Orientador: Rafael Zadorosny / Resumo: As propriedades diferenciadas de materiais nanoestruturados, provenientes do efeito de escala, tem chamado muita atenção nos últimos anos. Tais características, fazem desses materiais propícios para o emprego em nanoeletrônica, nanofiltração, engenharia tecidual e outros. Isso, aliado a miniaturização dos dispositivos, tem gerado uma grande demanda por materiais com características aprimoradas, desenvolvimento de novas técnicas de produção e aprimoramento das já existentes, tudo isso associado a um menor custo de produção e uma maior produtividade. Neste trabalho é apresentado um estudo sobre o emprego da técnica de “Solution Blow-spinning” (SBS) na produção de nano e microfios supercondutores dos sistemas cerâmicos (TR)BCO e BSCCO. Esta recente técnica tem se destacado por apresentar maior taxa de produção, baixo custo e fácil implementação quando comparado com técnicas já consolidadas. Primeiramente foram produzidas fibras de PVP puro onde foi possível extrair informações referentes às variáveis de produção tais como: taxa de injeção, pressão do ar, distância de trabalho e escolha do diâmetro da agulha interna. Em seguida, a produção dos nano/microfios de YBa2Cu3O7- δ (YBCO) obtidos por SBS revelaram detalhes referente à produtividade, reprodutibilidade e das características morfológicas dos fios cerâmicos obtidos com o emprego da referida técnica. Posteriormente, as melhores condições de síntese observadas na produção do YBCO foram utilizadas na obtenção dos nano/microfios... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The single properties presented by nanostructured materials is due to a scale effect and have been attracted much attention in recent years. Such characteristics make these materials suitable for applications in nanoelectronics, nanofiltration, tissue engineering and so on. These issues coupled with the miniaturization of the devices, have generated a great demand for materials with improved characteristics, development of new production techniques and improvement of the existing ones. All such things are associated with lower production costs and higher productivity. In this work is presented a study focused on the use of the "Solution Blow-spinning" technique (SBS) in the production of superconducting nano and microwires of the ceramic systems (TR)BCO and BSCCO. This new technique has payed attention due to its higher production rate, low cost and easy implementation when compared to other consolidated techniques. First, pure PVP fibers were produced to obtain information related to the production variables such as: injection rate, air pressure, working distance and choice of the internal needle diameter. Then, the production of nano/microwires of YBa2Cu3O7- δ (YBCO), obtained by SBS, revealed details regarding the productivity, reproducibility and morphological characteristics of the ceramic wires. Consequently, the best synthesis conditions were used to obtain the GdBa2Cu3O7- δ (GdBCO) and Bi2Sr2CaCu2O8+x (BSCCO) superconducting nanowires. Finally, SEM analysis confirmed ... (Complete abstract click electronic access below) / Doutor

>Magister Scientiae - MSc / In this thesis we report on the deposition of silicon nanostructures using a 3-zone thermal chemical vapour deposition process at atmospheric pressure. Nickel and gold thin films, deposited by DC sputtering on crystalline silicon substrates, were used as the catalyst material required for vapour-solid-liquid growth mechanism of the Si nanostructures. The core of this work is centred around the effect of catalyst type, substrate temperature and the source-to-substrate distance on the structural and optical properties of the resultant Si nanostructures, using argon as the carrier gas and Si powder as the source. The morphology and internal structure of the Si nanostructures was probed by using high resolution scanning and transmission electron microscopy, respectively. The crystallinity was measured by x-ray diffraction and the high resolution transmission electron microscopy. For composition and elemental analysis, Fourier transform infrared spectroscopy was used to quantify the bonding configuration, while electron energy-loss spectroscopy in conjunction with electron dispersion spectroscopy reveals the composition. Photoluminescence and UV-visible spectroscopy was used to extract the emission and reflection properties of the synthesized nanostructures.

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Submitted by MAYCON ROTTA null (maycon.rotta@ifms.edu.br) on 2018-03-02T00:23:16Z No. of bitstreams: 1 Maycon rotta_Tese.pdf: 4933056 bytes, checksum: 41743cf4709dbf478bee8fb5876fed76 (MD5) / Approved for entry into archive by Cristina Alexandra de Godoy null (cristina@adm.feis.unesp.br) on 2018-03-02T13:47:29Z (GMT) No. of bitstreams: 1 rotta_m_dr_ilha.pdf: 4933056 bytes, checksum: 41743cf4709dbf478bee8fb5876fed76 (MD5) / Made available in DSpace on 2018-03-02T13:47:29Z (GMT). No. of bitstreams: 1 rotta_m_dr_ilha.pdf: 4933056 bytes, checksum: 41743cf4709dbf478bee8fb5876fed76 (MD5) Previous issue date: 2018-02-05 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / As propriedades diferenciadas de materiais nanoestruturados, provenientes do efeito de escala, tem chamado muita atenção nos últimos anos. Tais características, fazem desses materiais propícios para o emprego em nanoeletrônica, nanofiltração, engenharia tecidual e outros. Isso, aliado a miniaturização dos dispositivos, tem gerado uma grande demanda por materiais com características aprimoradas, desenvolvimento de novas técnicas de produção e aprimoramento das já existentes, tudo isso associado a um menor custo de produção e uma maior produtividade. Neste trabalho é apresentado um estudo sobre o emprego da técnica de “Solution Blow-spinning” (SBS) na produção de nano e microfios supercondutores dos sistemas cerâmicos (TR)BCO e BSCCO. Esta recente técnica tem se destacado por apresentar maior taxa de produção, baixo custo e fácil implementação quando comparado com técnicas já consolidadas. Primeiramente foram produzidas fibras de PVP puro onde foi possível extrair informações referentes às variáveis de produção tais como: taxa de injeção, pressão do ar, distância de trabalho e escolha do diâmetro da agulha interna. Em seguida, a produção dos nano/microfios de YBa2Cu3O7- δ (YBCO) obtidos por SBS revelaram detalhes referente à produtividade, reprodutibilidade e das características morfológicas dos fios cerâmicos obtidos com o emprego da referida técnica. Posteriormente, as melhores condições de síntese observadas na produção do YBCO foram utilizadas na obtenção dos nano/microfios supercondutores de GdBa2Cu3O7- δ (GdBCO)e Bi2Sr2CaCu2O8+x (BSCCO). Por fim, as análises de MEV confirmaram a obtenção de nano/microfios de YBCO com diâmetro médio de 359 nm e, para GdBCO e BSCCO, de 531 nm e 635 nm respectivamente. A obtenção das fases cerâmicas supercondutoras é mostrada nas análises de DRX. Medidas magnéticas AC e DC mostraram a transição de fase normal/supercondutora com Tc ~ 92 K para o YBCO, Tc ~ 93 K para o GdBCO e de Tc ~ 80 K para o BSCCO. / The single properties presented by nanostructured materials is due to a scale effect and have been attracted much attention in recent years. Such characteristics make these materials suitable for applications in nanoelectronics, nanofiltration, tissue engineering and so on. These issues coupled with the miniaturization of the devices, have generated a great demand for materials with improved characteristics, development of new production techniques and improvement of the existing ones. All such things are associated with lower production costs and higher productivity. In this work is presented a study focused on the use of the "Solution Blow-spinning" technique (SBS) in the production of superconducting nano and microwires of the ceramic systems (TR)BCO and BSCCO. This new technique has payed attention due to its higher production rate, low cost and easy implementation when compared to other consolidated techniques. First, pure PVP fibers were produced to obtain information related to the production variables such as: injection rate, air pressure, working distance and choice of the internal needle diameter. Then, the production of nano/microwires of YBa2Cu3O7- δ (YBCO), obtained by SBS, revealed details regarding the productivity, reproducibility and morphological characteristics of the ceramic wires. Consequently, the best synthesis conditions were used to obtain the GdBa2Cu3O7- δ (GdBCO) and Bi2Sr2CaCu2O8+x (BSCCO) superconducting nanowires. Finally, SEM analysis confirmed the production of nanoscale YBCO with average diameter of 359 nm and, for GdBCO and BSCCO, of 531 nm and 635 nm, respectively. The formation of the desired phases of the superconducting ceramic was confirmed by XRD analyzes. AC and DC magnetic measurements showed the normal/superconducting phase transition with Tc ~ 92 K for YBCO, Tc ~ 93 K for GdBCO and Tc ~ 80 K for BSCCO. / 1459610

Si nanowires have potential applications in a variety of technologies such as micro and nanoelectronics, sensors, electrodes and photovoltaic applications due to their size and specific surface area. Au particle-assisted vapour-liquid-solid or VLS growth method remains the dominant process for Si nanowire growth. A comprehensive kinetic model that addresses all experimental observations and provides a physico-chemical model of the VLS growth method is thus essential. The work done as part of this research is divided into two sections. A steady state kinetic model was first developed for the steady state growth rate of Si nanowires using SiCl4 and SiH4 as precursors. The steady state refers to a balance between the rates of injection and ejection of Si into the Au droplet. This balance results in a steady state supersaturation under which wire growth proceeds. In particular evaporation and reverse reaction of Si from the Au droplet and modes of crystal growth for wire growth have been considered in detail for the first time. The model is able to account for both, the radius independent and radius dependent growth rates reported in the literature. It also shows that the radius dependence previously attributed to purely thermodynamic considerations could also as well be explained just by steady state kinetics alone. Expressions have been derived for the steady state growth rate that require the desolvation energy, activation energy for precursor dissociation and supersaturation prevalent in the particle as inputs for calculation. In order to evaluate this model the incubation and growth of Si nanowires were studied on sapphire substrates in an indigenously built automated MOCVD reactor. Sapphire was chosen as the substrate, as opposed to Si which is commonly used, so as to ensure that the vapour phase is the only source of Si. A classical incubation period for nucleation, of the order of 4-8 minutes, was experimentally observed for the first time. Using the change in this incubation period with temperature a value of 15kT was determined to be the desolvation energy for growth using SiH4. The steady state growth rate of Si nanowires were measured and compared with the predictions of the model using the values of activation energies so determined. The thesis based on the current research work is organized as follows: Chapter 1 introduces the research area followed by a brief outline of the overall work Chapter 2 provides a summary of current literature, and puts the research described in this thesis in perspective. The diameter dependent growth rate of NWs which was initially solely attributed to the Gibbs-Thomson effect is first summarized. Experimental observations to the contrary are then highlighted. These contradictions provided the incentive for the research described in this thesis. Following a summary of the growth rate theories, the experimental observations on incubation available in the literature are summarized. All the other variants of the VLS method are also discussed. Chapter 3 describes the design, construction and working of an indigenously built semi- automated CVD reactor. This CVD reactor was used to conduct the Si NW growth experiments over sapphire substrates. Chapter 4 develops the physical chemistry model for Au catalyzed Si nanowire growth using SiCl4 and SiH4 precursors. The model originated from the contradictions present in the literature over the rate limiting step of the VLS growth mechanism and the steady state growth rate dependence on wire diameter. The development starts with explaining the thermodynamics of the steady state VLS process. The significance of the model lies in the detailed analysis of the all the atomistic process occurring during the VLS growth. In particular the evaporation and reverse reaction of Si from Au-Si droplet is explained in detail and possibly for the first time. Expressions for steady state growth rate by various modes, such as layer by layer growth (LL), by multilayer growth (ML) and growth by movement of a rough interface at the L-S growth interface are derived and presented. Chapter 5 discusses the results which emerge out the kinetic model from the previous chapter. Under a single framework of equations, the model is successful in explaining both the diameter independent and diameter dependent growth of NWs. As one of the major outcomes of the model, the growth rates of Si NWs are predicted and trends in growth rate are found to agree with those experimentally observed. Growth rate dependencies on pressure and temperature are implicitly included in the equations derived. An estimate of supersaturation has been extracted for the first time using the framework of equations. Chapter 6 contains the experimental results of the Si NW growth over sapphire substrates. An incubation period in the order of 3-8 minutes has been observed for Si NW growth on sapphire. The data has been compared with existing literature data and interpreted using classical transient nucleation theory. The incubation period data has been utilized to extract the kinetic parameter, QD, which is the desolvation enegy. These parameters and the measured steady state growth rates have been used to estimate the supersaturation existing in the droplet using the framework developed in chapters 4 and 5. Chapter 7 summarizes the outcome of the current research and highlights the future directions for the research problem addressed in this thesis.

The innovation of multifunctional efficient, and safer treatments is a major challenge in nanomedicine. For example, the combination of magneto-mechanical and the photothermal strategies into one single therapeutic stage is one of the promising developments in cancer treatment. Without specificity, however, these therapies would target and harm both cancer and healthy cells. Therefore, the goal of precision medicine is to focus on delivering therapies to specific cells and minimize the side effects on healthy. Therefore, in this study, biocompatible, magnetic iron nanowires were functionalized with antibodies directed against CD44, a cell surface marker that is overexpressed in a large number of cancer cells. To test the functionality of the antibodies following conjugation to the iron nanowires, immunostaining and immunoprecipitation were performed and confirmed that the antigenicity of the antibodies was preserved following their conjugation to the nanowires. Indeed, the antibody coated nanowires were shown to play a major role in enhancing the accumulation and the internalization of nanowires to the cell surface in both adherent cells (e.g. colon cancer cells) and suspension cells (e.g., leukemia cells). Moreover, inductively coupled plasma mass spectrometry was used to quantify the attached and internalized nanowires. After only 1 h, the presence of antibodies enhanced the ability of the NWs to specifically target cancer cells, by more than 60% in both colon and leukemic cancers, compared to their negative controls. In addition, the presence of antibodies did not affect the magnetization of the nanowires. Therefore, the combination of both magneto-mechanical and photothermal strategies in the presence of the antibodies functionalized nanowires was applied to two types of cancer cells, colon cancer and leukemia. Strikingly, the targeted nanowires resulted in more than 76±3.5% and 45.5±0.4% cell death of colon cancer and leukemic target cells and less than 40% of cells died from the non-targeted NWs. These results represent a significant finding, as this is the first study which examines the role antibodies play in the internalization of iron nanowires, and more importantly, the efficacy to kill cancer cells. It also confirmed the possibility of targeting cancer cells with functionalized nanowires and destroying these cells utilizing combined strategies.

Thesis advisor: Michael J. Naughton / In this dissertation, I first discuss many different kinds of transparent conductors in Chapter one. In Chapter two, I focus on transparent conductors based on crackle temples. I and my colleagues developed three (one sputter-free and two fully all-solution) methods to fabricate metallic networks as transparent conductors. The first kind of all-solution process is based on crackle photolithography and the resulting silver networks outperform all reported experimental values, including having sheet resistance more than an order of magnitude lower than ITO, yet with comparable transmittance. The second kind of all-solution proceed transparent conductor is obtained by integrating crackle photolithography-based microwires with nanowires and electroplate welding. This combination results in scalable film structures that are flexible, indium-free, vacuum-free, lithographic-facility-free, metallic-mask-free, with small domain size, high optical transmittance, and low sheet resistance (one order of magnitude smaller than conventional nanowire-based transparent conductors). / Thesis (PhD) — Boston College, 2019. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

In recent years, magnetic nanowires (NWs) have been widely used for their therapeutic potential in biomedical applications. The use of iron (Fe) NWs combines two important properties, biocompatibility and remote manipulation by magnetic fields. In addition the NWs can be coated and functionalized to target cells of interest and, upon exposure to an alternating magnetic field, have been shown to induce cell death on several types of adherent cells, including several cancer cell types. For suspension cells, however, using these NWs has been much less effective primarily due to the free-floating nature of the cells minimizing the interaction between them and the NWs. Leukemic cells express higher levels of the cell surface marker CD44 (Braumüller, Gansauge, Ramadani, & Gansauge, 2000), compared to normal blood cells. The goal of this study was to functionalize Fe NWs with a specific monoclonal antibody towards CD44 in order to target leukemic cells (HL-60 cells). This approach is expected to increase the probability of a specific binding to occur between HL-60 cells and Fe NWs. Fe NWs were fabricated with an average diameter of 30-40 nm and a length around 3-4 μm. Then, they were coated with both 3-Aminopropyl-triethoxysilane and bovine serum albumin (BSA) in order to conjugate them with an anti-CD44 antibody (i.e. anti-CD44-iron NWs). The antibody interacts with the amine group in the BSA via the 1-Ethyl-3-3-dimethylaminopropyl-carbodiimide and N-Hydroxysuccinimide coupling. The NWs functionalization was confirmed using a number of approaches including: infrared spectroscopy, Nanodrop to measure the concentration of CD44 antibody, as well as fluorescent-labeled secondary antibody staining to detect the primary CD44 antibody. To confirm that the anti-CD44-iron NWs and bare Fe NWs, in the absence of a magnetic field, were not toxic to HL-60 cells, cytotoxicity assays using XTT (2,3-Bis-2-Methoxy-4-Nitro-5-Sulfophenyl-2H-Tetrazolium-5-Carboxanilide) were performed and resulted in a high level of biocompatibility. In addition, the internalization of the coated NWs have been studied by coating them with a pH dependent dye (pHrodoTM Red) that showed a signal once the NWs were internalized by the cell.

Dans ce manuscrit, je présente mon travail dédié à la réalisation et à la caractérisation des émetteurs et détecteurs de lumière à base de nanofils de nitrures. Je détaille la fabrication des dispositifs utilisant des outils de nanofabrication à l’état de l’art, ainsi que l'étude de leurs propriétés électriques et optiques.Le premier chapitre résume brièvement les propriétés de base des semi-conducteurs nitrures et décrit les méthodes d’élaboration des nanofils. Dans le deuxième chapitre, je présente mon travail sur la fabrication et la caractérisation de LED à nanofil unique InGaN/GaN ayant un contact transparent en graphène pour l’injection des trous. L'électroluminescence des LEDs à nanofils uniques montre l'impact de la forme du contact sur les propriétés d'émission. En particulier, la position du contact détermine l'évolution spectrale avec le courant d'injection. À savoir, pour un contact étendu et un contact localisé sur le plan m, l’émission passe du vert au bleu en fonction du courant d’injection alors que pour un contact localisé sur la jonction entre le plan m et le plan semipolaire l'émission reste verte.Dans le troisième chapitre, je décris la fabrication et la caractérisation des LEDs à nanofils uniques fabriqués à partir d'une matrice de nanofils verticaux avec une morphologie des contacts identique à celle mise en œuvre pour les LEDs à base d’ensemble de nanofils. L'émission montre une évolution similaire à celle observée pour les LEDs à nanofils uniques avec un contact latéral. L’influence de la morphologie des contacts sur l'électroluminescence ouvre la possibilité de contrôler la couleur d'émission de la LED à l'étape de la fabrication. J'ai utilisé un traitement par plasma de fluor afin de réduire la conductivité de la coquille GaN dopé p et d’inhiber l'injection électrique dans la région riche en In du puits quantique. En outre, j'ai analysé l'effet de l’inhomogénéité d'injection. Afin d'améliorer l’homogénéité, j'ai développé un système de contact par le haut permettant d’injecter les électrons directement dans la sous-couche n-GaN. Les LEDs fabriquées selon cette procédure montrent un rendement amélioré avec 65% de nanofils actifs contre 19% pour une procédure standard.Le dernier chapitre est consacré à l'étude des photodétecteurs à nanofils de nitrure. Je décris d'abord la fabrication et la caractérisation d'un photodétecteur de rayonnement ultraviolet basé sur un ensemble de nanofils de GaN avec un contact transparent en graphène. Ensuite, des détecteurs à nanofils uniques InGaN / GaN ont été fabriqués fonctionnant dans la gamme spectrale du visible à ultraviolet. L'influence de la morphologie de contact est également étudiée en comparant deux types de contacts, à savoir un contact métallique localisé et un contact étendu en oxyde d'indium-étain (ITO). Dans la dernière partie, je présente une technique pour la fabrication de photodétecteurs flexibles basée sur des ensembles de nanofils verticaux et je discute leurs performances. / In this manuscript, I present my work dedicated to the realization and characterization of nitride nanowire light emitters and detectors. I detail the device fabrication using state-of-the-art nanofabrication tools as well as the investigation of their electrical and optical properties.First chapter briefly summarizes the nitride semiconductor basic properties and discusses the present status of nanowire elaboration. In the second chapter, I present my work on the fabrication and in-depth characterization of single nanowire InGaN/GaN LEDs with a transparent graphene contact for hole injection. Reference single wire LEDs with metal contacts are also investigated for comparison. The electroluminescence of single nanowire LEDs evidences the impact of the contact layout on the emission properties. In particular, the position of the contact determines the spectral evolution with injection current. Namely, for an extended contact and a contact localized on the m-plane, a transition from the green to blue emission is observed whereas for a localized contact on the m-plane/semipolar plane junction the emission remains green.In the third chapter, I describe the fabrication and characterize single wire LEDs made out of a vertical NW array with the contacting scheme identical to array LEDs. The emission shows a similar evolution as the lateral-contacted single nanowire LEDs. The dependence of the electroluminescence on the contact morphology opens the way to control the LED emission color at the device processing stage. I used fluorine plasma treatment to reduce the conductivity of the p-doped GaN shell for inhibiting the electrical injection in the In-rich region of the quantum well. Furthermore, I analyze the injection inhomogeneity effect. In order to avoid this effect, I developed a top down contacting scheme with electrons injected directly into n-GaN underlayer, which is called “front contacting” process. The “front contacting” LEDs show an enhanced yield of active nanowires from 19% to 65%.The last chapter is dedicated to the study of nitride nanowire photodetectors. I first describe the fabrication and characterization of a GaN ultraviolet (UV) photodetector based on a NW array with a transparent graphene contact. Moreover, single NW InGaN/GaN detectors were fabricated operating in the visible to ultraviolet spectral range. The influence of the contact morphology is also investigated by comparing two types of contacts, namely a partial metal contact and an indium tin oxide (ITO) conformal contact, respectively. In the last part, I present an up-to-date technique for fabricating flexible photodetectors based on vertical NW arrays and I discuss their performances.

Current cancer therapies are highly cytotoxic and their delivery to exclusively the affected site is poorly controlled, resulting in unavoidable and often severe side effects. In an effort to overcome such issues, magnetic nanoparticles have been recently gaining relevance in the areas of biomedical applications and therapeutics, opening pathways to alternative methods. This led to the concept of magnetic particle hyperthermia in which magnetic nano beads are heated by a high power magnetic field. The increase in temperature kills the cancer cells, which are more susceptible to heat in comparison to healthy cells. In this dissertation, the possibility to kill cancer cells with magnetic nanowires is evaluated. The idea is to exploit a magnetomechanical effect, where nanowires cause cancer cell death through vibrating in a low power magnetic field. Specifically, the magnetic nanowires effects to cells in culture and their ability to induce cancer cell death, when combined with an alternating magnetic field, was investigated. Nickel and iron nanowires of 35 nm diameter and 1 to 5 μm long were synthesized by electrodeposition into nanoporous alumina templates, which were prepared using a two-step anodization process on highly pure aluminum substrates. For the cytotoxicity studies, the nanowires were added to cancer cells in culture, varying the incubation time and the concentration. The cell-nanowire interaction was thoroughly studied at the cellular level (mitochondrial metabolic activity, cell membrane integrity and, apoptosis/necrosis assay), and optical level (transmission electron and confocal microscopy). Furthermore, to investigate their therapeutic potential, an alternating magnetic field was applied varying its intensity and frequency. After the magnetic field application, cells health was measured at the mitochondrial activity level. Cytotoxicity results shed light onto the cellular tolerance to the nanowires, which helped in establishing the appropriate nanowire concentrations to use the nanowires + alternating magnetic field combination as a cancer treatment. Different levels of cancer cell death were achieved by changing the incubation time of the nanowires with the cells and the alternating magnetic field parameters. Cell viability was significantly affected in terms of mitochondrial activity and cell membrane integrity after applying the treatment (nanowires + alternating magnetic field) using a low-frequency alternating magnetic. Theoretical calculations considering the magnetic and viscous torques showed that the nanowires vibrate as a consequence of the applied magnetic field. This, alongside the fact that no temperature increase was measured during the treatment, makes the magnetomechanical effect the most probable action mechanism in the applied treatment that is inducing cell death. Inducing cancer cell death via magnetomechanical action using magnetic nanowires resulted in killing up to 60% of cancer cells with only 10 minutes of treatment. The required magnetic field for treatment is in a low power regime, which is safe, does not cause any discomfort to the patients, and can be generated with compact and cheap instruments.