Multifunctional nanocomposites are promising for a variety of applications ranging from microwave devices to biomedicine. High demand exists for magnetically tunable nanocomposite materials. My thesis focuses on synthesis and characterization of novel nanomaterials such as polymer nanocomposites (PNCs) and multi-walled carbon nanotubes (MWCNTs) with magnetic nanoparticle (NP) fillers. Magnetite (Fe3O4) and cobalt ferrite (CoFe2O4) NPs with controlled shape, size, and crystallinity were successfully synthesized and used as PNC fillers in a commercial polymer provided by the Rogers Corporation and poly(vinylidene fluoride). Magnetic and microwave experiments were conducted under frequencies of 1-6 GHz in the presence of transverse external magnetic fields of up to 4.5 kOe. Experiments confirm strong magnetic field dependence across all samples. When incorporated in to a cavity resonator device, tangent losses were reduced, quality factor increased by 5.6 times, and tunability of the resonance frequency was demonstrated, regardless of NP-loading. Work on PNC materials revealed the importance of NP interactions in confined spaces and motivated the study of confinement effects of magnetic NPs in more controlled environments, such as MWCNTs with varying diameters. MWCNTs were synthesized with diameters of 60 nm, 100 nm, 250 nm, and 450 nm to contain magnetic NP fillers (~10 nm) consisting of ferrites of the form MFe2O4, where M = Co2+, Ni2+, or Fe2+. All confined samples exhibit superparamagnetic-like behavior with stronger magnetic response with respect to increasing MWCNT diameter up to 250 nm due to the enhancement of interparticle interactions. This thesis provides the first systematic study of this class of nanocomposites, which paves the way to inclusion of novel nanostructured materials in real-world applications.

High-quality platelet single crystals of Tl₂Ba₂CuO₆±δ (Tl-2201) have been grown using a novel time-varying encapsulation scheme, minimizing the thallium oxide loss that has plagued other attempts and reducing cation substitution. This encapsulation scheme allows the melt to be decanted from the crystals, a step previously impossible, and the remaining cation substitution is homogenized via a high-temperature anneal. Oxygen annealing schemes were developed to produce sharp superconducting transitions from 5 to 85 K without damaging the crystals. The crystals' high homogeneity and high degree of crystalline perfection are further evidenced by narrow rocking curves; the crystals are comparable to YSZ-grown YBa₂Cu₃O₆₊δ by both metrics. Electron probe microanalysis (EPMA) ascertained the crystals' composition to be Tl₁.₉₂₀₍₂₎Ba₁.₉₆₍₂₎Cu₁.₀₈₀₍₂₎O₆₊δ; X-ray diffraction found the composition of a Tc = 75 K crystal to be Tl₁.₉₁₄₍₁₄₎Ba₂Cu₁.₀₈₆₍₁₄₎O₆.₀₇₍₅₎, in excellent agreement. X-ray refinement of the crystal structure found the crystals orthorhombic at most dopings, and their structure to be in general agreement with previous powder data. Cation-substituted Tl-2201 can be orthorhombic, orthorhombic crystals can be prepared, and these superconduct, all new results. X-ray diffraction also found evidence of an as yet unidentified commensurate superlattice modulation. The Tl-2201 crystals' electronic structure were studied by X-ray absorption and emission spectroscopies (XAS/XES). The Zhang-Rice singlet band gains less intensity on overdoping than expected, suggesting a breakdown of the Zhang-Rice singlet approximation, and one thallium oxide band does not disperse as expected. The spectra correspond very closely with LDA band structure calculations, and do not exhibit the upper Hubbard bands arising from strong correlations seen in other cuprates. The spectra are noteworthy for their unprecedented (in the high-Tc cuprates) simplicity. The startling degree to which the electronic structure can be explained bodes well for future research in the cuprates. The overdoped cuprates, and Tl-2201 in particular, may offer a unique opportunity for understanding in an otherwise highly confusing family of materials. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

Topological insulators and topological crystalline insulators are materials that have a bulk band structure that is gapped, but that also have toplogically protected non-gapped surface states. This implies that the bulk is insulating, but that the material can conduct electricity on some of its surfaces. The robustness of these surface states is a consequence of time-reversal symmetry, possibly in combination with invariance under other symmetries, like that of the crystal itself. In this thesis we review some of the basic theory for such materials. In particular we discuss how topological invariants can be derived for some specific systems. We then move on to do band structure calculations using the tight-binding method, with the aim to see the topologically protected surface states in a topological crystalline insulator. These calculations require the diagonalization of block tridiagonal matrices. We finish the thesis by studying the properties of such matrices in more detail and derive some results regarding the distribution and convergence of their eigenvalues.

Despite the tremendous application potentials of carbon nanotubes (CNTs) proposed by researchers in the last two decades, efficient experimental techniques and methods are still in need for controllable production of CNTs in large scale, and for conclusive characterizations of their properties in order to apply CNTs in high accuracy engineering. In this dissertation, horizontally well-aligned high quality single-walled carbon nanotubes (SWCNTs) have been successfully synthesized on St-cut quartz substrate by chemical vapor deposition (CVD). Effective radial moduli (Eradial) of these straight SWCNTs have been measured by using well-calibrated tapping mode and contact mode atomic force microscopy (AFM). It was found that the measured Eradial decreased from 57 to 9 GPa as the diameter of the SWCNTs increased from 0.92 to 1.91 nm. The experimental results were consistent with the recently reported theoretical simulation data. The method used in this mechanical property test can be easily applied to measure the mechanical properties of other low-dimension nanostructures, such as nanowires and nanodots. The characterized sample is also an ideal platform for electrochemical tests. The electrochemical activities of redox probes Fe(CN)63-/4-, Ru(NH3)63+, Ru(bpy)32+ and protein cytochrome c have been studied on these pristine thin films by using aligned SWCNTs as working electrodes. A simple and high performance electrochemical sensor was fabricated. Flow sensing capability of the device has been tested for detecting neurotransmitter dopamine at physiological conditions with the presence of Bovine serum albumin. Good sensitivity, fast response, high stability and anti-fouling capability were observed. Therefore, the fabricated sensor showed great potential for sensing applications in complicated solution.

The increasing demand of renewable energy is the big driving force for the research and development of more efficient solar energy conversion solutions. Solar cells, which use the photovoltaic effect to convert the photon energy to electrical current, are an important solar energy conversion technique. One solar cell technology is thin-film solar cells. Thin-film solar cells use an absorption layer with a direct band gap. A direct band gap has the advantage that the photons will penetrate less deep until a photoexcitation occur compared to semiconductors with an indirect band gap (e.g. silicon). For this reason the thin-film solar cells can be made very thin.CIGS is a common thin-film solar cell absorber material containing copper (Cu), indium (In), gallium (Ga) and selenium (Se). One objective of this work has been to determine element concentrations of CIGS absorption layers from sample measurements. The GGI ratio determines the band gap, which is an important factor for optimising the efficiency of the solar cell.1 The copper vacancy is the main acceptor dopant in CIGS. The Cu concentration has shown to be important for the efficiency and for other properties of the absorber [2].The measuring technique used in this work has been photoelectron spectroscopy (PES). PES produces a spectrum showing distinct peaks corresponding to electron binding energy levels for specific element subshells. Measurements with different photon energies have been performed on samples with and without post deposition treatment (PDT). A great deal of the effort has been to calculate relative element concentrations based on the PES peak intensities. Two important parameters when performing the calculations are the photoionization cross section (including the angular dependence of the cross section) and the inelastic mean free path of the photoelectrons.The results show that the GGI and the corresponding band gap will be almost the same with and without PDT except for close to the surface where PDT lowers the GGI.The calculations showed that the copper concentration is lowest at the surface. Moreover, PDT with RbF results in lower copper concentration closer to the junction.The results show a discrepancy of the GGI and CGI ratios when using the angular dependent cross sections in [10] and [11] compared to using the cross sections in [6] and [7]. / Det ökande behovet av förnybar energi gör att forskning och utveckling av solenergilösningar är av största vikt. Solceller, vilka utnyttjar den fotovoltaiska effekten, är den vanligaste tekniken för omvandling av solenergi till elektricitet. Tunnfilmssolceller är en typ av solceller vars absorbent har ett direkt bandgap, till skillnad från kisel som har ett indirekt bandgap. Fördelen med ett direkt bandgap är att det ljusabsorberande materialet kan göras mycket tunt.En vanlig tunnfilmssolcell är CIGS. Det är en komposit bestående av koppar (Cu), indium (In), gallium (Ga) och selen (Se). Ett syfte med detta självständiga arbete har varit att beräkna koncentrationerna av de ingående ämnena i halvledarskiktet av CIGS. GGI-kvoten bestämmer bandgapet, vilket är en viktig faktor för solcellens verkningsgrad. Kopparvakansen är den huvudsakliga halvledaracceptorn i CIGS. Kopparkoncentrationen har visat sig vara viktig för bl.a. solcellens verkningsgrad [2].Mättekniken som används i detta arbete kallas fotoelektronspektroskopi (PES). PES-mätningar ger ett spektrum där spektrallinjerna representerar olika nivåer av elektroners bindningsenergi för olika grundämnen. Mätningar med olika fotonenergier, på prover med och utan ytbehandling (PDT), har utförts. En stor del av arbetet har varit att beräkna relativa koncentrationer av de olika grundämnena från spektrallinjerna i spektrumet. Viktiga parametrar som man behöver ta hänsyn till i uträkningarna är sannolikheten för en fotoemissionsprocess hos fotonerna, vinkelberoendet och den fria medelväglängden hos fotoelektronerna.Resultaten visar att GGI-kvot och bandgap blir nästan detsamma med eller utan PDT, förutom närmast ytan där PDT minskar GGI-kvoten.Resultaten visar också att kopparkoncentrationen är lägst på ytan och att PDT med RbF minskar kopparkoncentrationen närmast ytan.Resultaten visar att det blir skillnader mellan GGI- och CGI-kvoterna beroende på om beräkningarna baserats på vinkelberoende träffytor enligt [10] och [11] eller baserats på träffytor enligt [6] och [7].

abstract: Wurtzite (In, Ga, Al) N semiconductors, especially InGaN material systems, demonstrate immense promises for the high efficiency thin film photovoltaic (PV) applications for future generation. Their unique and intriguing merits include continuously tunable wide band gap from 0.70 eV to 3.4 eV, strong absorption coefficient on the order of ∼105 cm−1, superior radiation resistance under harsh environment, and high saturation velocities and high mobility. Calculation from the detailed balance model also revealed that in multi-junction (MJ) solar cell device, materials with band gaps higher than 2.4 eV are required to achieve PV efficiencies greater than 50%, which is practically and easily feasible for InGaN materials. Other state-of-art modeling on InGaN solar cells also demonstrate great potential for applications of III-nitride solar cells in four-junction solar cell devices as well as in the integration with a non-III-nitride junction in multi-junction devices. This dissertation first theoretically analyzed loss mechanisms and studied the theoretical limit of PV performance of InGaN solar cells with a semi-analytical model. Then three device design strategies are proposed to study and improve PV performance: band polarization engineering, structural design and band engineering. Moreover, three physical mechanisms related to high temperature performance of InGaN solar cells have been thoroughly investigated: thermal reliability issue, enhanced external quantum efficiency (EQE) and conversion efficiency with rising temperatures and carrier dynamics and localization effects inside nonpolar m-plane InGaN quantum wells (QWs) at high temperatures. In the end several future work will also be proposed. Although still in its infancy, past and projected future progress of device design will ultimately achieve this very goal that III-nitride based solar cells will be indispensable for today and future’s society, technologies and society. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2020

The amphiphilic property of phospholipids drives the spontaneous formation of various molecular aggregates in response to their surrounding environment. In this study the concentration of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipids in water was varied in order to investigate the naturally occurring arrangements over time, and specifically the propensity to form monolayers on the water-vacuum interface. Several forms of aggregates developed during the 1000 ns long simulations, including monolayers and spherical- as well as cylindrical micelles. In all simulations the majority of lipids remained in the bulk and with varying sized patches of monolayers on the 8×8 nm surfaces formed. During a large portion of time the micelles kept close to the surface without ever opening up. By constructing and simulating 245 new unique systems with one of the micelles placed close to the surface, it could be confirmed that the possibility of these lipids forming a monolayer become greatly enhanced when no other lipids are present on the surface. Once a micelle had started to open up, it never reversed back to its original form but transformed, or could be expected to transform, into monolayers in all cases. In the concentration simulations it was furthermore found that a single lipid could be attached to the surface monolayer as well as a micelle simultaneously for over 400 ns. Not a single instance could be found where a lipid with both its tails on the surface travelled back to the bulk, in any of the simulations performed.

Neste trabalho apresentamos uma revisão de métodos de simulação de energia eletrostática de sistemas de cargas e uma proposta de adaptação de algoritmo ultilizado na literatura de sistemas gravitacionais para estudo das propriedades estatísticas de sistemas coulombianos. Na primeira parte do estudo, revisamos os fundamentos teóricos do método de Ewald e suas condições de aplicabilidade, procurando esclarecer as referências mais importantes no assunto, que são de difícil compreensão, gerando equívocos na utilização do termo de dipolo. Detalhamos o estudo sobre a análise da convergência da série em que a técnica se baseia, bem como sua interpretação física mostrando a equivalência entre as duas abordagens . Na segunda parte do trabalho analisamos os fundamentos do Fast Multipole Method desenvolvido para interação gravitacional, para o qual construímos programas em linguagem C para uma versão na rede. Criamos um algoritmo que denominamos Fast Multipole Monte Carlo (FMMC) e desenvolvemos um programa para cálculo das propriedades termodinâmicas de sistemas coulombianos. Os programas são testados comparando resultados para a energia e propriedades térmicas do modelo LRPM com resultados de simulação através de cálculo direto. / In this work we present a review of methods of simulation for the electrostatic energy of charged systems and an adaptation of an algorithm from the literature on gravitational systems for the study of the statistical properties of Coulomb systems. In the first part of the work, we review the fundamentals for the theoretical method of Ewald and its conditions of applicability, seeking to clarify the most important references on the subject, which because of the involved mathematics, have led to misuse of the so-called dipole correction. We detail the study on the convergence of the series for the electrostatic potential on which the Ewald technique is based, as well as the physical interpretation given elsewhere, showing the equivalence between the two approaches. In the second part of this work, we analyse the foundations of the Fast Multipole Method developed for gravitational interactions, and present programs in C language for a network version of neutral charged systems. Finally, an algorithm, which we name Fast Multipole Monte Carlo, and the corresponding code for calculating the thermodynamic properties of Coulomb systems are presented. The programs are tested by comparing results for the energy and thermal properties of the Lattice Restricted Primitive model with results of simulations based on direct calculations for the Coulomb energies.

There is a movement in the electronic industry toward building electronic devices with dimensions smaller than is currently possible. Atomically thin 2D material, such as graphene, bilayer graphene, hBN and MoS2 are great candidate for this goal and they have a potential set of novel electronic properties compare to their bulk counterparts due to the exhibition of quantum confinement effects. To this goal, we have investigated the electric field screening of multilayer 2D materials due to the presence of impurity charge in the interface and vertical electric fifield from back gate. Our result shows a dramatic difference of screening behavior in high and low charging limit, which depends on the number of layers as well. We also have an extensive study on quantum tunneling effect in graphene and bilayer graphene heterojunctions. The peculiar electronic properties of graphene lead to an unusual scattering effect of electron in graphene n-p junction. We implement the cohesive tunneling effect to explain the nonlinear electron transport in ultrashort channel graphene devices. This nonlinear behavior could make them tremendously useful for ultra-fast electronic applications.

abstract: Lateral programmable metallization cells (PMC) utilize the properties of electrodeposits grown over a solid electrolyte channel. Such devices have an active anode and an inert cathode separated by a long electrodeposit channel in a coplanar arrangement. The ability to transport large amount of metallic mass across the channel makes these devices attractive for various More-Than-Moore applications. Existing literature lacks a comprehensive study of electrodeposit growth kinetics in lateral PMCs. Moreover, the morphology of electrodeposit growth in larger, planar devices is also not understood. Despite the variety of applications, lateral PMCs are not embraced by the semiconductor industry due to incompatible materials and high operating voltages needed for such devices. In this work, a numerical model based on the basic processes in PMCs – cation drift and redox reactions – is proposed, and the effect of various materials parameters on the electrodeposit growth kinetics is reported. The morphology of the electrodeposit growth and kinetics of the electrodeposition process are also studied in devices based on Ag-Ge30Se70 materials system. It was observed that the electrodeposition process mainly consists of two regimes of growth – cation drift limited regime and mixed regime. The electrodeposition starts in cation drift limited regime at low electric fields and transitions into mixed regime as the field increases. The onset of mixed regime can be controlled by applied voltage which also affects the morphology of electrodeposit growth. The numerical model was then used to successfully predict the device kinetics and onset of mixed regime. The problem of materials incompatibility with semiconductor manufacturing was solved by proposing a novel device structure. A bilayer structure using semiconductor foundry friendly materials was suggested as a candidate for solid electrolyte. The bilayer structure consists of a low resistivity oxide shunt layer on top of a high resistivity ion carrying oxide layer. Devices using Cu2O as the low resistivity shunt on top of Cu doped WO3 oxide were fabricated. The bilayer devices provided orders of magnitude improvement in device performance in the context of operating voltage and switching time. Electrical and materials characterization revealed the structure of bilayers and the mechanism of electrodeposition in these devices. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2020