> from CO<sub>2</sub> and other gasses obtained from the water shift reaction of coal-derived syngas. Commercial crystalline Pd-Ag membranes are widely used for this purpose; however, Pd is an expensive strategic metal. Thus, inexpensive Ni-Nb-Zr alloys are studied.The permeation property of amorphous membranes are known, however, the mechanism of permeation and the nature of the local atomic order of the amorphous membranes was not fully understood. </p><p> In this study, atom dynamics studied by synchrotron x-ray photon correlation spectroscopy (XPCS) showed the movement of heavier elements such as Ni, Nb, and Zr, at room temperature and 373K. The addition of hydrogen significantly accentuates the motion of atoms as the hydrogen occupies the tetrahedral sites within the icosahedra leading to expansion and short-range diffusion, and no long-range diffusion is observed estimated to be ∼10<sup>-22</sup> m<sup>2</sup>/s. Vacuum removal of hydrogen from these membranes showed a contraction of the icosahedra and approached to its original position. This suggests that the process reversible due to the pressure gradient. The XPCS results did not reveal the specific position of hydrogen atoms in the icosahedra; hydrogen goes into the tetrahedral sites of Zr<sub>4</sub> and distorted Nb<sub>4</sub> sites as determined by neutron vibrational spectroscopy. Total neutron scattering and DFT-MD simulation determine the short-range order of up to 1.8 nm and the nearest neighbor bond distances. Determination of cluster formation was first attempted by using small neutron scattering, but it did not have appropriate “Q” range. Thus atom probe tomography (APT) was attempted. This APT study revealed Nb-rich and Zr-rich clusters embedded in Ni-rich matrix, whose compositions are reported. DFT-MD simulation reveals interconnected icosahedra in the metal matrix. The atom dynamics (NVS and XPCS), atom probe tomography, total neutron scattering studies are discussed which have implication in the mechanisms of hydrogen permeation in amorphous metallic membranes.</p><p>
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