Made available in DSpace on 2014-06-11T19:35:05Z (GMT). No. of bitstreams: 0 Previous issue date: 2005-04-14Bitstream added on 2014-06-13T20:06:19Z : No. of bitstreams: 1 marques_vpb_dr_araiq.pdf: 6875606 bytes, checksum: 6e3a2c49ede6d05f9db32af09bf934fc (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Estudos preliminares foram realizados em cerâmicas com propriedades varistoras, à base, SnO2-TiO2-Co2O3, com adições de Nb2O5, Ta2O5, Cr2O3 e Al2O3, preparados por meio de misturas de óxidos em moinho de alta energia, sinterizados em forno tubular na temperatura de 1250ºC durante 90 min em atmosfera de oxigênio, argônio e ambiente. Foram caracterizados quanto à densidade e propriedades elétricas.Terminada essa etapa, o sistema escolhido foi aquele que melhor se adaptou ao propósito do estudo desse trabalho. O sistema escolhido, SnO2-0,75TiO2-0,1Co2O3-0,05Nb2O5 mol %, foi preparado nas mesmas condições que na fase preliminar, sinterizados em atmosfera ambiente, tratados termicamente a 900ºC durante 60 min em atmosfera de oxigênio, e a pressão reduzida (10- 2torr). Em seqüência, essas amostras foram caracterizadas quanto as suas propriedades elétricas (medida tensão-corrente, espectroscopia de impedância e microscopia de força eletrostática) e microestruturais (difração de raios x, microscopia eletrônica de varredura, analise de EDX, analise de EDS, microscopia eletrônica de transmissão e espectroscopia de fotoelétrons induzida por raios x). A medida da altura da barreira foi obtida por meio da técnica de microscopia de força eletrostática através de uma modelagem matemática. / In the present thesis it was studied nonohmic electronic ceramics based on SnO2.TiO2.Co2O3 ternary systems doped with Nb2O5, Ta2O5, Cr2O3 and Al2O3. These systems were prepared using traditional ball milling oxide mixture process. The sintering was conducted using tubular furnace at 1250 ºC for 90 min in different atmospheres: oxygen, argon and ambient atmosphere. Structural, density and electrical properties were investigated in all of the systems. The system presenting superior electrical properties was chosen to be studied concerning relationship between microstructural features and electrical properties. Therefore, SnO2-0.75TiO2-0.1Co2O3-0.05Nb2O5 % mol composition was thermal treated at 900 ºC for 60 min at oxygen-rich and oxygen-poor (10-2torr) atmospheres. After this step, the system was characterized by using different electrical, structural and microstructural techniques (current-voltage, impedance spectroscopy and electronic force image, X-ray diffraction, scanning electronic microscopy (SEM) and energy dispersive x-ray (EDX), energy dispersive spectroscopy (EDS) and transmission electron microscopy (TEM). The potential barrier was mathematical modeled according to electrostatic force images. The mathematical treatment is based on a matrix systems applied to each potential difference existing in the sample. From the solution of the matrix system it is possible to obtain the barrier height as a function of the applied potential.

Polymer and organic electronic memory devices offer the potential for cheap, simple memories that could compete across the whole spectrum of digital memories, from low cost, low performance applications, up to universal memories capable of replacing all current market leading technologies, such as hard disc drives, random access memories and Flash memories. Polymer memory devices (PMDs) are simple, two terminal metal-insulator-metal (MIM) bistable devices that can exist in two distinct conductivity states, with each state being induced by applying different voltages across the device terminals. Currently there are many unknowns and much ambiguity concerning the working mechanisms behind many of these PMDs, which is impeding their development. This research explores some of these many unanswered questions and presents new experimental data concerning their operation. One prevalent theory for the conductivity change is based on charging and charge trapping of nanoparticles and other species contained in the PMD. The work in this research experimentally shows that gold nanoparticle charging is possible in these devices and in certain cases offers an explanation of the working mechanism. However, experimental evidence presented in this research, shows that in many reported devices the switching mechanism is more likely to be related to electrode effects, or a breakdown mechanism in the polymer layer. Gold nanoparticle charging via electrostatic force microscopy (EFM) was demonstrated, using a novel device structure involving depositing gold nanoparticles between lateral electrodes. This allowed the gold nanoparticles themselves to be imaged, rather than the nanoparticle loaded insulating films, which have previously been investigated. This method offers the advantages of being able to see the charging effects of nanoparticles without any influence from the insulating matrix and also allows charging voltages to be applied via the electrodes, permitting EFM images to capture the charging information in near real-time. Device characteristics of gold nanoparticle based PMDs are presented, and assessed for use under different scenarios. Configurations of memory devices based on metal-insulator-semiconductor (MIS) structures have also been demonstrated. Simple interface circuitry is presented which is capable of performing read, write and erase functions to multiple memory cells on a substrate. Electrical properties of polystyrene thin films in the nanometre thickness range are reported for the first time, with insulator trapped charges found to be present in comparable levels to those in silicon dioxide insulating films. The dielectric breakdown strength of the films was found to be significantly higher than bulk material testing would suggest, with a maximum dielectric strength of 4.7 MV•cm-1 found, compared with the manufacturers bulk value of 0.2 – 0.8 MV•cm-1. Conduction mechanisms in polystyrene were investigated with the dominant conduction mechanism found to be Schottky emission.

Orientador: Mario Cilense / Banca: Carlos de Oliveira Paiva Santos / Banca: Paulo Roberto Bueno / Banca: Edson Roberto Leite / Banca: Dulcina Maria Pinatti Ferreira de Souza / Resumo: Estudos preliminares foram realizados em cerâmicas com propriedades varistoras, à base, SnO2-TiO2-Co2O3, com adições de Nb2O5, Ta2O5, Cr2O3 e Al2O3, preparados por meio de misturas de óxidos em moinho de alta energia, sinterizados em forno tubular na temperatura de 1250ºC durante 90 min em atmosfera de oxigênio, argônio e ambiente. Foram caracterizados quanto à densidade e propriedades elétricas.Terminada essa etapa, o sistema escolhido foi aquele que melhor se adaptou ao propósito do estudo desse trabalho. O sistema escolhido, SnO2-0,75TiO2-0,1Co2O3-0,05Nb2O5 mol %, foi preparado nas mesmas condições que na fase preliminar, sinterizados em atmosfera ambiente, tratados termicamente a 900ºC durante 60 min em atmosfera de oxigênio, e a pressão reduzida (10- 2torr). Em seqüência, essas amostras foram caracterizadas quanto as suas propriedades elétricas (medida tensão-corrente, espectroscopia de impedância e microscopia de força eletrostática) e microestruturais (difração de raios x, microscopia eletrônica de varredura, analise de EDX, analise de EDS, microscopia eletrônica de transmissão e espectroscopia de fotoelétrons induzida por raios x). A medida da altura da barreira foi obtida por meio da técnica de microscopia de força eletrostática através de uma modelagem matemática. / Abstract: In the present thesis it was studied nonohmic electronic ceramics based on SnO2.TiO2.Co2O3 ternary systems doped with Nb2O5, Ta2O5, Cr2O3 and Al2O3. These systems were prepared using traditional ball milling oxide mixture process. The sintering was conducted using tubular furnace at 1250 ºC for 90 min in different atmospheres: oxygen, argon and ambient atmosphere. Structural, density and electrical properties were investigated in all of the systems. The system presenting superior electrical properties was chosen to be studied concerning relationship between microstructural features and electrical properties. Therefore, SnO2-0.75TiO2-0.1Co2O3-0.05Nb2O5 % mol composition was thermal treated at 900 ºC for 60 min at oxygen-rich and oxygen-poor (10-2torr) atmospheres. After this step, the system was characterized by using different electrical, structural and microstructural techniques (current-voltage, impedance spectroscopy and electronic force image, X-ray diffraction, scanning electronic microscopy (SEM) and energy dispersive x-ray (EDX), energy dispersive spectroscopy (EDS) and transmission electron microscopy (TEM). The potential barrier was mathematical modeled according to electrostatic force images. The mathematical treatment is based on a matrix systems applied to each potential difference existing in the sample. From the solution of the matrix system it is possible to obtain the barrier height as a function of the applied potential. / Doutor

Ce manuscrit présente une étude expérimentale de phase isolante non-conventionnelle, l'isolant d'Anderson, induit par le désordre, l'isolant de Mott, induit par les interactions de Coulomb, et les isolants topologiques.Dans une première partie du manuscrit, je décrirais le développement d'une méthode pour étudier la réponse de charge de nanoparticules par Microscopie à Force Electrostatique (EFM). Cette méthode a été appliquée à des nanoparticules de magnétite (Fe3O4), un matériau qui présente une transition métal-isolant, i.e. la transition de Verwey, lors de son refroidissement en dessous d'une température TV~120 K.Dans une seconde partie, ce manuscrit présente une étude détaillée de l'évolution de la densité d'états au travers de la transition métal-isolant entre un isolant de type Anderson-Mott et une phase métallique dans le matériau SrTiO3, et ceci, en fonction de la concentration de dopants, les lacunes d'oxygènes. Nous avons trouvé que dans un dispositif memoresistif de type Au-SrTiO3-Au, la concentration de dopants pouvait être ajustée par migration des lacunes d'oxygènes à l'aide d'un champ. Dans cette jonction tunnel, l'évolution de la densités d'états au travers de la transition métal-isolant peut être étudiée de façon continue. Finalement, dans une troisième partie, le manuscrit présente le développement d'une méthode pour la microfabrication d'anneaux de Aharonov-Bohm avec l'isolant topologique, Bi2Se3, déposée par épitaxie à jet moléculaire. Des résultats préliminaires sur les propriétés de transport quantique de ces dispositifs seront présentés. / This manuscript presents an experimental study of unconventional insulating phases, which are the Anderson insulator, induced by disorder, the Mott insulator, induced by Coulomb interactions, and topological insulators.In a first part of the manuscript, I will describe the development of a method to study the charge response of nanoparticles through Electrostatic Force Microscopy (EFM). This method has been applied to magnetite Fe3O4 nanoparticles, a material that presents a metal-insulator transition, i.e. the Verwey transition, upon cooling the system below a temperature Tv=120K. In a second part, this manuscript presents a detailed study of the evolution of the Density Of States (DOS) across the metal-insulator transition between an Anderson-Mott insulator and a metallic phase in the material SrTiO3 and this, as function of dopant concentration, i.e. oxygen vacancies. We found that in this memristive type device Au-SrTiO3-Au, the dopant concentration could be fine-tuned through electric-field migration of oxygen vacancies. In this tunnel junction device, the evolution of the DOS can be followed continuously across the metal-insulator transition. Finally, in a third part, the manuscript presents the development of a method for the microfabrication of Aharonov-Bohm rings with the topological insulator material, Bi2Se3, grown by molecular beam epitaxy. Preliminary results on the quantum transport properties of these devices will be presented.

Les interphases sont souvent considérées comme responsables des propriétés physiques des nanodiélectriques inexplicables par les lois de mélange. La prédiction de la permittivité diélectrique des nanodiélectriques nécessite de reconsidérer la permittivité intrinsèque et le volume de l'interphase. Malgré le besoin d'une caractérisation locale de ces régions interfaciales nanométriques, aucune méthode expérimentale fiable n'a encore été développée. La Microscopie à Force Electrostatique (EFM) constitue une technique prometteuse pour atteindre ce but. L'objectif de cette thèse est de développer des protocoles expérimentaux et des méthodes d’interprétations du signal appropriés pour évaluer l’aptitude de l’EFM à l'étude des interphases dans les nanodiélectriques. Nous avons eu recours d’abord à des simulations numériques par éléments-finis pour approfondir notre compréhension de l'interaction entre une sonde EFM et plusieurs types d'échantillons nanostructurés, permettant par la suite de simuler la réponse spécifique face à un nanocomposite possédant une interphase. Nous avons proposé un modèle électrostatique de nanodiélectrique possédant trois phases, selon lequel, nous avons conçu et synthétisé des échantillons modèles aux propriétés connues afin de jouer le rôle de matériaux nanodiélectriques de référence pour les mesures EFM. Par conséquent, nous avons pu développer plusieurs protocoles expérimentaux et d’analyses du signal utilisant des modes DC et AC de détection du gradient de force pour caractériser les interphases dans des nanocomposites. Ces techniques constituent un ensemble polyvalent de méthodes d’étude des interphases avec un impact réduit des effets parasites communément convolués dans les signaux EFM. Enfin, une quantification de la permittivité de l'interphase de nos échantillons modèles a été possible par corrélation avec nos simulations numériques. / Interphases are usually considered to be responsible for the physical properties of nanodielectrics unexplainable by general mixture laws. The prediction of the effective dielectric permittivity of these materials needs to reconsider the intrinsic permittivity and the volume of the interphase. Despite the urge for a local characterization of these nanometric interfacial regions, no reliable experimental method has been developed yet. The Electrostatic Force Microscope (EFM) constitutes a promising technique to fulfill this objective. The aim of this thesis is to develop appropriate experimental protocols and signal analysis to explore the ability of EFM to the study of interphases in nanodielectrics. We first resorted to finite-element numerical simulations in order to deeper our understanding of the interaction between an EFM probe and several types of nanostructured samples, allowing to simulate afterwards the specific response to a nanocomposite possessing an interphase. We proposed a three-phase electrostatic model of a nanodielectric, upon which, we designed and synthesized model samples of known properties to play the role of a reference nanodielectric material for EFM measurements. Consequently, we were able to develop several experimental protocols and signal analysis with both DC and AC force gradient EFM modes. These techniques offer versatile methods to characterize interphases with reduced impact of the parasitic effects commonly convoluted within EFM signals. Finally, a quantification of the interphase in our nanodielectric model samples was possible thanks to correlation with our numerical simulations.

The present research work mainly focuses on the fabrication of 0.85PMN-0.15PT thin film relaxor ferroelectrics for energy harvesting applications. Chapter 1 gives a brief review about why energy harvesting is required and the different ways it can be scavenged. An introduction to relaxor ferroelectrics and their characteristics structural features are discussed. A brief introduction is given about charge storage, electrocaloric effect , DC-EFM and integration over Si substrate is discussed. Finally, the specific objectives of the current research are outlined. Chapter 2 deals with the various experimental studies carried out in this research work. It gives the details of the experimental set up and the basic operation principles of various structural and physical characterizations of the materials prepared. A brief explanation of material fabrication, Microstructural and physical property measurements is discussed. Chapter3 involves the optimization process carried out to contain a phase pure PMN-PT structure without any pyrochlore phase. The optimization process is an important step in the fabrication of a thin film as the quality of any device is determined by their structural and Microstructural features. XRD, SEM, AFM were used to characterize the observed phase formation in these films. The optimizing domain images of polycrystalline 0.85PMN-0.15PT thin films on La0.5Sr0.5CoO3/ (111) Pt/TiO2/SiO2/Si substrates deposited at different oxygen partial pressures are presented. The oxygen pressure has a drastic influence on the film growth and grain morphology which are revealed through XRD and SEM characterization techniques. The presence of oxygen vacancies have found to influence the distribution of polar nanoregions and their dynamics which are visualized using domain images acquired by DC-EFM In Chapter 7 the piezoelectric response of 0.85PMN-0.15PT thin films are studied due to the electric field induced bias. From this the d33 value is calculated. d33 value is an important parameter which determines whether a material is suitable for device application (PZT). But, for a device fabrication it is important to integrate them with Si wafer which is not a straightforward work .Hence, buffer layers are used to obtain a pure perovskite PMN-PT film. We have deposited 0.85PMN-0.15PT thin films of 500 nm on a SOI wafer and tried to investigate their piezoelectric application. Chapter 8 summarizes the present study and discusses about the future work that could give more insight into the understanding of the0.85PMN-0.15 PT relaxor ferroelectric thin film.

Nanocomposites of polyethylene and metal oxide nanoparticles have shown to be a feasible approachto the next generation of insulation in high voltage direct current cables. In order to reach an operationvoltage of 1 MV new insulation materials with reduced conductivity and increased breakdown strengthas compared to modern low-density polyethylene (LDPE) is needed.In this work polyethylene MgO nanocomposites for electrical insulation has been produced andcharacterized both from an electrical and material perspective. The MgO nanoparticles weresynthesized into polycrystalline nanoparticles with a large specific surface area (167 m2 g–1). Meltprocessing by extrusion resulted in evenly dispersed MgO nanoparticles in LDPE for the silane surfacemodified MgO as compared to the unmodified MgO. All systems showed a reduction in conductivityby up to two orders of magnitude at low loading levels (1–3 wt.%), but where the surface modifiedsystems were able to retain reduced conductivity even at loading levels of 9 wt.%. A maximuminteraction radius to influence the conductivity of the MgO nanoparticles was theoretically determinedto ca. 800 nm. The interaction radius was in turn experimentally observed around Al2O3 nanoparticlesembedded in LDPE using Intermodulation electrostatic force microscopy. By applying a voltage on theAFM-tip charge injection and extraction around the Al2O3 nanoparticles was observed, visualizing theexistence of additional localized energy states on, and around, the nanoparticles. Ptychography wasused to reveal nanometre features in 3D of electrical trees formed under DC-conditions. Thevisualization showed that the electrical tree grows by pre-step voids in front of the propagatingchannels, facilitating further growth, much in analogy to mechanical crack propagation (Griffithconcept). An electromechanical effect was attributed as possible mechanism for the formation of the voids. / Nanokompositer av polyeten och metalloxidpartiklar anses vara möjliga material att använda i morgondagens isolationshölje till högspänningskablar för likström. För att nå en transmissionsspänning på 1 MV behövs isolationsmaterial som i jämförelse med dagens polyeten har lägre elektrisk ledningsförmåga, högre styrka mot elektriskt genomslag och som kan kontrollera ansamling av rymdladdningar. De senaste årens forskning har visat att kompositer av polyeten med nanopartiklar av metalloxider har potential att nå dessa egenskaper. I det här arbetet har kompositer av polyeten och nanopartiklar av MgO för elektrisk isolation producerats och karaktäriserats. Nanopartiklar av MgO har framställts från en vattenbaserad utfällning med efterföljande calcinering, vilket resulterade i polykristallina partiklar med en mycket stor specifik ytarea (167m2 g-1). MgO-nanopartiklarna ytmodifierades i n-heptan genom att kovalent binda oktyl(trietoxi)silan och oktadekyl(trimetoxi)silan till partiklarna för att skapa en hydrofob och skyddande yta. Extrudering av de ytmodifierade MgO nanopartiklarna tillsammans med polyeten resulterade i en utmärkt dispergering med jämnt fördelad partiklar i hela kompositen, vilket ska jämföras med de omodifierade partiklarna som till stor utsträckning bildade agglomerat i polymeren. Alla kompositer med låg fyllnadsgrad (1–3 vikt% MgO) visade upp till 100 gånger lägre elektrisk konduktivitet jämfört med värdet för ofylld polyeten. Vid högre koncentrationer av omodifierade MgO förbättrades inte de isolerande egenskaperna på grund av för stor andel agglomerat, medan kompositerna med de ytmodifierade fyllmedlen som var väl dispergerade behöll en kraftig reducerad elektrisk konduktivitet upp till 9 vikt% fyllnadshalt. Den minsta interaktionsradien för MgO-nanopartiklarna för att minska den elektriska konduktiviten i kompositerna fastställdes med bildanalys och simuleringar till ca 800 nm. Den teoretiskt beräknade interaktionsradien kompletterades med observation av en experimentell interaktionsradie genom att mäta laddningsfördelningen över en Al2O3-nanopartikle i en polyetenfilm med intermodulation (frekvens-mixning) elektrostatisk kraftmikroskop (ImEFM), vilket är en ny AFM-metod för att mäta ytpotentialer. Genom att lägga på en spänning på AFM-kantilevern kunde det visualiseras hur laddningar, både injicerades och extraherades, från nanopartiklarna men inte från polyeten. Det tolkades som att extra energinivåer skapades på och runt nanopartiklarna som fungerar för att fånga in laddningar, ekvivalent med den gängse tolkningen att nanopartiklar introducera extra elektronfällor i den polymera matrisen i nanokompositer. Nanotomografi användes för att avbilda elektriska träd i tre dimensioner. Avbildningen av det elektriska trädet visade att tillväxten av trädet hade skett genom bildning av håligheter framför den framväxande trädstrukturen. Håligheterna leder till försvagning av materialet framför det propagerande trädet och förenklar på det sättet fortsatt tillväxt. Bildningen av håligheter framför trädstrukturen uppvisar en analogi till propagering av sprickor vid mekanisk belastning, i enlighet med Griffiths koncept. / <p>QC 20161006</p>