Chemo-mechanics studies the material behavior and phenomena at the interface of mechanics and chemistry. Material failures due to coupled chemo-mechanical effects are serious roadblocks in the development of renewable energy technologies. Among the sources of renewable energies for the mass market, hydrogen and lithium-ion battery are promising candidates due to their high efficiency and easiness of conversion into other types of energy. However, hydrogen will degrade material mechanical properties and lithium insertion can cause electrode failures in battery owing to their high mobilities and strong chemo-mechanical coupling effects. These problems seriously prevent the large-scale applications of these renewable energy sources. In this thesis, the atomistic and continuum modeling are performed to study the chemical-mechanical failures. The objective is to understand the hydrogen embrittlement of grain boundary engineered metals and the lithium insertion-induced fracture in alloy electrodes for lithium-ion batteries. Hydrogen in metallic containment systems such as high-pressure vessels and pipelines causes the degradation of their mechanical properties that can result in sudden catastrophic fracture. A wide range of hydrogen embrittlement phenomena was attributed to the loss of cohesion of interfaces (between grains, inclusion and matrix, or phases) due to interstitially dissolved hydrogen. Our modeling and simulation of hydrogen embrittlement will address the question of why susceptibility to hydrogen embrittlement in metallic materials can be markedly reduced by grain boundary engineering. Implications of our results for efficient hydrogen storage and transport at high pressures are discussed. Silicon is one of the most promising anode materials for Li-ion batteries (LIB) because of the highest known theoretical charge capacity. However, Si anodes often suffer from pulverization and capacity fading. This is caused by the large volume changes of Si (~300%) upon Li insertion/extraction close to the theoretical charging/discharging limit. In particular, large incompatible deformation between areas of different Li contents tends to initiate fracture, leading to electro-chemical-mechanical failures of Si electrodes. In order to understand the chemo-mechanical mechanisms, we begin with the study of basic fracture modes in pure silicon, and then study the diffusion induced deformation and fracture in lithiated Si. Results have implications for increasing battery capacity and reliability. To improve mechanical stability of LIB anode, failure mechanisms of silicon and coated tin-oxide nanowires have been studied at continuum level. It's shown that anisotropic diffusivity and anisotropic deformation play vital roles in lithiation process. Our predictions of fracture initiation and evolution are verified by in situ experiment observations. Due to the mechanical confinement of the coating layers, our study demonstrates that it is possible to simultaneously control the electrochemical reaction rate and the mechanical strain of the electrode materials through carbon or aluminum coating, which opens new avenues of designing better lithium ion batteries. This thesis addresses the nano-chemo-mechanical failure problems in two green energy-carrier systems toward improving the performance of Li-ion battery anode and hydrogen storage system. It provides an atomistic and continuum modeling framework for the study of chemo-mechanics of advanced materials such as nano-structured metals and alloys. The results help understand the chemical effects of impurities on the mechanical properties of host materials with different metallic and covalent bonding characteristics.

Undoped body multi gate (MG) Metal Oxide Semiconductor Field Effect Transistors (MOSFET) are appearing as replacements for single gate bulk MOSFET in forthcoming sub-45nm technology nodes. It is therefore extremely necessary to develop compact models for MG transistors in order to use them in nano-scale integrated circuit design and simulation. There is however a sharp distinction between the electrostatics of traditional bulk transistors and undoped body devices. In bulk transistor, where the substrate is sufficiently doped, the inversion charges are located close to the surface and hence the surface potential solely controls the electrostatic integrity of the device. However, in undoped body devices, gate electric field penetrates the body center, and inversion charge exists throughout the body. In contrast to the bulk transistors, depending on device geometry, the potential of the body center of undoped body devices could be higher than the surface in weak inversion regime and the current flows through the center-part of the device instead of surface. Several crucial parameters (e.g. Sub-threshold slope) sometimes become more dependable on the potential of body center rather than the surface. Hence the body-center potential should also be modeled correctly along with the surface-potential for accurate calculation of inversion charge, threshold voltage and other related parameters of undoped body multi-gate transistors. Although several potential models for MG transistors have been proposed to capture the short channel behavior in the subthreshold regime but most of them are based on the crucial approximation of coverting the 2D Poisson’s equation into Laplace equation. This approximation holds good only at surface but breaks down at body center and in the moderate inversion regime. As a result all the previous models fail to capture the potential of body center Correctly and remain valid only in weak-inversion regime. In this work we have developed semiclassical compact models for potential distribution for double gate (DG) and cylindrical Gate-All-Around (GAA) transistors. The models are based on the analytical solution of 2D Poisson’s equation in the channel region and valid for both: a) weak and strong inversion regimes, b) long channel and short channel transistors, and, c) body surface and center. Using the proposed model, for the first time, it is demonstrated that the body potential versus gate voltage characteristics for the devices having equal channel lengths but different body thicknesses pass through a single common point (termed as crossover point). Using the concept of “crossover point” the effect of body thickness on the threshold voltage of undoped body multi-gate transistors is explained. Based on the proposed body potential model, a new compact model for the subthreshold swing is formulated. Some other parameters e.g. inversion charge, threshold voltage roll-off etc are also studied to demonstrate the impact of body center potential on the electrostatics of multi gate transistor. All the models are validated against professional numerical device simulator.

Ab initio calculations of the electronic structure of freestanding Cu and Na nanowires with a diameter of few atoms are presented. The calculations are based on density functional theory in local density approximation using a Screened Korringa-Kohn-Rostoker-Green's function method. The method was extended for the description of quasi-onedimensional systems. Translational invariance in direction of the wire is assumed. The dependence of the bandstructure and the density of states from thickness and shape of the cross-section is discussed. The quantum confinement of the eigenstates is analysed. By comparing the results of the Na and Cu wires, the influence of the d-electrons is shown. Based on the Landauer theory of transport the conductance is obtained within a Green's function formalism. The numerical description of the conductance is tested for ideal translationally invariant Na and Cu wires. The influence of substitutional transition metal impurities on the electronic structure and the conductance of the 2x2 Cu wire is studied. A spin-dependent discussion is given for magnetic impurities. / Es werden ab initio Berechnungen der elektronischen Struktur freistehender Na- und Cu-Nanodrähte mit einem Durchmesser von wenigen Atomen präsentiert. Für die Berechnung wird eine Screened Korringa-Kohn-Rostoker-Grennsche Funktionsmethode genutzt, die auf der Spindichtefunktionaltheorie in lokaler-Spindichtenäherung basiert. Diese Methode wurde für die Beschreibung von quasieindimensionalen Systemen erweitert. Die Drähte werden als translationsinvariant in Drahtrichtung beschrieben. Es wird die Abhängigkeit der Bandstruktur und der Zustandsdichte von der Dicke und der Form des Querschnitts diskutiert. Das Quantenconfinement der Eigenzustände wird analysiert. Durch den Vergleich der Resultate für den Na- und den Cu-Draht kann der Einfluss der d-Elektronen gezeigt werden. Ausgehend von der Landauer-Theorie des Transports wird der Leitwert im Rahmen eines Greenschen Funktions-Formalismus berechnet. Diese neue numerische Beschreibung des Leitwertes wird an idealen translationsinvarianten Drähten getestet. Es wird der Einfluss von substitutionellen 3d-Übergangsmetall-Störungen auf die elektronische Struktur und auf den Leitwert von 2x2-Cu-Drähten studiert. Im Fall magnetischer Defekte wird dieser Einfluss spinabhängig diskutiert.

Magnetic thin films and patterned nanostructures have been studied with respect to their magnetic properties using SQUID-magnetometry, magnetic force microscopy, electrical measurements, and micromagnetic calculations. Properties of vortex domain walls, trapped in Permalloy nanowires with artificial constrictions, were investigated experimentally and by numerical calculations. In particular, the geometrical extent and strength of the pinning potential were evaluated. In these wires, long-range vortex domain wall displacement induced by spin polarized alternating currents was obtained numerically at reduced threshold current densities as compared with the direct current case. Due to the asymmetry of the energy potential, the long-range displacement direction is determined by the vortex chirality. Strained FeCo/Pt superlattices with strong perpendicular anisotropy were investigated experimentally. The strain was controlled by varying the thickness of each alternating layer with monolayer precision and was found to have a dominating effect on the total anisotropy. Epitaxial films of the diluted magnetic semiconductor (Ga,Mn)As were studied with focus on how the ferromagnetic transition temperature could be controlled by post-growth annealing. The ferromagnetic transition temperature was enhanced by approximately 85% for a Mn-doping concentration of 6% under certain conditions. A method to manipulate micrometer sized magnetic particles on patterned arrays of elliptical Permalloy microstructures was studied. Controlled motion and separation of the magnetic particles were obtained using applied rotating magnetic fields. The domain structure of the elliptical elements was studied numerically.

Ce mémoire de thèse traite de la caractérisation de microfils et nanofils semi conducteurs dopés individuels par microscopie à émission de photoélectrons X (XPEEM) complétée par des techniques de champ proche électrique: Kelvin force microscopy (KFM) et scanning capacitance microscopy (SCM). L'objectif est d'évaluer l'apport des méthodes locales de surface « sans contact », grâce à la mesure du travail de sortie local et de l'énergie de liaison des niveaux de cœur, pour l'étude des phénomènes liés au dopage dans ces objets, comme par exemple l'uniformité longitudinale. Nous mettons d'abord en évidence l'importance de la préparation des échantillons pour la mise en œuvre des techniques citées: méthodes de transfert des fils, adéquation du substrat, influence des caractérisations pré-analyse. Nous présentons ensuite deux principales études de cas en lien avec une problématique technologique : les microfils de nitrure de gallium dopés Si (diamètre 2 µm) pour applications dans l'éclairage à l'état solide, et les jonctions pn à nanofils de Si (diamètre 100 nm) pour la nanoélectronique basse puissance. Dans le premier cas, nous avons mis en œuvre la SCM pour l'identification rapide de l'hétérogénéité axiale du dopage n, puis avons utilisé l'imagerie XPEEM spectroscopique avec excitation synchrotron pour, d'abord, estimer le travail de sortie local et la courbure de bande en surface; ensuite, élucider les modes d'incorporation du silicium en surface, qui pointent notamment sur la sensibilité des conditions d'élaboration dans la part du dopage intentionnel (Si en sites Ga) et non intentionnel (Si sur sites lacunaires en azote). (Des mesures complémentaires sur sections radiales et longitudinales de fils, par microscopie Auger et spectrométrie ToF-SIMS montrent une incorporation du Si limitée à la surface des microfils). Concernant les jonctions pn à nanofils de silicium étudiées après retrait partiel de l'oxyde de surface, nous avons mis en relation des résultats obtenus indépendamment par KFM et par XPEEM. Ils mettent conjointement en lumière une très faible différence de travail de sortie local entre partie n et partie p, et qui semble en partie expliquée par un ancrage du niveau de Fermi en surface. / This thesis addresses the characterization of individual doped semiconductors microand nanowires by photoemission electron microscopy (XPEEM) and near field techniques : Kelvin probe force microscopy (KFM) and scanning capacitance microscopy. The aim of this study is to evaluate the benefits of contactless surface methods, thanks to local work function and core level binding energy measurements, for the study of phenomena linked to doping in such objects, like for example axial uniformity. First, we highlight the importance of sample preparation required for these techniques: wires transfer methods, substrate/wire match, and preanalysis characterization influence. Then we present two case studies addressing technological issues: Si doped gallium nitride microwires (2μm diameter) for solid state lighting, and p-n junction nanowires (100 nm diameter) for low power microelectronics. In the first case, we have performed SCM for quick identification of n doping axial heterogeneity, then performed spectroscopic XPEEM using synchrotron radiation to, first, estimate local work function and surface band bending, then clarify surface silicon incorporation highlighting growth process influence over intentional (si on Ga sites) and unintentional doping (si on nitrogen vacancy). Complementary measurements on both axial and radial section of wires have been led by Auger microscopy and ToF-SIMS, highlighting silicon incorporation preferentially at the surface of the microwires. Regarding p-n junctions, after partial removal of surface oxide, we have linked results obtained independently by KFM and XPEEM. Both methods highlighted a weak local work function difference between n-doped and p-doped part, partly explained by Fermi level pinning induced by surface states.

Le carbure de silicium est pressenti comme un matériau prometteur dans plusieurs domaines de l’électroniquetels que la nano-électronique, l’électronique de puissance ou les capteurs travaillant en milieuxhostiles (hautes températures, milieux corrosifs, milieux biologiques) du fait de ses propriétés physicochimiquessupérieures à celles du silicium, notamment. Cependant, parmi les différentes méthodesd’élaboration par voie descendante ou ascendante permettant de fabriquer des nano-objets à 1D enSiC, aucune n’a pour l’instant permis d’obtenir du SiC d’excellente qualité cristalline.Le travail de cette thèse a porté sur la démonstration de l’élaboration de nanostructures 1D àbase de SiC, à savoir nanofils coeur-coquille Si-SiC, nanofils de SiC et nanotubes de SiC, par unprocédé original de carburation de nanofils de silicium, eux-mêmes élaborés par gravure plasma. Cettedémonstration a été possible grâce au contrôle de la pression de carburation, ce qui permet la maîtrisede l’exodiffusion des atomes de silicium à travers le carbure de silicium.À pression atmosphérique l’exodiffusion des atomes de silicium est restreinte ce qui permet d’élaborerdes nanofils coeur-coquille Si-SiC avec une coquille de SiC monocristalline et entièrement recouvrante.En se servant de la biocompatibilité du SiC et du bon contrôle électronique dans le silicium, ilest possible d’envisager l’utilisation de ces nanofils coeur-coquille Si-SiC pour des bio-nano-capteurs.En diminuant la pression au cours de la carburation, il est possible d’augmenter l’exodiffusion etainsi d’obtenir des nanotubes de SiC cubique de très bonne qualité cristalline avec des parois denses.Ces nanotubes de SiC sont largement modulables en termes de dimensions, et la faisabilité de leurouverture a été démontrée, permettant ainsi l’utilisation du fort rapport surface sur volume de telsnano-objets pour des capteurs électroniques notamment.Un premier pas a été franchi vers les applications des nanofils coeur-coquille Si-SiC et des nanotubesde SiC, puisque les mesures électriques réalisées sur des nano-transistors à effet de champ utilisant cesdeux types de nano-objets comme canal sont prometteurs. / Due to their superior physical and chemical properties —such as high breakdown field, high thermalconductivity and biocompatibility— compared to other semiconductors, silicon carbide is forseento be a promising materials for power electronics, bio-nano-sensors and nano-electronics in harsh environments.However, among the numerous top-down or bottom-up methods used to synthesise siliconcarbide 1D nano-objects, none has been able yet to produce SiC with a high cristalline quality.The aim of this project is to demonstrate the synthesis of silicon carbide- based 1D nanostructures—e.g. core-shell Si-SiC nanowires, SiC nanowires and SiC nanotubes— through an original processbased on the carburization of plasma-etched silicon nanowires. This demonstration is based on thecontrol of the pressure during the carburization process, which leads to the monitoring of the outdiffusionof silicon atoms through silicon carbide.Thus if the pressure is kept at the atmospheric pressure, the out-diffusion of silicon is limited andSi-SiC core-shell nanowires can be synthesized with a single-crystalline cubic SiC shell. Thanks to thebiocompatibility of the SiC shell and the good electronic transport into the Si core, bio-nano-sensorscan be considered.If the pressure is decreased during the carburization process, the outdiffusion of silicon atomsthrough SiC is enhanced, and leads to SiC nanotubes synthesis. SiC nanotubes sidewalls are dense,with an excellent crystalline quality. These original SiC nanotubes have a high surface to volume ratioand thus can be used for sensors or storage devices.The first step for direct applications has also been demonstrated since first results on electricalperformances of nano-field effect transistors, with these nano-objects as channel, are promising.

Magnetic nanorings are the object of increasing scientific interest because they possess the vortex (stray field free) state which ensures lower magnetostatic interactions between adjacent ring elements in high packing density memory devices. In addition, they have other potential applications such as single magnetic nanoparticle sensors, microwave-frequency oscillators and data processing. The stabilization of magnetization state, types of domains and domain wall structures depends on the competing energies such as magnetostatic, exchange and anisotropy. The nucleation/ pinning of domain walls depends on the local inhomogeneity in shape such as roughness, notches etc, which play an important role in stabilizing domain configurations that can be controlled by magnetic field/spin polarized current etc. The information gained by the study of magnetization reversal in the nanoring devices could help in understanding the possible stable magnetization states, which can be incorporated into the development of magnetic logic and recording devices in a NR-based architecture. The magnetization reversal and the stable states in the symmetric cobalt nanorings (NRs) attached with nanowires (NWs) (at diametrically opposite points), is studied through magnetoresistance (MR) measurements by application of in-plane magnetic field (H). Here, a strong in-plane shape anisotropy is introduced in cobalt thin films by patterning them into NR and NWs. The presence or absence of a DW in the device is detected utilizing the AMR property of the material, where the presence of DW leads to a decrease in the resistance of the probed section of the device. It is demonstrated that the magnetization reversal of the device with smaller width, proceeds through four distinct magnetization states, one of these is the stabilized vortex state that persists over a field range of 0.730 kOe. The effect of width (from 70 nm to 1 µm) and diameter (from 2 µm to 6 µm) on the switching behavior is demonstrated. The magnetization states observed in the MR measurements are well supported by micromagnetic simulations. A statistical analysis of switching fields in these devices was demonstrated by histogram plot (of switching counts) to understand the repeatability and reproducibility of switching characteristics. In addition, the magnetization reversal of permalloy NR is also studied by MR experiment when two NWs are attached to it in two different configurations. It has been demonstrated that a vortex state can be stabilized if the NWs are attached in a way that they are at an obtuse angle with respect to each other (type-II device) which is not the case if the NWs are attached at diametrically opposite points (type-I device). This occurs because the NWs reverse at different fields as they are asymmetric with respect to applied magnetic field at every angle. The angular dependence study of the magnetization states indicates that the vortex state could be always stabilized in the type-II device irrespective of the direction of in-plane applied magnetic field while it is not the case in type-I device. The experimental observations are in good agreement with micromagnetic simulations performed on similar device structures. Further, in the last part of the thesis, the magnetization reversal of geometrically engineered cobalt NR (of width 80 nm) devices are studied by application of H. Two types of cobalt nanoring devices were fabricated. In type-1 devices the NR is attached with two nanowires (NWs) at diametrically opposite positions. In type-2 devices the NR is attached with one NW, whose other end is attached to a 5 µm x 5 µm square pad. In type-2 device, the pad reverses first, thus causing the generation of a DW at the junction of the nucleation pad and the NW. The device type-2 possesses five distinct magnetization states, one of these is the vortex state. Easy nucleation of domain walls (DWs) results in a decrease of switching field corresponding to the reversal of the nanowire. This leads to an increase in the range of fields, where the vortex state exists. In addition, angular dependence of the switching behavior indicates that the vortex state can be stabilized at all in-plane orientations of H. This occurs because of the fact that symmetry was broken due to the presence of single domain wall pinning center which was the junction of the NR and NW. The results of our micromagnetic simulations are in a good agreement with the experimental results. These results are important to understand the role of NWs which allows the formation of vortex state at every angle of the in-plane H. In type-1 device, the simulation shows that when the field is applied at any angle away from the axis of the NW, the vortex state cannot be stabilized. The width dependent study of switching fields indicates, that the switching fields decrease with increasing the width of NR devices due to a reduction of the demagnetization field.

L'objectif de cette thèse porte sur la fabrication et la caractérisation de cellules solaires à jonction radiale à base d'assemblée de nanofils de silicium cristallin. Une étude sur la croissance des nanofils à partir de deux catalyseurs métalliques (cuivre et aluminium) dans une machine de dépôt chimique en phase vapeur (CVD) à pression réduite est présentée. L'influence des conditions de croissance sur la morphologie, le dopage et la contamination des nanofils par le catalyseur est analysée par des mesures électriques, chimiques (SIMS, Auger) et structurales (SEM, TEM, Raman). Le cuivre est utilisé pour la fabrication d'une cellule solaire avec des nanofils de type p et une jonction radiale créée avec du silicium amorphe de type n. Les performances photovoltaïques de la cellule solaire sont ensuite mesurées et interprétées. Un rendement de conversion de 5% est mesuré sur une cellule avec des nanofils de hauteur 1,5µm. / The objective of this PhD is the study of the fabrication and characterization of radial junction solar cells based on crystalline silicon nanowires. A study of the nanowire growth with two metallic catalysts (copper and aluminum) in a reduced pressure chemical vapor deposition system is presented. The influence of the growth conditions on the morphology, doping density and catalyst contamination inside the nanowires is analyzed by electrical, chemical (SIMS) and structural (SEM, TEM, Raman) characterizations. Copper catalyst is used to fabricate a solar cell with p-type nanowire with a radial junction created by n-type amorphous silicon (a-Si:H) deposition. Photovoltaic performances are measured and interpreted. A conversion efficiency of 5% is measured on a solar cell with 1.5µm high silicon nanowires.

Submitted by Vasti Diniz (vastijpa@hotmail.com) on 2017-09-13T12:17:27Z No. of bitstreams: 1 arquivototal.pdf: 26917769 bytes, checksum: 9ff17103475ce4130305b157369d8448 (MD5) / Made available in DSpace on 2017-09-13T12:17:27Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 26917769 bytes, checksum: 9ff17103475ce4130305b157369d8448 (MD5) Previous issue date: 2015-03-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In the present work, we use first-principles calculations based on density functional theory, as implemented in the SIESTA code, to investigate the changes in the structural and electronic properties of the carbon, BN, and hybrid BxCyNz nanotubes produced by one or two of the following mechanisms: doping with carbon atoms, the application of external electric fields, by flattening of the cross section, the encapsulation of a carbon nanowire or the adsorption of hydrogen atoms (hydrogenation). We start with the study of double-walled boron nitride nanotubes (DWBNNTs), zig-zag and armchair, doped with carbon atoms, with chiral vectors (8,0)@(16,0) and (5,5)@(10,10), respectively. Two types of doping were considered: one C atom substituting a B atom on the inner wall (IW) and one C atom substituting a N atom on the outer wall (OW), which we call of CB[IW]@CN[OW], and the opposite situation results in CN[IW]@CB[OW]. In this sense, we generate a (type-p semiconductor)@(type-n semiconductor) and a (type-n semiconductor)@(type-p semiconductor), where the resulting DWBNNTs can be thought of as p-n junctions. At the same time, we apply an external electric field, with magnitude of 0,3 V/Å, in different directions, namely, perpendicular (Ey), parallel (Ex), and antiparallel (E􀀀x) to the line formed by the dopants. Thus, depending on the direction of the applied field, we observe an increase or decrease in the band gap energy between the defect levels (Eig), and such cases are related to the reverse and direct polarization of the p-n junction, respectively. Afterwards, we study the insertion of a carbon nanowire (CNW) inside a (10.0) zigzag carbon nanotube and inside a (10.0) zig-zag BN nanotube. Such systems were called CNW@SWCNT and CNW@SWBNNT, respectively. We produce the flattening of the nanotubes and verify the behavior of the atomic structure of the nanowire as the flattening of the nanotube increases. From the obtained results, it was possible to conclude that, for both CNW@SWCNT and CNW@SWBNNT, there is a critical distance dc (distance between the parallel planes of the flattened nanotubes (d)), with the value of 3.60 Å, so that we can summarize our findings as follows: in the case d > dc, the carbon nanowire does not undergo any deformation; and in the reverse case (d < dc), the carbon nanowire binds to the wall of the nanotube and undergoes deformations. Regarding the electronic properties, we verify that the encapsulation of the CNW inside the SWCNT and SWBNNT, produces a significant reduction of the band gap energy (Eg) of such systems. Moreover, we observe ABSTRACT viii the creation of Dirac points for some flattening ratios of the nanotubes. Finally, we carry out a study on the adsorption of hydrogen atoms (hydrogenation) on the surface of double-walled boron nitride nanotubes (DWBNNTs) and hybrid nanotubes of boron nitride and carbon (DW(BN)xCyNTs). Due to the fact that the nanotubes have two walls, we consider the following cases: (i) coverages of 2H, 4H, 8H, 12H, and 16H on the inner wall, (ii) coverages of 2H, 4H, 8H, 16H, and 32H on the outer wall, and (iii) coverages of 2H, 4H, 8H, 16H, and 32H on both walls. Curiously, we find that for all hydrogen coverages considered, a strong deformation occurs in the hydrogen regions, causing the cross section of the nanotubes take different polygonal shapes: ellipsoidal, rectangular, hexagonal or octahedral. For coverages of 16H and 32H only on the outer wall, we observe that some hydrogens desorbed from the wall forming isolated H2 molecules without preferential orientation. We verify that, in some cases, the bond angles between the B, N and H or C and H atoms exhibit characteristics of the sp3 hybridization. Regarding the structural stability, we verify that the adsorption of H atoms in DWBNCNTs is more favorable than in DWBNNTs. Moreover, we conclude that is possible to control the band gap energy of the nanotubes through the hydrogen coverage. / No presente trabalho, usamos cálculos de primeiros princípios baseados na Teoria do Funcional da Densidade, como implementado no código SIESTA, para investigarmos as alterações nas propriedades estruturais e eletrônicas de nanotubos de carbono, de BN e híbridos BxCyNz, produzidas por um ou dois dos seguintes mecanismos: dopagem com átomos de carbono, aplicação de campos elétricos externos, pelo achatamento da secção transversal, encapsulamento de um nanofio de carbono ou pela adsorção de átomos de hidrogênio (hidrogenação). Iniciamos com o estudo de nanotubos de nitreto de boro de parede dupla (DWBNNTs), zig-zag e armchair, dopados com átomos de carbono, com vetores quirais (8,0)@(16,0) e (5,5)@(10,10), respectivamente. Duas situações de dopagem foram consideradas: um átomo de C substituindo um átomo de B na parede interna (IW) e um átomo de C substituindo um átomo de N na parede externa (OW) a qual chamamos de CB[IW]@CN[OW], e a situação oposta resulta em CN[IW]@CB[OW]. Neste sentido, construímos um (semicondutor do tipo-p)@(semicondutor do tipo-n) e um (semicondutor do tipo-n)@(semicondutor do tipo-p) onde os DWBNNTs resultantes podem ser pensados como junções p-n. Paralelamente, aplicamos um campo elétrico externo, com magnitude de 0,3 V/Å, em diferentes direções, a saber, perpendicular (Ey), paralelo (Ex) e anti-paralelo (E􀀀x) a linha formada pelos dopantes. Assim, dependendo da direção do campo aplicado, observamos um aumento ou diminuição do gap de energia entre os níveis de defeitos (Eig) e tais casos estão relacionados a polarização reversa e direta da junção p-n, respectivamente. Em seguida, estudamos a inserção de um nanofio de carbono (CNW) no interior de um nanotubo de carbono e de BN, ambos com vetor quiral (10.0). Tais sistemas foram chamados de CNW@SWCNT e CNW@SWBNNT, respectivamente. Nós produzimos o achatamento dos nanotubos e verificamos o comportamento da estrutura atômica do nanofio a medida que o achatamento do nanotubo aumenta. A partir dos resultados obtidos, foi possível concluir que para ambos os CNW@SWCNT e CNW@SWBNNT, existe uma distancia crítica dc (distância entre os planos paralelos dos nanotubos achatados (d)), com um valor de 3.60 Å, de tal forma que nós podemos resumir as nossas descobertas como: no caso de d > dc, o nanofio de carbono não sofre nenhuma deformação; e no caso reverso (d < dc), o nanofio de carbono liga-se a parede do nanotubo e sofre deformações. Em relação as propriedades eletrônicas, verificamos que o encapsulamento do CNW nos SWCNT e SWBNNT, produz uma significativa redução do gap de energia (Eg) de tais sisteRESUMO vi mas. Além disso, observamos a formação de pontos de Dirac para algumas taxas de achatamento dos nanotubos. Por último, nós realizamos um estudo da adsorção de átomos de hidrogênio (hidrogenação) sobre a superfície de um nanotubo de parede dupla de nitreto de boro (DWBNNTs) e um nanotubo híbrido de nitreto de boro e carbono (DW(BN)xCyNTs). Devido ao fato dos nanotubos possuírem duas paredes, consideramos os seguintes casos: (i) coberturas de 2H, 4H, 8H, 12H e 16H na parede interna, (ii) coberturas de 2H, 4H, 8H, 16H e 32H na parede externa e (iii) coberturas de 2H, 4H, 8H, 16H e 32H em ambas as paredes. Curiosamente, verificamos que em todas as coberturas de hidrogênio consideradas, uma forte deformação ocorre nos locais de hidrogênio, fazendo a secção transversal dos nanotubos se transformar em diferentes formas poligonais: elipsoidal, retangular, hexagonal ou octaedral. Para coberturas de 16H e 32H apenas na parede externa, observamos que alguns hidrogênios se dessorveram da parede formando moléculas de H2 isoladas sem orientação preferencial. Verificamos que em alguns casos, os ângulos de ligação entre os átomos de B, N e H ou C e H exibem características da hibridação sp3. Com relação a estabilidade estrutural, verificamos que a adsorção de átomos de H em DWBNCNTs é mais favorável do que em DWBNNTs. Ademais, concluímos que é possível controlar o gap de energia dos nanotubos através da cobertura de hidrogênio.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-06-08T19:22:26Z No. of bitstreams: 1 danilotoscano.pdf: 27568683 bytes, checksum: f844e19659c551e6e7a4e5b53adf1497 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-06-26T20:13:05Z (GMT) No. of bitstreams: 1 danilotoscano.pdf: 27568683 bytes, checksum: f844e19659c551e6e7a4e5b53adf1497 (MD5) / Made available in DSpace on 2017-06-26T20:13:05Z (GMT). No. of bitstreams: 1 danilotoscano.pdf: 27568683 bytes, checksum: f844e19659c551e6e7a4e5b53adf1497 (MD5) Previous issue date: 2015-02-25 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Durante as últimas décadas a dinâmica da magnetização em sistemas nano-estruturados tornou-se um assunto de importância fundamental não apenas para o Micromagnetismo, mas também às suas aplicações tecnológicas. Nanomagnetos são sistemas interessantes para estudar estruturas magnéticas exóticas, tais como vórtices, skyrmions e paredes de domínio. A compreensão das propriedades estáticas e dinâmicas dessas configurações de spins em nano-escala é um requerimento crucial para a realização de futuros dispositivos baseados em spintrônica. Devido à anisotropia de forma que se origina da interação dipolar, as configurações magnéticas que surgem em sistemas nano-estruturados são bastante sensíveis à forma geométrica e às dimensões do nanomagneto. Este trabalho é focado no estudo de nanomagnetos planares, nos formatos de disco e fita, feitos com um material magnético macio como o Permalloy. O vórtice magnético é observado num nanodisco com dimensões adequadas, porque ele é um estado intermediário entre os regimes de mono e multi-domínio. Sob condições apropriadas, uma única parede de domínio transversal pode ser experimentalmente injetada num nanofio retangular. Tanto o núcleo do vórtice quanto a parede de domínio comportam-se como quasipartículas, cujas propriedades podem ser manipuladas por um agente externo (campo magnético ou corrente de spin-polarizado). Para pequenas amplitudes de excitação, é sabido que o núcleo do vórtice descreve um movimento circular (modo girotrópico), enquanto que a parede de domínio transversal fica restrita a um movimento unidimensional. Neste regime, cada quasipartícula evolui sem mudar a sua polaridade; uma propriedade estrutural associada a um estado duplamente degenerado. Para uma amplitude de excitação forte o suficiente, a quasipartícula sofre uma deformação na sua estrutura, tal que a ocorre a inversão da polaridade. Do ponto de vista tecnológico, o controle do mecanismo de reversão da polaridade é fundamental, porque essa degenerescência de dois estados pode funcionar como "zero"ou "um", sendo útil para codificar informação no armazenamento de dados ou mesmo para realizar operações lógicas. Alguns trabalhos reportaram que nanomagnetos contendo defeitos podem influenciar ou modificar fortemente a dinâmica da quasipartícula. Imperfeições são geradas durante o processo de fabricação dos nanomagnetos, ou então elas podem ser intencionalmente incorporadas para uma finalidade específica. Como exemplo, a fim de controlar o movimento da parede de domínio é muito importante impor determinadas posições ao longo do nanofio onde a parede possa parar. Há várias maneiras de se estabelecer tais pontos críticos para a quasipartícula. Variações na geometria do nanomagneto, cavidades, entalhes e assim por diante podem ser classificadas como defeitos não-magnéticos. Em geral, esse tipo de defeito funciona como um centro atrator para a quasipartícula. Um defeito magnético surge a partir de uma falta de homogeneidade do meio magnético, ou seja, uma variação local das propriedades magnéticas. Num trabalho anterior, nosso grupo modelou uma impureza magnética como uma variação local da constante de troca. Como um resultado imediato da inserção de uma impureza magnética no nanomagneto, demonstramos via simulações numéricas, que impurezas magnéticas podem induzir dois tipos de armadilhas para a quasipartícula: uma redução local da constante de troca corresponde a um sítio de aprisionamento (poço de potencial), enquanto que um aumento local da constante de troca representa um sítio de bloqueio (barreira de potencial). Esta tese investiga a dinâmica da quasipartícula confinada por uma distribuição de impurezas magnéticas: para o caso do núcleo do vórtice considerou-se um anel de impurezas, concêntrico ao nanodisco; para o caso da parede de domínio foi considerado dois aglomerados de impurezas, idênticos e equidistantes do eixo da largura do nanofio. Os resultados obtidos para o nanodisco modificado mostraram que é possível modular a frequência girotrópica do núcleo do vórtice, que depende fortemente da razão de aspecto do disco (espessura/diâmetro). Num disco com o anel de impurezas, um ajuste fino na frequência girotrópica pode ser obtido pela variação dos parâmetros do anel. Além disso, foi observado que a inversão da polaridade do núcleo do vórtice pode ocorrer devido à interação entre o núcleo do vórtice com o anel; a reversão da polaridade num disco com o anel requer amplitudes de excitação menores do que aquelas requeridas no disco sem o anel. Os resultados obtidos para o nanofio modificado indicaram que é possível controlar posição da parede de domínio transversal; a parede pode ser de movida de um aglomerado até o outro pela simples inversão do sentido do campo magnético aplicado. A reversão da polaridade da parede de domínio transversal também foi investigada e o uso dessa distribuição de impurezas mostrou-se útil para estabilizar o movimento da parede que ocorre após a inversão da polaridade; assim a mudança da polaridade ocorre de uma forma rápida e reversível. Como um exemplo de aplicação desse nanofio modificado, propomos o seu uso como uma célula num dispositivo de memória não-volátil, que usa 2 bits por célula; ou seja, a informação pode ser armazenada tanto na posição quanto na polaridade da parede de domínio transversal. Embora os resultados apresentados aqui sejam para simples distribuições de impurezas magnéticas acreditamos que as suas consequências possam ser planejadas e estendidas para o desenvolvimento e realização de futuros dispositivos. / During the last decades the magnetization dynamics in nanostructured systems has become a subject of relevance from fundamental micromagnetism as well as for their new potential technological applications. Nanomagnets are interesting systems to study exotic magnetic structures like vortices, skyrmions and domain walls. The detailed understanding of the static and dynamic properties of these nanoscale spin configurations is a crucial requirement for the realization of future spintronic device. Due to the shape anisotropy that originates from dipolar interaction, the magnetic configurations that emerge in nanostructured systems are very sensitive to the geometric form and dimensions of the nanomagnet. This work is focused on the study of planar nanomagnets, in the formats of disk and strip, made of a soft magnetic material like Permalloy. The magnetic vortex is observed in a nanodisk with appropriate dimensions, because it is an intermediate state between the mono and multi-domain regimes. Under suitable conditions, a single transverse domain wall can be experimentally injected into a rectangular nanowire. Both the vortex core and the wall behaves as a quasiparticle, whose the properties can be manipulated by an external agent (magnetic field or spin polarized current). At low excitation amplitudes, it is known that the vortex describes a circular movement, whereas the wall is restricted to an unidirectional movement. In this regime, each quasiparticle evolves without changing its polarity; a structural property associated with a two-fold degenerate state. For an excitation amplitude strong enough, the quasiparticle experiences a deformation on its structure so that, it occurs the switching of the polarity. From the technological point of view, the control of the polarity reversing mechanism is fundamental, because this two-fold degeneracy can work as "zero"or "one", being useful to encode information for data storage or even to perform logical operations. Some works reported that nanomagnets containing defects can influence or modify strongly the dynamic of the quasiparticle. Imperfections are generated during the fabrication process of the nanomagnets or else they can be intentionally incorporated for a specific purpose. As an example, in order to control the domain wall motion it is very important to impose certain positions along the nanowire where the wall can stop. There are several means of establishing such critical points for the quasiparticle. Variations of geometry, cavities, notches, and so on can be classified as non-magnetic defects. Generally, this type of defect acts as a pinning site for the quasiparticle. A magnetic defect emerges from an inhomogeneity of the magnetic environment, in other words, a local variation of the magnetic properties. In a previous study, our team has modeled a magnetic impurity as a local variation of the exchange constant. As an immediate result of the insertion of a magnetic impurity into a nanomagnet, we have demonstrated via numerical simulations that magnetic impurities can induce two types of traps for the quasiparticle: a local reduction of the exchange constant corresponds to a pinning site (potential well), whereas a local increase of the exchange constant represents a blocking site (potential barrier). This thesis investigates the dynamic of the quasiparticle confined by a distribution of magnetic impurities: for the case of the vortex core it has been considered a ring of impurities, concentric to the nanodisk; and for the case of the domain wall it has been considered two clusters of impurities, identical and equidistant from the nanowire width axis. The found results for the modified nanodisk have shown that it is possible to modulate the gyrotropic frequency that depends strongly on the disk aspect ratio (thickness/diameter). In a disk with the ring of magnetic impurities, a fine tuning of the gyrotropic frequency can be obtained by varying of the ring parameters. Furthermore, it was found that the polarity switching of the vortex core can occur due to the interaction between the vortex core and the ring; the polarity reversing in a disk with a ring requires smaller excitation amplitudes than the disk without the ring does. The found results for the nanowire have indicated that it is possible to control the transverse domain wall position; the wall can be moved from a cluster to the other by simply reversing of the magnetic field direction. The switching of the transverse domain wall polarity was also investigated and the use of this impurity distribution demonstrated to be useful to stabilize the motion wall motion after occurring polarity reversal; thus the changing of the polarity occurs in a fast and reversible way. As an example of the application of this modified nanowire, we propose its use as a cell in a nonvolatile memory device based on 2 bits per cell, in other words, the information can be encoded in the position as well as the polarity of the transverse domain wall. Although the results presented here are for a very simple distribution of magnetic impurities, we believe their consequences can be planned and extended for the design and realization of future devices.