Orientador: Walter Katsumi Sakamoto / Banca: Aparecido Augusto de Carvalho / Banca: Darcy Hiroe Fujii Kanda / Banca: Washington Luiz de Barros Melo / Banca: Mauro Henrique de Paula / Resumo: Apresenta-se nesse trabalho a preparação, caracterização e aplicação de um compósito na forma de filme com três concentrações diferentes de cerâmica, objetivando observar seu comportamento quando submetido a radiação ionizante (raios X) e não ionizante (infravermelho). Os compósitos são constituídos da cerâmica titanato de chumbo modificado com cálcio (PTCa) imersa em uma matriz polimérica constituída de poliéter éter cetona (PEEK). Os filmes foram obtidos por prensagem a quente. O compósito foi caracterizado com a medida do coeficiente piezoelétrico (d33), variando a concentração de cerâmica, a temperatura de polarização, a intensidade de campo aplicado e o tempo de polarização. Posteriormente, foi medido o coeficiente piroelétrico, perda dielétrica e permissividade dielétrica, para as três concentrações de cerâmica proposta. Para a amostra com 60% de cerâmica foi determinado a figura de mérito piroelétrica (FOM) e finalmente, nessa fase de caracterização, foi determinado o campo coercivo e a polarização remanescente através da curva de histerese ferroelétrica. Os resultados obtidos revelaram que a atividade piezo e piroelétrica do compósito são compatíveis com outros compósitos existentes e cerâmicas. Após a caracterização, o compósito foi submetido à radiação infravermelha próximo e à radiação X na faixa de ortovoltagem. Os resultados encontrados revelaram que o compósito responde na faixa de radiação ionizante e não ionizante revelando uma opção interessante como sensor. / Abstract: The present work is regarding to preparation and characterization of a ceramic/polymer composite film with three different ceramic loadings. The target was to observe the composite behavior when ionizing (X-ray) and non-ionizing (infrared) radiations was applied on it. The composites were made of calcium modified lead titanate (PTCa) ferroelectric ceramic immersed in poly(ether-ether-ketone) (PEEK) polymer matrix by hot pressing the powders mixture. Characterization was made using the longitudinal piezoelectric coefficient (d33) measurement as a function of ceramic content, poling temperature, poling electric field and poling time. Pyroelectric coefficient, dielectric permittivity and dielectric loss, coercive field and remanent polarization were also measured. The pyroelectric figure of merit (FOM) for sample with 60 vol% of ceramic was determined. The values of piezo and pyroelectric coefficient obtained for this composite indicates that it is comparable with other composites reported in literature. The application of the composite as thermal transducer for near infrared and X-ray radiation showed a real possibility to use PTCa/PEEK composite film as radiation detector in a wide range of energy. / Doutor

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No. of bitstreams: 1 oliveira_ma_dr_ilha.pdf: 7398841 bytes, checksum: acb7f174226b997e4c4c4192ff05e406 (MD5) Previous issue date: 2017-08-18 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O titanato de bário (BaTiO3, BT) é um material ferroelétrico com diversas aplicações, dentro do mercado de componentes eletrônicos, devido às excelentes propriedades físicas que manifesta, em relação a outros sistemas ferroelétricos, continuando a atrair durante várias décadas o interesse científico e comercial. Dentre o grande número de trabalhos sobre o sistema BT reportados na literatura muitos são associados à vasta gama de aplicações para a indústria eletro-eletrônica, dentre as quais se destacam o uso em dispositivos para capacitores, termistores, entre outros. A dopagem do BaTiO3 com íons doadores implica na mudança de algumas propriedades físicas, que conduzem a comportamentos anómalos em determinados parâmetros físicos, cuja natureza ainda não tem sido muito esclarecida, embora muitos trabalhos tenham se empenhado para tentar justificar tais efeitos. Neste contexto, neste trabalho, as propriedades físicas do sistema BaTiO3 serão investigadas considerando a adição de elementos doadores, nos sítios A e B da estrutura. Em particular, os íons de gadolínio (Gd3+) e nióbio (Nb5+) serão usados como modificadores da estrutura perovskita em substituição dos íons de bário (Ba2+) e titânio (Ti4+) nos sítios A e B, respectivamente, considerando as fórmulas químicas Ba1-xGdxTiO3 e BaTi1-x NbxO3 (sendo x = 0.001, 0.002, 0.003, 0.004 e 0.005). As propriedades estruturais e microestruturais foram investigadas à temperatura ambiente, enquanto as propriedades dielétricas e elétricas foram analisadas em uma ampla faixa de temperatura e frequência. Em particular, os efeitos condutivos proporcionados pela dopagem dos íons doadores em diferentes sítios cristalográficos, cujo estudo ainda não foi reportado na literatura, foram cuidadosamente investigados para melhor compreender os fatores que influenciam e determinam as propriedades semicondutoras de tais materiais, visando aprimorar no entendimento a nível microscópico e macroscópico dos fatores que influenciam e originam os mecanismos condutivos nestes materiais, fatores determinantes para uma posterior aplicação na indústria eletroeletrônica. Os materiais foram obtidos a partir do método de Pechini (ou Método dos Precursores Poliméricos), bem conhecido na literatura por ser um método muito eficiente, quando comparado com métodos convencionais para síntese de materiais policristalinos, pois apresenta inúmeras vantagens, tais como a síntese em baixas temperaturas, baixa contaminação, maior controle estequiométrico, alta homogeneização e possibilidade de obtenção de pós em escala nanométrica. / Barium titanate (BaTiO3, BT) is a ferroelectric material with several applications for the electronic components market, due to its excellent physical properties when compared to other ferroelectric systems. So that, BT continues up today attracting the scientific and commercial interest for several decades. Among the large number of papers on the BT system reported in the literature, many are associated with the wide range of applications in the electric and electronic industry, where the use in capacitors, thermistors and other devices stands out. By doping BaTiO3 with donor ions implies in the change of some physical properties leading to abnormal behaviors in certain physical parameters. The nature of these changes is not yet very clear, although many papers have been reported trying to justify such effects. In this context, this work aims the investigation of the physical properties of the BaTiO3 system, considering the addition of donor elements in the A- and B-sites of the structure. In particular, the gadolinium (Gd3+) and niobium (Nb5+) ions will be used as modifiers on the perovskite structure by substitution of barium (Ba+2) and titanium (Ti+4) ions in the A- and B-site, respectively, considering the Ba1-xGdxTiO3 and BaTi1-x NbxO3 ( where x = 0.001, 0.002, 0.003, 0.004 and 0.005). The structural and microstructural properties were investigated at room temperature, while the electrical and dielectric properties were analyzed in a wide range of temperature and frequency. Particularly, the conductive effects provided by the doping with donor ions in different crystallographic sites, whose study has not yet been reported in the literature, were carefully investigated to better understand the factors that influence and determine the semiconductor properties of such materials. The objective is to enhance the understanding of the factors that influence and originate the conductive mechanisms in these materials at the microscopic and macroscopic level, therefore determining factors for a subsequent application in the electronics industry. The materials were obtained from the Pechini method (known as the Polymeric Precursors Method). This method is well known in the literature because it is a very efficient method, when compared with conventional methods for synthesis of polycrystalline materials, because of the numerous advantages it presents, such as the synthesis at low temperatures, low contamination, greater stoichiometric control, high homogenization and possibility of obtaining nanoscale powders.

Die Bedeutung von keramischen Materialien mit funktionalen Eigenschaften ist über die letzten Jahrzehnte kontinuierlich gestiegen. Ein besonderes Interesse liegt dabei in der elektronischen Speicherung von Informationen. Die Realisierung war jedoch lange Zeit problematisch, da die erforderlichen Feldstärken, die notwendig sind, um die Polarisation zu schalten, für Massivmaterialien zu hoch sind. Heutzutage ist dies dank moderner Dünnschichttechnologien kein Problem mehr, so dass nichtflüchtige ferroelektrische Datenspeicher kommerziell verfügbar sind. Aufgrund der ausgezeichneten dielektrischen und elektromechanischen Eigenschaften von ferroelektrischen Materialien werden diese auch für Anwendungen in Aktuatoren, Kondensatoren oder mikro-elektro-mechanischen Systemen verwendet. Neben den klassischen Ferroelektrika wie Pb(Zr,Ti)O3 spielen dabei vor allem Relaxor-Ferroelektrika wie Pb(Mg1/3Nb2/3O3-PbTiO3 (PMN-PT) eine entscheidende Rolle. Eine weitere sehr interessante funktionale Eigenschaft von ferroelektrischen Materialien, die besonders in den letzten zehn Jahren das Forschungsinteresse geweckt hat, ist der elektrokalorische Effekt (electro caloric effect, ECE). Besonders hohe ECE konnten in der Vergangenheit mit Blei-basierenden Materialien, wie beispielsweise PMN-PT, erzielt werden. Um den Einfluss der Struktur auf die funktionalen Eigenschaften zu untersuchen ist es vorteilhaft, mit texturierten Schichten zu arbeiten. Als Materialsystem wurde in dieser Arbeit PMN-PT verwendet, da dieses besonders gute ferroelektrische und elektrokalorischen Eigenschaften zeigt und es aufgrund der vielfältigen veröffentlichten Untersuchungen als Modellsystem genutzt werden kann. Als geeignete Herstellungsmethode von Dünnschichten komplexer Oxide hat sich die gepulste Laserabscheidung herausgestellt, die auch in dieser Arbeit genutzt wurde. Die Schwerpunkte der strukturellen Untersuchungen beschäftigen sich mit der Stabilisierung der Perowskit-Phase des PMN-PT, der detaillierten Aufklärung des Gefüges sowie der Realisierung von Schichten mit unterschiedlicher Orientierung und auf verschiedenen Substratmaterialien. Hinsichtlich der funktionalen Eigenschaften wird auf den Einfluss der Pyrochlor-Phase auf die Ferroelektrizität, die Anisotropie der ferroelektrischen und elektrokalorischen Eigenschaften sowie auf eine Möglichkeit der direkten Messung der elektrokalorischen Temperaturänderung von PMN-PT Dünnschichten eingegangen.

Neste trabalho, cerâmicas de BaTiO3 foram preparadas pelo método de Pechini com o propósito de estudar as suas propriedades dielétricas, incluindo as anomalias dielétricas de origem interfacial nestes ferroelétricos. Após calcinação das soluções precursoras a 600 oC por 2h, os pós compactados foram sinterizados a várias temperaturas entre 1150 e 1450 oC. Subseqüentemente, foram realizadas caracterizações (micro)estruturais aplicando as técnicas de microscopia eletrônica de varredura e difração de raios X, além de estudos dielétricos utilizando a técnica de espectroscopia de impedância. Destas caracterizações, verificou-se a obtenção de materiais cerâmicos com tamanhos de grãos variando entre 0,8 e 37 micrometros ao aumentar a temperatura de sinterização. Os resultados de dinâmica térmica de densificação indicam a contribuição de dois mecanismos independentes: (i) sinterização com participação de fase líquida, induzindo altas densidades dos materiais a partir de ~1300 oC (perto do ponto eutético), e (ii) sinterização via reação de estado sólido, implicando alta sinterabilidade mesmo abaixo dos 1300 oC, em se tratando de pós nanométricos, ou seja, com alta densidade de defeitos e, portanto, processos de difusão iônica intensificados. Por outro lado, a resposta dielétrica dos grãos evidenciou o cumprimento da lei de Curie-Weiss, típica de ferroelétricos, enquanto um fenômeno de anomalia dielétrica (não cumprimento desta lei) foi observado para as respostas totais destes materiais em altas temperaturas e baixas freqüências. A análise dos resultados de espectroscopia de impedância via circuito equivalente, sendo considerado o modelo de camadas (grãos e contornos de grãos) em série, revelou a predominância das propriedades dielétricas das interfaces intergranulares como a causa desta anomalia. Considerando a relação entre propriedades macroscópicas e microscópicas no modelo, a variação da intensidade da anomalia é discutida em função do tamanho dos grãos, sendo este parâmetro uma medida (função inversa) da densidade das interfaces intergranulares. Em geral, este trabalho revela uma excelente correlação entre microestruturas, circuito equivalente e propriedades dielétricas exibidas por estes materiais eletrocerâmicos. / BaTiO3 ceramics were prepared in this work, following the Pechinis method, with the purpose of studying their dielectric properties, including especially the occurrence and characteristics of dielectric anomalies associated to internal interfaces, as often found in ferroelectrics. After calcination of the precursor solutions at 600 oC for 2h, the synthesized green compacts were sintered at several temperatures from 1150 to 1450 oC. Subsequently, (micro)structural characterizations were carried out by applying scanning electron microscopy and X-ray diffraction techniques, followed by dielectric measurements using the impedance spectroscopy technique. From these characterizations, the production of ceramic bodies with average grain sizes varying from 0.8 to 37 micrometer was verified when increasing the sintering temperature. The results of thermal dynamics of densification indicate the contribution of two independent mechanisms, namely (i) liquid phase-assisted sintering, inducing high materials density from ~1300 oC (close to the eutectic point) above, and (ii) solid-state sintering, implying high sinterability even below 1300 oC, as dealing with nanoparticles-sized powders, meaning high density of surface defects and, thus, enhanced ionic diffusion processes. On the other hand, while the dielectric response of the grains satisfied the Curie-Weiss law, typical of ferroelectrics, a dielectric anomaly (departure from this law) phenomenon was observed for the total dielectric response of these materials towards higher temperatures and lower frequencies. The analysis of the results from impedance spectroscopy via equivalent circuit, involving consideration of the series layer (grains and grain boundaries) model, revealed that the predominance of the dielectric properties from the intergranular interfaces is responsible for occurrence of this anomaly. Considering the relation between macroscopic and microscopic properties holding in this model, the variation of the anomaly strength is here discussed in terms of the value of average grain size in these ceramics, a microstructural parameter that represents a measure (inverse function) of the density of the intergranular interfaces. In general, the present study reveals a really good correlation between microstructures, equivalent circuit and dielectric properties exhibited by these electroceramic materials.

Les architectures d’ordinateur classiques sont optimisées pour le traitement déterministe d’informations pré-formatées et ont donc des difficultés avec des données naturelles bruitées (images, sons, etc.). Comme celles-ci deviennent nombreuses, de nouveaux circuits neuromorphiques (inspirés par le cerveau) tels que les réseaux de neurones émergent. Des nano-dispositifs, appelés memristors, pourraient permettre leur implémentation sur puce avec une haute efficacité énergétique et en s’approchant de la haute connectivité synaptique du cerveau.Dans ce travail, nous étudions des memristors basés sur des jonctions tunnel ferroélectriques qui sont composées d’une couche ferroélectrique ultramince entre deux électrodes métalliques. Nous montrons que le renversement de la polarisation de BiFeO3 induit des changements de résistance de quatre ordres de grandeurs et établissons un lien direct entre les états de domaines mixtes et les niveaux de résistance intermédiaires.En alternant les matériaux des électrodes, nous révélons leur influence sur la barrière électrostatique et les propriétés dynamiques des memristors. Des expériences d’impulsion unique de tension montrent un retournement de polarisation ultra-rapide. Nous approfondissons l’étude de cette dynamique par des mesures d’impulsions cumulées. La combinaison de leur analyse avec de l’imagerie par microscopie à force piézoélectrique nous permet d’établir un modèle dynamique du memristor. Suite à la démonstration de la spike-timing-dependent plasticity, une règle d’apprentissage importante, nous pouvons prédire le comportement de notre synapse artificielle. Ceci représente une avance majeure vers la réalisation de réseaux de neurones sur puce dotés d’un auto-apprentissage non-supervisé. / Classical computer architectures are optimized to process pre-formatted information in a deterministic way and therefore struggle to treat unorganized natural data (images, sounds, etc.). As these become more and more important, the brain inspires new, neuromorphic computer circuits such as neural networks. Their energy-efficient hardware implementations will greatly benefit from nanodevices, called memristors, whose small size could enable the high synaptic connectivity degree observed in the brain.In this work, we concentrate on memristors based on ferroelectric tunnel junctions that are composed of an ultrathin ferroelectric film between two metallic electrodes. We show that the polarization reversal in BiFeO3 films can induce resistance contrasts as high as 10^4 and how mixed domain states are connected to intermediate resistance levels.Changing the electrode materials provides insights into their influence on the electrostatic barrier and dynamic properties of these memristors. Single-shot switching experiments reveal very fast polarization switching which we further investigate in cumulative measurements. Their analysis in combination with piezoresponse force microscopy finally allows us to establish a model describing the memristor dynamics under arbitrary voltage signals. After the demonstration of an important learning rule for neural networks, called spike-timing-dependent plasticity, we successfully predict new, previously unexplored learning curves. This constitutes an important step towards the realization of unsupervised self-learning hardware neural networks.

Ferroelectrics are promising for nonvolatile memories. However, the diffi culty of fabricating ferroelectric layers and integrating them into complementary metal oxide semiconductor (CMOS) devices has hindered rapid scaling. Hafnium oxide is a standard material available in CMOS processes. Ferroelectricity in Si-doped hafnia was first reported in 2011, and this has revived interest in using ferroelectric memories for various applications. Ferroelectric hafnia with matured atomic layer deposition techniques is compatible with three-dimensional capacitors and can solve the scaling limitations in 1-transistor-1-capacitor (1T-1C) ferroelectric random-access memories (FeRAMs). For ferroelectric field-effect-transistors (FeFETs), the low permittivity and high coercive field Ec of hafnia ferroelectrics are beneficial. The much higher Ec of ferroelectric hafnia, however, makes high endurance a challenge. This article summarizes the current status of ferroelectricity in hafnia and explains how major issues of 1T-1C FeRAMs and FeFETs can be solved using this material system.

We report on a two-layer based ferroelectric tunnel junction with hafnium zirconium oxide (HZO) as the ferroelectric layer and aluminum oxide as the tunneling layer. The experimental results focus on optimizing the thicknesses of the layer stack. The device operation relies on the polarization reversal of the HZO layer, while electron tunneling occurs through the dielectric layer. The ferroelectric response of the HZO shows high remanent polarization values and good endurance with only weak wake-up and fatigue behavior. Adding the additional dielectric tunneling layer, the device becomes operational as a ferroelectric tunnel junction in the nanoampere current range. It shows good on/off ratios and promising retention behavior, paving the way for future applications as a polarization-based resistive memory device.

This work is focused on the study of perovskite ferroelectric materials group and monitoring changes their dielectric parameters in temperature and frequency dependence Is described scrystallographic systems of barium titanate and their influence on material properties. The measured values are mathematically interpreted using the Curie – Weiss law and discussed about the influence of strontium titanite on important dielectric parameters.

Die Bedeutung von keramischen Materialien mit funktionalen Eigenschaften ist über die letzten Jahrzehnte kontinuierlich gestiegen. Ein besonderes Interesse liegt dabei in der elektronischen Speicherung von Informationen. Die Realisierung war jedoch lange Zeit problematisch, da die erforderlichen Feldstärken, die notwendig sind, um die Polarisation zu schalten, für Massivmaterialien zu hoch sind. Heutzutage ist dies dank moderner Dünnschichttechnologien kein Problem mehr, so dass nichtflüchtige ferroelektrische Datenspeicher kommerziell verfügbar sind. Aufgrund der ausgezeichneten dielektrischen und elektromechanischen Eigenschaften von ferroelektrischen Materialien werden diese auch für Anwendungen in Aktuatoren, Kondensatoren oder mikro-elektro-mechanischen Systemen verwendet. Neben den klassischen Ferroelektrika wie Pb(Zr,Ti)O3 spielen dabei vor allem Relaxor-Ferroelektrika wie Pb(Mg1/3Nb2/3O3-PbTiO3 (PMN-PT) eine entscheidende Rolle. Eine weitere sehr interessante funktionale Eigenschaft von ferroelektrischen Materialien, die besonders in den letzten zehn Jahren das Forschungsinteresse geweckt hat, ist der elektrokalorische Effekt (electro caloric effect, ECE). Besonders hohe ECE konnten in der Vergangenheit mit Blei-basierenden Materialien, wie beispielsweise PMN-PT, erzielt werden. Um den Einfluss der Struktur auf die funktionalen Eigenschaften zu untersuchen ist es vorteilhaft, mit texturierten Schichten zu arbeiten. Als Materialsystem wurde in dieser Arbeit PMN-PT verwendet, da dieses besonders gute ferroelektrische und elektrokalorischen Eigenschaften zeigt und es aufgrund der vielfältigen veröffentlichten Untersuchungen als Modellsystem genutzt werden kann. Als geeignete Herstellungsmethode von Dünnschichten komplexer Oxide hat sich die gepulste Laserabscheidung herausgestellt, die auch in dieser Arbeit genutzt wurde. Die Schwerpunkte der strukturellen Untersuchungen beschäftigen sich mit der Stabilisierung der Perowskit-Phase des PMN-PT, der detaillierten Aufklärung des Gefüges sowie der Realisierung von Schichten mit unterschiedlicher Orientierung und auf verschiedenen Substratmaterialien. Hinsichtlich der funktionalen Eigenschaften wird auf den Einfluss der Pyrochlor-Phase auf die Ferroelektrizität, die Anisotropie der ferroelektrischen und elektrokalorischen Eigenschaften sowie auf eine Möglichkeit der direkten Messung der elektrokalorischen Temperaturänderung von PMN-PT Dünnschichten eingegangen.

Morphotrope PZT-Keramiken sind Festkörperlösungen aus Bleizirkonat und Bleititanat mit chemischen Zusammensetzungen um die 47% Ti-Anteil. Sie weisen im gepolten Zustand die größten piezoelektrischen Koppelkonstanten auf und sind daher von speziellem Interesse. Zur Vorhersage des Polungszustandes und der Bauteilfestigkeit in komplexen Bauteilen werden elektromechanisch gekoppelte Materialmodelle benötigt. In dieser Arbeit wird ein mikromechanischer Modellansatz aus der Literatur aufgegriffen. Ausgangspunkt ist ein dreidimensionales tetragonales Modell, welches ein repräsentatives Volumenelement des Kornverbundes und ein mikroskopisches Kornmodell vereint. Damit gelingt die Beschreibung der Korninteraktionen infolge unterschiedlicher Polungszustände der Körner. Die Domänenstruktur der Körner wird mittels der Volumenanteile der kristallographischen Varianten dargestellt. Ein vereinfachter Satz an mikroskopischen Materialkonstanten wird anhand experimenteller Daten und theoretischer Betrachtungen aus der Literatur abgeleitet. Die für zwei Lastfälle berechneten makroskopischen Materialantworten zeigen explizit, dass das tetragonale Modell nicht in der Lage ist, das Verhalten morphotroper PZT-Keramiken nachzubilden. Aus diesem Grund wird das Modell im Hinblick auf die besondere kristallographische Struktur morphotroper PZT-Keramiken um eine rhomboedrische Phase in veränderlichen Anteilen erweitert. Die somit berechneten makroskopischen Antworten stimmen sowohl quantitativ als auch qualitativ gut mit experimentellen Ergebnissen überein. Der Einfluss der im Modell berücksichtigten Kristallstruktur auf die makroskopische Materialantwort wird in der Arbeit ausführlich analysiert. / Morphotropic PZT ceramics are solid solutions made of lead zirconate and lead titanate with chemical composition around 47% Ti-content. When poled they possess the greatest piezoelectric coupling constants for which they are of special interest. Predicting the poling condition and the strength in complex devices requires electromechanically coupled material models. Within this work, a micromechanical modelling approach is utilised. Starting point is a three-dimensional tetragonal model, which combines a representative volume element of the grain compound together with a microscopic grain model. This allows the consideration of grain interaction due to different poling conditions of the grains. The domain structure of the grains is captured by volume fractions of the crystallographic variants. A simplified set of microscopic material constants is derived from experimental and theoretical data given in the literature. The macroscopic material response, which is computed for two load cases, shows explicitly that the tetragonal model is not capable of reproducing the behaviour of morphotropic PZT ceramics. Therefore, the model is extended by the rhombohedral phase in varying quantity with view of the specific crystallographic structure of morphotropic PZT ceramics. The so computed macroscopic response shows a quantitatively as well as qualitatively good agreement with experimental results. The effect of the crystallographic structure which is considered within the model on the macroscopic material response is extensively analysed.