As existing energy sources have been depleting at a fast pace, thermoelectric (TE) materials have received much attention in recent years because of their role in clean energy generation and conversion. Thermoelectric materials hold promise in terrestrial applications such as waste heat recovery. Bismuth selenide (Bi2Se3), lead telluride (PbTe), skutterudites CoSb3, and Bi-Sb alloys are among the widely investigated thermoelectric materials. Synthesis of above mentioned thermoelectric materials in nanostructured form and their characterization were investigated. Highly crystalline Bi2Se3, undoped and indium (In) doped PbTe, unfilled and ytterbium (Yb) filled CoSb3 nanomaterials were synthesized using hydrothermal/solvothermal technique and Ca-doped Bi-Sb alloy was synthesized using ball milling method. The mechanism of indium doping to the PbTe matrix was investigated using X-ray diffraction, laser-induced breakdown spectroscopy (LIBS) and a first principle calculation. It was found that indium doping, at a level below 2%, is substitution on Pb site. The effects of the amount of sodium borohydride (NaBH4) as the reducing agent and the annealing treatment on the phase transition of CoSb3 were investigated. It was found that a sufficient amount of NaBH4 along with the specific annealing condition was needed for the formation of pure phase CoSb3. Thermoelectric properties of Bi2Se3 and Ca-doped Bi85Sb15 were also investigated. A lower thermal conductivity and a higher Seebeck coefficient were achieved for a Bi2Se3 sample prepared in dimethyl formamide (DMF) at 200ºC for 24 h as compared to bulk Bi2Se3. The decrease in thermal conductivity can be attributed to the increased phonon scattering at the interfaces of the nanostructures and at the grain boundaries in the bulk nanocomposite. The increase in the Seebeck coefficient of Bi2Se3 nanostructures is likely the result of the quantum confinement of the carriers in nanostructures. The effect of calcium doping on Bi85Sb15 nanostructures were investigated. It was found that 2% calcium doped Bi-Sb alloy showed the best TE efficiency due to the enhanced power factor and reduced thermal conductivity.

abstract: Programmable Metallization Cell (PMC) devices are, in essence, redox-based solid-state resistive switching devices that rely on ion transport through a solid electrolyte (SE) layer from anode to cathode. Analysis and modeling of the effect of different fabrication and processing parameter/conditions on PMC devices are crucial for future electronics. Furthermore, this work is even more significant for devices utilizing back-end- of-line (BEOL) compatible materials such as Cu, W, their oxides and SiOx as these devices offer cost effectiveness thanks to their inherent foundry-ready nature. In this dissertation, effect of annealing conditions and cathode material on the performance of Cu-SiOx vertical devices is investigated which shows that W-based devices have much lower forming voltage and initial resistance values. Also, higher annealing temperatures first lead to an increase in forming voltage from 400 °C to 500 °C, then a drastic decrease at 550 °C due to Cu island formation at the Cu/SiOx interface. Next, the characterization and modeling of the bilayer Cu2O/Cu-WO3 obtained by annealing the deposited Cu/WO3 stacks in air at BEOL-compatible temperatures is presented that display unique characteristics for lateral PMC devices. First, thin film oxidation kinetics of Cu is studied which show a parabolic relationship with annealing time and an activation energy of 0.70 eV. Grown Cu2O shows a cauliflower-like morphology where feature size on the surface increase with annealing time and temperature. Then, diffusion kinetics of Cu in WO3 is examined where the activation energy of diffusion of Cu into WO3 is calculated to be 0.74 eV. Cu was found to form clusters in the WO3 host which was revealed by imaging. Moreover, using the oxidation and diffusion analyses, a Matlab model is established for modeling the bilayer for process and annealing-condition optimization. The model is built to produce the resulting Cu2O thickness and Cu concentration in Cu-WO3. Additionally, material characterization, preliminary electrical results along with modeling of lateral PMC devices utilizing the bilayer is also demonstrated. By tuning the process parameters such as deposited Cu thickness and annealing conditions, a low-resistive Cu2O layer was achieved which dramatically enhanced the electrodeposition growth rate for lateral PMC devices. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2020

<div><div><div><p>When confined to a finite, two-dimensional area and exposed to a strong magnetic field, electrons exhibit a complicated, highly correlated quantum behavior known as the quantum Hall effect. This dissertation consists of finite size numerical investigations of this effect. One line of study develops treatment of the fractional quantum Hall effect using the hyperspherical method, in conjunction with applications to the few-body quantum Hall systems, e.g., highly-controlled atomic systems. Another line of research fully utilizes the developed numerical techniques to study on the platform of finite size fractional quantum Hall states the bulk-edge correspondence principle, which is universal for phases in topological orders. It has been demonstrated that the eigenstates associated with the entanglement spectrum reveal more information about the ground state than the spectrum alone.</p></div></div></div>

Information on the sensitivity of explosives is highly valuable, and the short time scales in which chemical reactions occur in explosives, along with the ability of microstructure to have significant effects on sensitivity, often make this information difficult and expensive to acquire and interpret. Significant changes in impact and shock sensitivity are expected as a result of inducing structural damage in an explosive sample, and thermally damaged HMX-based samples can incur a solid-solid phase transition from beta to delta with non-extreme thermal inputs. Changes in sensitivity due to this phase transition, as well as the simultaneously induced damage, and their relative influence on sensitivity, are of interest to determine experimentally. <div><br></div><div>Drop-weight impact tests are a commonly used measure of explosive impact sensitivity. Often, simply the L50 of a given material is reported and compared with that of other materials to give a sense of its impact sensitivity. The practice of reporting the impact sensitivity as a single number, the L50, is likely inadequate. It is important to additionally report a measure of the spread of the distribution of reaction probabilities in order to assess the hazard of reaction in situations that may induce a stimulus level well below the L50 of a material. Additionally, multiple distribution forms have been suggested previously for fitting of binary sensitivity data; these distributions typically deviate from each other most near the tails (low and high stimulus levels). The consequences of choosing one distribution form over another in the analysis of explosive drop-weight impact results is explored.<br></div><div><br></div><div>Changes in impact sensitivity due to phase change have received some previous exploration, though the phase change influence is generally conflated with the induced damage upon said phase transition; however, sensitivity changes in the shock regime due to beta to delta-phase change have received little attention. Work is shown which includes methods to isolate variables of HMX phase transition and damage typically incurred upon said phase transition.<br></div>

Although band theory is about a century old, it remains relevant today as a tool for the treatment of electrons in solids. The confluence of mathematical ideas like geometry and topology with band theory has proven to be a ripe avenue for research in the past few decades. The importance of Fermi surface geometry, especially in conjunction with electronic correlation, has been well recognized. One particular thread in this direction is probing the occurrence of non-trivial Fermi surface geometry, and its influence on macroscopic properties of materials. A notable example of exotic Fermi surface geometry arises from singular points of the dispersion, and these have been known since 1953. The investigation into these was reignited recently, culminating in the work presented in this thesis. In this dissertation, I investigate two broad categories of singular points in bands. At a singular point, either the dispersion or the Fermi surface fail to be smooth. This may cause distinct signatures in transport and spectroscopic properties when the singular point occurs close to the Fermi level. In the two dimensional setting, I classify using catastrophe theory, the point singularities arising from higher order saddles of the dispersion. These are the more exclusive cousins of the regular van Hove saddle that cause, among other things, a power law divergence in the density of states. The role of lattice symmetries in aiding or preventing the occurrence of these singularities is also carefully explored. In the case of three dimensional bands, I investigate the spectroscopic properties of the nodal point singularity, arising from a linear band crossing. In particular, I determine the distinct signature of nodal points in the analytic, momentum resolved, joint density of states (JDOS) and the numerically calculated resonant inelastic x-ray scattering (RIXS) spectrum, within the fast collision approximation that ignores core hole effects. The results presented here will be the stepping stone towards a careful future calculation, incorporating the potential edge singularity effects through core hole potential. Such a calculation may be directly comparable with ongoing experiments.

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No description available.

Multi-component coatings and high entropy alloys have in recent years attracted great interest for research, since they have shown to exhibit properties greater than the com- ponents of their parts. Today’s climate challenges requires transitioning from fossil fuels to renewable energy sources which demands use of new technology and new innovations. The hydrogen fuel cell is a technology which produces no carbon emissions, and the drive for innovation has led researchers to apply multi-component (high entropy alloys) coatings to invent the next generation hydrogen fuel cells and help the transition to renewable energy sources. This thesis has investigated the process-structure-property relationships of four deposi- tion growth parameters: target current (Itarget), argon pressure (PAr). substrate bias (Vsubstrate) and deposition time (tdeposition) on TiNbZrTa-coatings, grown by magnetron sputtering using an industrial deposition system. The range of the parameters have been: Itarget from 2.5 to 6 A, PAr from 1 to 17 mTorr, Vsubstrate from 30 to 200 V and tdeposition from 3.6 to 12 minutes (depending on Itarget). Coatings have been grown on Si (001) and stainless steel 304 and 316L substrates. The coating microstructure was analyzed by X-ray diffraction and electron microscopy. The results have yielded that all coatings are equimolar and that the coatings exhibit three different morphologies, two different topologies and two different corresponding structures. The different morphologies are wave, coarse columnar and fine columnar morphology. The two topologies are nodular and dune surface topology. The two different structures are a solid solution BCC (110) phase and an amorphous or nanocrystalline phase. The results indicate that parameters affecting the temperature of the substrate (Tsubstrate) is the prime decider for the final morphology of the coatings. High Itarget and Vsubstrate, low PAr and long tdeposition all increases Tsubstrate and results in a coating which exhibits a fine columnar morphology, dune topology and a solid solution BCC phase. These types of coatings have also proven to have improved corrosion resistance compared to the other type of coatings seen in this thesis. The other kind of coating is grown with low Itarget and Vsubstrate, high PAr and short tdeposition, which causes minimal increase of Tsubstrate. These growth parameters result in a coating with coarse columnar morphology, nodular topology and amorphous or nanocrystalline phase, with less corrosion resistance. / FunMat II

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Due to the complex nature of phase interfaces, acquiring precise interfacial energies is usually a big challenge for both experimental measurements and computational modelings. In this thesis, we put forward an efficient route for assessing the temperature dependence of the interfacial energy using density functional theory (DFT). For our investigations, we select the Cu-Co binary system as a model with large miscibility gap. Most of the first-principles calculations presented here are carried out using the exact muffin-tin orbitals (EMTO) method in combination with the coherent potential approximation (CPA), but other alternative DFT methods are also included in the various stages of the project.The first step is to acquire an accurate thermodynamical description of the Cu-Co binary system. We assess the quality of the predicted thermodynamic properties by an effort to reproduce the phase diagram for the entire range of composition using first-principles calculations and alloy theory. The calculations are performed for the random Cu-Co alloys with face-centered cubic (fcc) structure at both ferromagnetic (FM) and paramagnetic (PM) states, depending on the composition. We demonstrate that the equilibrium volumes and magnetic states are crucial for the proper description of the magnetic entropy of the Cu-Co system at elevated temperatures. More specifically, the contribution of magnetic entropy to the free energy in the Cu-rich region obtained for the PM state turns out to be critical. Furthermore, the adopted equilibrium volumes strongly affect the contribution of the vibrational entropy to the free energy. When all effects are properly accounted for, we find that the ab initio phase diagram of the Cu-Co system agrees well with the Thermo-Calc phase diagram and the experimental observations.The Cu-Co system has a large miscibility gap. The interface between the decomposed Cu-rich and Co-rich phases plays critical roles in the precipitation nucleation and growth, therefore having huge effects on the physical and mechanical properties of the alloys. Therefore, adopting the thermodynamical properties of the bulk Cu-Co alloys successfully obtained by our ab initio calculations, we go further and investigate the interfacial properties of the Cu-Co alloys using a coherent interface model. The chemical, magnetic, and strain energy contributions to the formation energy of the interfaces are analyzed separately. We find that the chemical interfacial energies generally decrease with increasing concentrations, namely when the compositions accross the interface become more homogenous. We identify a sizable contribution to the interfacial energies from the magnetic effects. The temperature dependence of the interfacial energy is estimated, to the first-order approximation, through considering how the equilibrium compositions of the two phases vary at different temperatures. Our results show that the temperature dependence of the interfacial energy originates primarily from the temperature-induced increase of the mutual solubility of the alloy constituents and the loss of the magnetic long range order near the Curie temperature. Our ab initio results are compared with the experimental data as well as with those extracted from Thermo-Calc modeling. The present thesis provides an atomic-level description of the bulk and interfacial properties of the Cu-Co binary system using quantum mechanics simulations. This approach is believed to be useful for a complete thermodynamical description of other similar immiscible alloy systems as well from first-principles. / På grund av fasgränssnittens komplexa karaktär är det vanligtvis en stor utmaning att få exakta gränssnittsenergier för både experimentella mätningar och beräkningsmodeller. I denna avhandling presenterar vi en effektiv väg för att bedöma temperaturberoendet för gränssnittsenergin med hjälp av densitetsfunktionell teori (DFT) i ett modellsystem, Cu-Co-legeringar. Våra första principberäkningar är baserade på den exakta muffins-tennorbitalmetoden (EMTO) i kombination med den koherenta potential-approximationen (CPA).Det första steget är att skaffa en noggrann termodynamisk beskrivning för det binära systemet. Vi bedömer kvaliteten på de förutsagda termodynamiska egenskaperna genom ett försök att reproducera fasdiagrammet för hela kompositionen med hjälp av första principberäkningar och legeringsteori. Beräkningarna utförs för de slumpmässiga Cu-Co-legeringarna med ansiktscentrerad kubisk (fcc) struktur vid både ferromagnetiska (FM) och paramagnetiska (PM) tillstånd, beroende på sammansättningen. Vi visar att jämviktsvolymer och magnetiska tillstånd är avgörande för en korrekt beskrivning av den magnetiska entropin i Cu-Co-systemet vid förhöjda temperaturer. Närmare bestämt visar sig den magnetiska entropins bidrag till den fria energin i den Cu-rika regionen som erhålls vid PM-tillståndet vara kritisk. Vidare påverkar de antagna jämviktsvolymerna starkt vibrationsentropins bidrag till den fria energin. När alla effekter är korrekt redovisade kommer vi fram till att ab initio fasdiagrammet för Cu-Co-systemet överensstämmer väl med experimentellt resultat.Cu-Co-systemet har ett stort blandningsgap. Gränssnittet mellan de sönderdelade Cu-rika och Co-rika faserna spelar en avgörande roll för nederbördskärnbildning och tillväxt och har därför enorma effekter på legeringarnas fysiska och mekaniska egenskaper. Här, med de termodynamiska egenskaperna hos bulk-Cu-Co-legeringarna framgångsrikt erhållna med våra ab initio-tillvägagångssätt, går vi vidare och undersöker gränssnittsegenskaperna för Cu-Co-legeringarna med en koherent gränssnittsmodell. De kemiska, magnetiska och stamenergibidragen till gränssnittets bildningsenergi analyseras separat. Vi finner att de kemiska gränssnittsenergierna generellt minskar med ökande koncentrationer, nämligen när kompositionerna över gränssnittet blir mer homogena. Vi identifierar ett betydande bidrag till gränssnittsenergierna från de magnetiska effekterna. Temperaturberoendet för gränssnittsenergin uppskattas, till första ordningens approximation, genom att överväga hur jämviktskompositionerna i de två faserna varierar vid olika temperaturer. Våra resultat visar att temperaturberoendet för gränssnittsenergin främst härrör från den temperaturinducerade ökningen av legeringskomponenternas ömsesidiga löslighet och förlusten av magnetisk långdistansordning nära Curie-temperaturen. Våra ab initio resultat jämförs med experimentella data såväl som med de som extraherats från Thermo-Calc-modellering.Föreliggande avhandling ger en atomnivåbeskrivning av bulk- och gränssnittsegenskaper hos Cu-Co-binära systemet med hjälp av kvantemekaniska simuleringar, vilket antas vara användbart för en fullständig termodynamisk beskrivning av liknande icke-blandbara legeringssystem med exakta initieringsmetoder.