The aim of this doctoral research is to understand domain evolution processes in ferroelectrics using piezoresponse force microscopy (PFM) and Monte Carlo simulation. The results provide improved knowledge of domain evolution processes, and systematic experimental methods for research on domain evolution. There has been extensive previous research on domain evolution in ferroelectrics, but the research was mainly constrained to simple domain patterns. However, ferroelectric domains tend to form complex patterns that generate low-energy domain configurations. In this research, several methods such as statistical analysis of PFM data, ex situ/in situ PFM observation under electrical/mechanical loading and combining PFM with electron backscatter diffraction are employed to study domain evolution processes in complex domain patterns. The results show that domain switching almost always takes place by the evolution of pre-existing domain patterns, rather than direct flipping of polarization. Also the net effect of domain evolution processes follows a primary principle that positive work is done by external loads. But this principle is not always followed for microscopic switching processes. Multiple types of domain switching occur simultaneously, and occasionally an overwriting process involves unfavourable as well as favourable domain switching. Domain switching is significantly constrained by the pre-existing domain patterns. Meanwhile, angle-resolved PFM is developed for the systematic interpretation of PFM signal. Using lateral PFM images taken from multiple sample orientations, angle-resolved PFM maps are generated based on the angle of phase reversal in the PFM signal. The resulting maps reliably show complex domain patterns which may not appear in vertical and lateral PFM images. A model of domain evolution is developed using Monte Carlo simulation. Polarization switching by electric field and mechanical stress in the model is shown to take place via the motion of domain walls between pre-existing domains. Typical domain broadening processes are reproduced through this simulation.

Ce travail de thèse vise à étudier les propriétés structurales et diélectriques des échantillons céramiques appartenant au système Ba1-xRxTi1-yZryO3 (R = Ca, Sr). Les échantillons sous forme de poudre, micro ou nano structurées, ont été respectivement obtenus par la méthode des mélanges d'oxydes et la méthode du précurseur polymèrique. À partir des échantillons sous forme de poudre micro ou nano-structurés, les échantillons céramiques ont été obtenus grâce à un procédé de frittage à haute température. Les échantillons sous forme de céramiques en poudres micrométriques ont été obtenus par la méthode traditionnelle de frittage à haute température alors que céramiques constituées de particules de taille nanométrique ont été obtenus en utilisant la technique de Spark Plasma (ou Spark Plasma Sintering, SPS). Les propriétés structurales et électriques de ces deux séries d'échantillons ont été caractérisées par diffraction des rayons X à haute résolution (XRD), spectroscopie d'impédance complexe, spectroscopie d'absorption des rayons X et la spectroscopie Raman. Grâce aux données de diffraction des rayons X il a été possible de suivre le processus de transition de phase dû à la substitution des atomes de titane par du zirconium. Les mesures électriques montrent que lorsque la quantité de Zr augmente, l'échantillon passe d'u n état ferroelectrique normal à un état ferroélectrique relaxeur. Les mesures du spectre d'absorption et le spectre Raman ont été utilisées pour établir une relation entre la structure locale et des propriétés électriques de ces matériaux. Enfin, l'analyse des résultats obtenus avec des céramiques nanostructurés montrent que la réduction de la taille des particules entraîne une diminution de la température maximale et un petit élargissement de la courbe de la permittivité diélectrique. Toutefois, il n'y avait aucun changement de l'état ferroélectrique, normal ou relaxeur, de ces échantillons / The aims of this work is to study the structural and electrical properties of ceramic samples belonging to the Ba1-xRxTi1-yZryO3 (R = Ca, Sr) system. The powder samples presenting a micro or nanosize were respectively obtained by using a mixture of oxides and by the modified polymeric precursor methods. From the samples in a powder form, micro or nanosize, sintered ceramic samples were obtained through a sintering process at high temperature. Micrometer scale ceramic samples were obtained through the traditional method of sintering at high temperature while nano-sized particles ceramics were obtained using the spark Spark Plasma Sintering SPS technique. The structural and electrical properties of these two sets of samples were characterized using High resolution X-ray diffraction (XRD), complex impedance spectroscopy and X-ray absorption and Raman spectroscopy's. Through the data of XRD it was possible to follow the processes of phase transition due to the substitution of Ti by Zr atoms. Electrical measurements showed that as the amount of Zr increases, the sample passes from a normal ferroelectric state to a relaxor state. Measurements of the absorption and Raman spectra were used to establish a relationship between local structure and electrical properties displayed by these materials. These properties were characterized by the shape of the dielectric permittivity curves versus temperatures. Two principal characteristics were analysed : the maximum Tm and the width ∆T. Finally, the analysis of results obtained with nanostructured ceramic samples showed that reducing the particle size leads to a decrease of Tm, and a small increase of ∆T. However, there was no change from normal to relaxor ferroelectric states

Owing to the large electric-field-dependent permittivity, ferroelectric thin films have attracted a great deal of attention on applications in miniature tunable microwave components with high performance and cost reduction, such as phase shifters, tunable oscillators, delay lines, and antennas. These tunable devices require large change in the dielectric constant with applied field and a low loss at microwave frequencies. As one of the promising ferroelectric materials, barium strontium titanate thin film, especially Ba0.5Sr0.5TiO3 (BST) films, have raises great research interests due to its high dielectric constant, which is tunable in an external electric field, combined with relative low loss at microwave frequencies. Tunable microwave components, such as phase shifter, based on the BST films have been widely investigated. Since the polarization, the significant characterization of ferroelectrics, is very sensitive to distortion in crystal structure of ferroelectrics, strain can be effectively utilized to tailor the dielectric properties of BST films. Due to the lattice-mismatch from the substrate and various deposition conditions, epitaxial BST thin film usually contains residual strain generated during film growth. Strain control by improved deposition technique and implementing thermal treatment as well as choosing suitable substrate has attracted intensive attentions in ferroelectric film fabrication. Theory predicts that high dielectric properties can be achieved when free strain or slightly tensile strain left in the BST thin film at room temperature. Microwave application, such as phase shifter, also expects the enhanced tunability by an applied electric field. In this dissertation, single crystalline BST thin films deposited by radio frequency magnetron sputtering on SrTiO3 and DyScO3 substrates were studied. The crystal structure characteristics, including lattice parameters and film strain, were determined using X-ray diffraction. A new growth technique, three-step technique, was introduced and implemented into BST thin film deposition. The application of this new technique in deposition dramatically reduced the compressive strain in the films. We use microwave measurements on coplanar waveguides to evidence the improvement on dielectric properties achieved by tailoring the film strain. Additionally, we studied the BST film deposited by pulsed laser deposition (PLD) with introducing a sputtered seed layer of BST thin film. Compared with the BST film directly deposited on the substrate by PLD deposition, the films with a seed layer showed a large enhancement on the dielectric constant and tunability. The discussion on the change in film strain and dielectric performance of the PLD deposited films further proved the influence of film strain on dielectric properties. We discussed the design, fabrication, and measurement of coplanar waveguide transmission lines as phase shifters fabricated BST films. The thin BST films (~700 nm) on DyScO3 substrates deposited by sputtering demonstrated that the three-step deposition technique improved differential phase shift and microwave figure of merit to a great extent. The introduction of the sputtered seed layer into the PLD deposition of a thicker BST film (~2.15 μm) showed a dramatically enhancement on differential phase shift and microwave figure of merit. The enhanced performance on different series of BST films in microwave frequencies is consistent with the improvement on crystal structure, especially with the change in film strain.

Ce travail porte sur la caractérisation de matériaux en couches minces par spectroscopie terahertz dépendant du temps. Dans ce but, nous avons élaboré un banc d’analyse spectroscopique dont l’émission et la détection terahertz reposent sur l’utilisation de laser femtoseconde, de semi-conducteurs, de photocommutateurs ultrarapides ou de cristaux électro-optiques. La réponse diélectrique quantitative de matériaux ferroélectriques (titanate de baryum/ - Ba1-xSrxTiO3) déposés sous forme de couches minces, a permis de mettre en évidence l’importance des modes mous de phonon par une étude en température. Enfin, le comportement électromagnétique de polymères conducteurs à base de polyaniline a été effectué notamment leur efficacité de blindage en bande millimétrique et submillimétrique. / This work concerns the characterization of thin film materials by terahertz time domain spectroscopy. For this purpose, we elaborated a terahertz setup in which the terahertz emission and terahertz detection are based on the use of femtosecond laser, semiconductors, ultrafast photoswitches or electro-optic crystals. The study of dielectric function of ferroelectrics thin film (barium titanate/-Ba1-xSrxTiO3) with temperature, give the importance of soft phonon mode. Finally, the electromagnetic behavior of conducting polymers based on polyaniline was made, in particular their shelding effectiveness in millimeter and sub-millimeter length.

Os objetivos deste trabalho foram a implantação e a otimização da técnica de sinterização a laser de corpos cerâmicos, o estudo da cinética do processo e a avaliação de propriedades físicas dos compostos Bi4Ti3O12 e Bi4Ge3O12 sinterizadas a laser, em comparação com as cerâmicas processadas em forno convencional. A escolha dos materiais baseou-se em seu potencial de aplicação: o Bi4Ge3O12 como dispositivo cintilador e o Bi4Ti3O12 como cerâmica eletrônica. A sinterização a laser mostrou-se eficiente para estes materiais, produzindo cerâmicas com densidade superior a 98 % e pequeno tamanho de grão. A combinação de pré-aquecimento e subida gradual da potência do laser evitou gradientes de temperatura e taxas de aquecimento excessivos, e reduziu consideravelmente a incidência de trincas e a porosidade nas cerâmicas. No estudo cinético da sinterização a laser, registraram-se energias de ativação inferiores às observadas no processamento convencional, exceto para o BIT no estágio final de sinterização, e os resultados sugerem um adiantamento no processo de sinterização, provocado por efeito da irradiação a laser. A caracterização física do BIT foi feita por espectroscopia de impedância e medidas de histerese ferroelétrica. Comparado à cerâmica convencional, o corpo cerâmico sinterizado a laser apresentou condutividade elétrica 3 vezes menor na região de bulk, maior permissividade dielétrica acima de 300 °C, com igual perda dielétrica, mesmo campo coercitivo e polarização remanescente 35 % superior. A caracterização física do BGO foi feita por medidas de absorção óptica, radioluminescência e termoluminescência. Os resultados mostraram que a cerâmica de BGO sinterizada a laser possui grau de transparência 50 % maior, densidade de defeitos estruturais 2 vezes menor, eficiência levemente superior e mesmo dano por radiação, se comparada à cerâmica sinterizada em forno elétrico. Os resultados obtidos foram interpretados com base na escala de tempo característica da sinterização a laser, que afeta a formação e distribuição dos defeitos durante o processo, e resulta em cerâmicas com microestrutura diferenciada. / The goals of this work were the implantation and optimization of the laser sintering technique for ceramic bodies, the kinetic study of the process and the evaluation of the physical properties of the laser sintered compounds Bi4Ti3O12 and Bi4Ge3O12, compared to ceramics sintered in conventional furnace. The choice of the materials was based on their potential applications: Bi4Ge3O12 as scintillator device and Bi4Ti3O12 as an electronic ceramic. Laser sintering showed to be efficient for these materials, producing ceramics with density higher than 98 % and small grain sizes. The combination of pre-heating with a gradual rising of the laser power prevented excessive temperature gradient and heating rate, and reduced considerably the incidence of cracks and pores in the ceramics. The kinetic study of the laser sintering revealed lower activation energies than that observed in the conventional processing, except for BIT ceramics during the final stage of sintering. The results suggest that the laser irradiation anticipates the stages of the sintering process. The physical characterization of BIT was done through impedance spectroscopy and ferroelectric hysteresis measurements. Compared to the conventional sample, this material presented bulk electrical conductivity 3 times smaller, higher dielectric permittivity above 300 °C, comparable dielectric loss, the same coercive field and 35 % higher remanent polarization. The physical characterization of BGO was done through optical absorption, radioluminescence and thermoluminescence measurements. The results showed that the transparency of the laser sintered BGO ceramic was 50 % higher than the transparency of the conventional BGO ceramic, the density of structural defects is 2 times lower, the radiation damage levels are comparable and the overall scintillating efficiency is slightly higher. The obtained results were interpreted on the basis of the time scale of the laser sintering, which affects the formation and distribution of defects during the process, and results in a particular microstructure.

A major area of interest in condensed matter physics over the past decades has been the emergence of new states of matter from strongly correlated electron systems. A few limited examples would be the emergence of unconventional superconductivity in the high-T$_c$ superconductors and heavy-fermion systems, the appearance of the skyrmion magnetic vortex state in MnSi and magnetically mediated superconductivity in UGe$_2$. While detailed studies of many of the emergent phases have been made, there are still many gaps in understanding of the underlying states and mechanisms that allow them to form. This work aims to add to knowledge of the basic physics behind such states, and the changes within them as they are tuned to approach new phases. The cubic perovskite material SrTiO$_3$ has been studied for many decades and is well-documented to be an incipient ferroelectric, theorised to exist in the absence of any tuning in the proximity of a ferroelectric quantum critical point. This work presents the first high-precision dielectric measurements under hydrostatic pressure carried out on a quantum critical ferroelectric, leading to a full pressure-temperature phase diagram for SrTiO$_3$. The influence of quantum critical fluctuations is seen to diminish as the system is tuned away from the quantum critical point and a novel low temperature phase is shown to be emergent from it. The Néel Temperature of the two-dimensional antiferromagnet FePS$_3$ was found to increase linearly with applied hydrostatic pressure. Evidence of an insulator-metal transition is also presented, and an unexplained upturn in the resistivity at low temperatures in the metallic phase.

There has been unprecedented growth in wireless technologies in recent years; wireless devices such as cellular telephones and wireless local area network (WLAN) transceivers are becoming ubiquitous. It is now common for a single hardware device, such as a cellular telephone, to be capable of multi-band operation. Implementing a dedicated radio frequency (RF) front-end for each frequency band increases the component count and therefore the cost of the device. Consequently, there is now a requirement to design RF and microwave circuits that can be reconfigured to operate at different frequency bands, as opposed to switching between several fixed-frequency circuits. Barium strontium titanate (BST) thin films show great promise for application in reconfigurable microwave circuits. The material has a high dielectric constant which can be controlled by the application of a quasi-static electric field, combined with relatively low losses at microwave frequencies. Tunable microwave components based on BST-thin films have the potential to replace several fixed components, thereby achieving useful size and cost reductions. This thesis is concerned with the growth and microwave circuit applications of BST thin films on c- and r-plane sapphire substrates. Sapphire is an ideal substrate for microwave integrated circuit fabrication due to its low cost and low loss. Electronically tunable capacitors (varactors) were fabricated by patterning interdigital electrode structures on top of the BST films. High capacitance tunabilities of 56% and 64% were achieved for the films grown on c-plane and r-plane sapphire, respectively, at 40 V bias. A novel electronically tunable 3 dB quadrature hybrid circuit was also developed. Prototypes of this circuit were initially implemented using commercial varactor diodes, in order to validate the design. An integrated version of the coupler was then fabricated using BST varactors on c-plane sapphire. The results achieved demonstrate the potential of sapphire-based BST thin films in practical microwave circuits.

A key non-destructive technique for analysis, optimization and developing of new functional materials such as sensors, transducers, electro-optical and memory devices is presented. The Thermal-Pulse Tomography (TPT) provides high-resolution three-dimensional images of electric field and polarization distribution in a material. This thermal technique use a pulsed heating by means of focused laser light which is absorbed by opaque electrodes. The diffusion of the heat causes changes in the sample geometry, generating a short-circuit current or change in surface potential, which contains information about the spatial distribution of electric dipoles or space charges. Afterwards, a reconstruction of the internal electric field and polarization distribution in the material is possible via Scale Transformation or Regularization methods. In this way, the TPT was used for the first time to image the inhomogeneous ferroelectric switching in polymer ferroelectric films (candidates to memory devices). The results shows the typical pinning of electric dipoles in the ferroelectric polymer under study and support the previous hypotheses of a ferroelectric reversal at a grain level via nucleation and growth. In order to obtain more information about the impact of the lateral and depth resolution of the thermal techniques, the TPT and its counterpart called Focused Laser Intensity Modulation Method (FLIMM) were implemented in ferroelectric films with grid-shaped electrodes. The results from both techniques, after the data analysis with different regularization and scale methods, are in total agreement. It was also revealed a possible overestimated lateral resolution of the FLIMM and highlights the TPT method as the most efficient and reliable thermal technique. After an improvement in the optics, the Thermal-Pulse Tomography method was implemented in polymer-dispersed liquid crystals (PDLCs) films, which are used in electro-optical applications. The results indicated a possible electrostatic interaction between the COH group in the liquid crystals and the fluorinate atoms of the used ferroelectric matrix. The geometrical parameters of the LC droplets were partially reproduced as they were compared with Scanning Electron Microscopy (SEM) images. For further applications, it is suggested the use of a non-strong-ferroelectric polymer matrix. In an effort to develop new polymerferroelectrets and for optimizing their properties, new multilayer systems were inspected. The results of the TPT method showed the non-uniformity of the internal electric-field distribution in the shaped-macrodipoles and thus suggested the instability of the sample. Further investigation on multilayers ferroelectrets was suggested and the implementation of less conductive polymers layers too. / In dieser Arbeit wird eine zerstörungsfreie Technik zur Analyse, Optimierung, und Entwicklung neuer funktioneller Materialien für Sensoren, Wandler, Speicher und elektrooptische Anwendungen vorgestellt. Die Wärmepuls-Tomographie (engl. Thermal-Pulse Tomography, TPT) liefert dreidimensionale Abbildungen hoher Auflösung von elektrischen Feldern und Polarisationsverteilungen eines Materials. Bei dieser thermischen Methode wird ein fokussierter, gepulster Laserstrahl durch eine undurchsichtige Oberflächenelektrode absorbiert, welche sich dadurch aufheizt. Die einsetzende Wärmediffusion führt – aufgrund der Wärmeausdehnung des Materials – zu Änderungen der Probengeometrie, welche in pyroelektrischen Materialien einen Kurzschlussstrom oder eine Änderung des Oberflächenpotentials zur Folge hat. Diese wiederum enthalten wichtige Informationen über die räumliche Verteilung elektrischer Dipole und Raumladungen im untersuchten Material. Aus dem gemessenen Kurzsschlussstrom kann anschließend das interne elektrische Feld und die Polarisationsverteilung im Material mittels verschiedener Skalentransformations- und Regularisierungsmethoden rekonstruiert werden. Auf diese Weise ermöglichte die TPT-Methode erstmals die Darstellung inhomogener ferroelektrischer Schaltvorgänge in polymeren ferroelektrischen Filmen, welche mögliche Materialien für die Datenspeicherung sind. Die Ergebnisse zeigen eine typische Haftschicht im ferroelektrischen Polymer und unterstützen die Hypothese einer ferroelektrischen Umpolung auf einer der Korngröße äquivalenten Längenskala über Keimbildung und anschließendes Wachstum. Um die Lateral- und Tiefenauflösung zu untersuchen, wurden sowohl die TPT-Methode als auch die äquivalente Methode in der Zeitdomäne (Focused Laser Intensity Modulation Method, FLIMM) auf ferroelektrischen Filme mit Gitterelektroden angewendet. Die Ergebnisse beider Techniken zeigen nach der Datenauswertung mit unterschiedlichen Regularisierungs- und Scale-Methoden eine vollkommene Übereinstimmung. Des Weiteren stellte sich heraus, dass bisherige Untersuchungen der lateralen Auflösung von FLIMM diese möglicherweise überschätzen. Damit behauptet sich TPT als effiziente und verlässliche thermische Methode. Nach einer Optimierung der Optik wurde die TPT-Methode in polymerdispergierten Flüssigkristallen (polymer-dispersed liquid crystals, PDLC), welche in elektrooptischen Anwendungen von Interesse sind, angewendet. Die Ergebnisse deuten auf eine mögliche elektrostatischeWechselwirkung zwischen den COH-Gruppen des Flüssigkristalls und den Fluoratomen der verwendeten ferroelektrischen Matrix hin. Die durch rasterelektronenmikroskopische Aufnahmen (scanning electron microscopy, SEM) gewonnenen geometrischen Parameter der Flüssigkristalltröpfchen konnten mittels TPT reproduziert werden. Für weitere Anwendungen werden schwach ferroelektrische Polymermatrices vorgeschlagen. Im Bestreben neue polymere Ferroelektrete zu entwickeln und deren Eigenschaften zu optimieren, wurden neuartige Mehrschichtsysteme untersucht. Die Ergebnisse aus der TPT-Methode zeigen eine Abweichung der Uniformität der inneren Verteilung des elektrischen Feldes in den geformten Makrodipolen, was auf eine Instabilität der Probe hindeutet. Ebenfalls wurden weitere Untersuchungen an Mehrschicht-Ferroelektreten und die Anwendung von halbleitenden Polymerschichten vorgeschlagen.

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