Desenvolveu-se um sistema para medir a constante dielétrica complexa de amostras dielétricas, de construção simples, versátil e de baixo custo. A medida é feita aplicando-se uma tensão senoidal e fazendo-se a aquisição do sinal aplicado e do sinal da resposta elétrica (carga elétrica). Emprega-se uma placa A/D para a aquisição de dados com taxa de amostragem de 100 Ksamples/seg e através da transformada de Fourier discreta destes sinais determina-se a impedância complexa da amostra, a partir da qual calcula-se a constante dielétrica complexa. A placa utilizada e o circuito de medida da carga elétrica introduzem defasagens indesejáveis nos sinais, cujas correções são feitas através de programa no computador usado para aquisição dos sinais. O sistema mostra um desempenho similar àqueles dos equipamentos comerciais para freqüências no intervalo de 0,1H.z a 1KHz, sendo testado com componentes resistivos e capacitivos e posteriormente em amostras de Teflon FEP, poli(fluoreto de vinilideno) e seus copolímeros com trifluoretileno. O sistema também foi utilizado para medir o deslocamento elétrico nos polímeros ferroelétricos sob a aplicação de campos elevados. Neste caso determinaram-se as curvas de histerese dielétrica e os deslocamentos de primeira, segunda e terceira ordem. / A low cost and a simple experimental system for measuring the complex dielectric constant of dielectric samples were developed. Measurements were performed measuring the electric charge response resulting from the application of a sinusoidal voltage. The system was based on an A/D acquisition board with sampling rate of 100 Ksamples/sec. The complex impedance was calculated using the discrete Fourier transform from which the complex dielectric constant was found. The phase differences introduced by the A/D board and the amplifiers circuits were connected by software. The setup showed that the results are comparable to that ones obtained with commercial impedance analyzers in the range of frequencies between 0.1 Hz and 1 KHz. Such measurements were obtained using resistors and/or capacitors and also using samples of Teflon FEP, PVDF and its copolymers with trifluorethylene. The setup was also capable to measure the electric displacement in ferroelectric polymers submitted to high fields. Hysteresis loops and the nonlinear electric displacement of first, second and third order were measured.

Esse trabalho de dissertação de mestrado teve como principal objetivo obter amostras do sistema Pb1-xLaxTiO3(PLT) com x = 0,10, 0,15 e 0,20 e, a partir desse material, produzir amostras cerâmicas e filmes finos nanoestruturados e caracterizar suas propriedades estruturais e elétricas. As nanopartículas para a produção das cerâmicas e a solução para a deposição de filmes finos foram obtidas através do método dos precursores poliméricos. As amostras cerâmicas foram sinterizadas através do método convencional e do método de prensagem e aquecimento simultâneo. A caracterização estrutural foi realizada através das técnicas de difração de raios X (DRX), espectroscopia Raman e espectroscopia de absorção de raios X. Através das técnicas de DRX e espectroscopia Raman foi possível observar os processos de transição de fase estrutural em função da quantidade de lantânio e do tamanho de partícula. Amostras calcinadas a 400°C, que foram caracterizadas como amorfas, apresentam um espectro de absorção de raios X diferente das demais amostras caracterizadas como cristalinas. As amostras cerâmicas sinterizadas em alta temperatura e a pressão atmosférica apresentaram um comportamento microestrutural (grãos micrométricos) e elétrico (ferroelétrico normal) semelhante ao das amostras preparadas através do método de reação do estado sólido. Por outro lado, a amostra cerâmica com x = 0,20 preparada em alta pressão (7,4 GPa) e a temperatura ambiente apresentou somente grãos nanométricos. A manutenção dos grãos em uma escala nanométrica fez com que essa amostra cerâmica apresentasse um comportamento característico de um material ferroelétrico relaxor ao passo que a mesma amostra preparada através do método de síntese convencional (grãos micrométricos) apresentou um comportamento típico de um material ferroelétrico normal. / The main objective of this work was to obtain ferroelectric materials of Pb1-xLaxTiO3 (PLT) composition, with x = 0.10, 0.15 and 0.20, in nanometer scale in order to prepare nanostructure ceramic and thin films and characterize their structural and electric properties. The nanoparticles used to prepared ceramic samples and the solution used to prepared thin films was obtained using the conventional high temperature sintering method and by using high pressure and high temperature simultaneously. The structural modification due to particle size and lanthanum amount was followed by X-Ray diffraction (XRD), Raman spectroscopy and X-Ray absorption techniques. The transition process was followed from XRD pattern and from the Raman spectra. Samples calcined at 400 oC that were characterized as amorphous present different X-ray absorption spectra. The ceramic samples sinterized at high temperature and ambient pressure presented a microstructure (microsized grains) and electrical properties (normal ferroelectric) similar to that observed in the same samples obtained from the solid-state reaction method. On the other hand, the ceramic sample with x = 0.20 prepared at high pressure and at room temperature formed only by nanoparticles present a behavior characteristic of a relaxor ferroelectric material showing the influence of the grain size on the electrical properties of these samples.

L’évolution rapide des communications sans fil a favorisé l’augmentation du nombre de standards alloués aux systèmes de communication fonctionnant sur différentes bandes de fréquences. Pour accompagner les derniers développements de systèmes sans fil, il est indispensable de concevoir des antennes miniatures intégrables. Cependant, la miniaturisation des antennes s’accompagne d’une réduction significative de la bande passante et de leur efficacité de rayonnement ainsi qu’à l’apparition d’un décalage fréquentiel de leurs fréquences de fonctionnement lorsqu’elles sont étudiées dans leur contexte d’utilisation. L’intégration de dispositifs accordables au sein d 'une antenne permet de répondre favorablement à ces problématiques. Parmi les solutions proposées dans la littérature, l’utilisation de matériaux ferroélectriques en couche mince permet de concevoir un condensateur accordable en fonction du champ électrique appliqué. Ces dispositifs réalisés à base de couches minces ferroélectriques ont été développés pour répondre aux exigences particulières et extrêmes des systèmes de télécommunication actuels (miniaturisation, faible coût, facilité de fabrication et d’intégration et bonne tenue en puissance). Cette thèse s’inscrit dans la continuité des recherches sur les antennes reconfigurables en fréquences à base de matériaux ferroélectriques. Deux axes principaux ont été développés au cours de ces travaux de recherche : le développement et la réalisation de condensateurs intégrant un film BST au sein du laboratoire XLIM et leurs caractérisations en hyperfréquence. La seconde partie de nos travaux concerne l’intégration de l’un de ces dispositifs accordables au sein d’une antenne miniature afin d’étudier son accordabilité en fréquence. / The rapid growth of wireless communication has promoted the increase of the number of standards for wireless applications. This progress requests new manufacturing processes of smart devices that are able to work on several frequency bands. However, the miniaturization of antennas is accompanied by a significant reduction of the bandwidth as well as its radiation efficiency and it becomes dependent on its using context. Tunable devices can be integrated within antennas in order to overcome these main issues. Among the solutions proposed in the literature, thin-film ferroelectric materials are used to realize tunable capacitors. The use of such materials allows the design of a tunable capacitor that can be tuned by an applied electric field. The advances of these ferroelectric thin-film devices were developed in order to meet particular and extreme requirements for today's telecommunication systems (miniaturization, low cost, ease of the manufacture process, integration and good power handling). This thesis is part of ongoing research over frequency reconfigurable antennas which are based on ferroelectric materials. Two main axes were developed during this work: The development and realization of capacitors that incorporate a BST film along with their microwave characterizations within XLIM lab. The second part of our work is dedicated to the realization of the complete tunable antenna.

This thesis focuses on studying the interaction and evolution of the needle domains in barium titanate single crystal through the simulation and experimental methods. The results are expected to assist in the interpretation of the arrangement and evolution of the needle domains and improve the design of future material. The existence of a needle domain gives rise to an internal stress field and electric field around the needle tip, which influences the polarization switching process and crack propagation in a single crystal. A model is established to study the interaction and evolution of the needle domains in barium titanate single crystals using the theory of dislocations. Considering the electrical and mechanical incompatibility at the needle tip, the fields produced by a needle domain are represented using the fields due to the equivalent edge dislocations and line charges distributed over the needle tip. Accordingly, the dislocation fields derived by Barnett and Lothe for anisotropic piezoelectric media are used to analyse the stress and electric fields around the needle domains. The calculation of the modified Peach-Koehler force and the total energy due to the needle domains is used to study the interaction among the needle domains and the stability of the needle pattern. Through experimental observation, we further know about the microstructure and common pattern of needle domains. X-ray diffraction is used to map the shape of needle tip and detect the strain field around the needle tip. The interaction of pairs of needle domains in an infinite piezoelectric body is studied. It is found that the needle tip interactions tend to be dominated by the electrostatic terms. Additionally, the stability of groups of needle domains is investigated. Stable configurations of needle domains in a herringbone pattern are identified, consistent with experimental evidence. However, comb-like arrays of needles are found to be unstable. This is contrary to experimental observations, where needle domains are observed in aligned arrays. This contradictory result leads to an analysis of the effect of charge produced by the polarization jump at a needle tip on domain interaction. The existence and position of stable equilibrium states are found to be sensitive to a change in the quantity of polarization charge. When the polarization charge is reduced to about 48% of its theoretical value, the modified model works well to interpret the stability of comb-like needle pattern and herringbone needle pattern. A viscous model is proposed to further analyse the evolution of the needle domains under the external perturbation. Based on the superposition theory proposed by Van der Giessen, boundary value problems are discussed. Single needles and pairs of needle domains are selected to analyse the effect of boundary condition on the distribution and arrangement of the needle domains. After that, the evolution of the comb-like needle domains under the applied external loads is studied. During the process of analysis, a lattice friction model, and the viscous model are compared.

De tous les matériaux multiferroïques, BiFeO3 est celui qui est le plus étudié. C’est un ferroélectrique, antiferromagnétique dont les températures de transition sont bien au-dessus de la température ambiante. De plus, le couplage magnétoélectrique entre ces deux paramètres d’ordre a été observé aussi bien dans les cristaux que dans les couches minces. BiFeO3 possède également la plus grande polarisation ferroélectrique jamais mesurée, 100µC/cm². De gros efforts sont fournis pour comprendre et exploiter les propriétés physiques de ce matériau. Dans ce but, il est important de pouvoir contrôler sa structure en domaines afin d’étudier les phénomènes émergeant aux parois de ces domaines. C’est l’objectif de cette thèse : étudier quelques une des propriétés de BiFeO3, comme la photoélectricité et le magnétisme, tout en prêtant en parallèle une attention particulière à la caractérisation de ces propriétés, dans un domaine et dans une paroi, avec des techniques originales telles que la microscopie de photocourants à balayage (MPB) et le rayonnement synchrotron ou les champs magnétiques intenses. Les images obtenues par MPB, révèlent qu’un champ dépolarisant proche d’une paroi de domaine à 180° peut améliorer de manière significative le rendement des effets photoélectriques : les parois de domaines peuvent être générées et positionnées dans le but de contrôler localement le rendement de l’effet photoélectrique. De plus, l’imagerie de la figure de diffraction de surface d’un réseau de parois de domaines dans des couches minces, par diffusion magnétique résonante de rayons X, permet de montrer que les parois de domaines entraînent la formation de structures magnétiques particulières qui pourraient donner lieu à une aimantation. / Among all multiferroics, BiFeO3 is a material of choice because its two ordering temperatures are well above 300K. It is a ferroelectric antiferromagnet, and magnetoelectric coupling has been demonstrated in bulk and in thin films. Remarkably, BiFeO3 has the largest polarization of all known ferroelectrics (100µC/cm²). A huge research effort is carried out worldwide to understand and exploit the physical properties of this material which requires to design and tailor BiFeO3 on many scales. In this sense, developing methods and tools to control the domain structure is essential to explore new emergent phenomena arising at domain walls. This is the aim of the present PhD work. Some of the original properties of BiFeO3 have been investigated including its photoelectric and magnetic properties. A particular attention is given to characterize in a parallel fashion bulk properties and domain walls properties, using original techniques of characterization such as Scanning Photocurrent Microscopy (SPCM), scattering synchrotron facilities or high field pulses. SPCM mapping reveals that depolarizing fields in the vicinity of a 180° domain wall can significantly improve the photovoltaic efficiency. Thus domain walls can be generated and precisely positioned in order to tailor the local photovoltaic efficiency. Moreover, X-ray resonant magnetic scattering on thin films with periodic domain structure shows that domain walls generate specific magnetic structures with possible uncompensated magnetization.

No description available.

Nous avons développé une nouvelle méthode de microscopie par effet électro-optique linéaire (effet Pockels), dite PLEOM, permettant de cartographier la susceptibilité du deuxième ordre Chi(2) d'un matériau non-centrosymétrique [1, 2]. Cette méthode est complémentaire de la microscopie de génération de seconde harmonique, et s’en distingue par différents aspects physiques et pratiques. Grâce à une détection interférométrique stabilisée, le retard de phase provoqué par une variation d'indice locale du matériau non-linéaire sous l'effet d'un champ électrique est détecté à 10-6 radians près, ouvrant la voie à l'imagerie d'échantillons biologiques ou au suivi du mouvement de nano-sondes [3]. PLEOM apporte un type de données nouveau, la "réponse en phase" du matériau, porteuse d'information physiques plus difficilement accessibles en microscopie biphotonique.Ce manuscrit décrit de nouveaux domaines de développement et d’application de PLEOM, qui a évolué vers une plateforme aux applications variées et multi-échelles, allant du nanométrique au millimétrique.Nous avons tout d’abord montré comment déterminer le vecteur de polarisation attaché à des nano-cristaux ferroélectriques uniques, en vue de leur utilisation comme nano-sondes. Cette nouvelle méthode permet, à notre connaissance de façon unique, de distinguer deux nano-cristaux mono-domaines d'orientations exactement opposées, dont les réponses en SHG ne peuvent pas être distinguées. Une image de phase électro-optique, combinée à un diagramme de polarisation, donne accès à l'orientation vectorielle d'un nano-cristal orienté aléatoirement dans le référentiel du laboratoire. Un verrou est ainsi levé pour des applications comme l'imagerie de nano-domaines ferroélectriques, celle de potentiels électrochimiques membranaires, où l'étude de la dynamique de rotation de molécules. Deux spécificités remarquables de PLEOM en font une méthode d'avenir : la faible intensité de pompage qui assure une bien meilleure biocompatibilité ainsi que la simplicité de la source laser continue utilisée.Nous avons ainsi pu utiliser PLEOM pour caractériser les domaines ferroélectriques d'un cristal de KTiOPO4 périodiquement réorienté en vue d’un quasi-accord de phase, ainsi que ceux d'un cristal bidimensionnel quasi-périodique de LiNbO3. Un retournement clair de la phase de 180 degree est observé au travers des parois de domaines, dont les coefficients électro-optiques apparaissent opposés dans le référentiel du laboratoire. PLEOM se présente ainsi comme un outil de caractérisation non destructif des propriétés de ces cristaux artificiels dont les motifs et les défauts (tels qu'une orientation localement incomplète) ont été caractérisés spatialement, et permet de mesurer localement leurs propriétés non-linéaires, dont le caractère tensoriel permet d’aller au-delà des informations acquises en microscopie classique.En outre, nous avons fait la preuve de principe d'une nouvelle expérience biomimétique, visant à étudier les potentiels membranaires cellulaires, en utilisant PLEOM sur des membranes phospholipidiques créées sur puce micro-fluidique et dopées en colorants. / Complementing Second-Harmonic Generation (SHG) microscopy, a new home-made nonlinear microscope named Pockels Linear Electro-Optical Microscopy (PLEOM) based on the linear electrooptic (Pockels) effect, has been developed and used to map the second-order susceptibility Chi(2) of non-centrosymmetric materials with high sensitivity due to a stabilized interferometric homodyne detection scheme [1, 2]. This enables PLEOM to detect the electrooptic phase retardation of light resulting from the variation of the refractive index of nonlinear materials down to 10-6 radian and to investigate nonlinear materials at the nano-scale [3] towards applications in imaging of biological samples and tracking of labels therein. With PLEOM, a new imaging method allows to access, besides the aplitude, the no less crucial phase response, which is not readily amenable to classical SHG microscopy. In the frame of this dissertation, we have further extended the range of applications of PLEOM to investigate nonlinear materials and structures from nano- to millimeter-scale.Firstly, we have proposed and demonstrated a new approach towards the full vector determination of the spontaneous polarization of single ferroelectric nano-crystals used as SHG nano-probes. This method allows to remove the ambiguity inherent to earlier polarization-resolved SHG microscopy experiments, and has permitted full determination of the orientation of single domain ferroelectric nano-crystals. The electrooptic phase response obtained in the form of phase images and polarization diagrams yields the full orientation in the laboratory frame of randomly dispersed single nano-crystals, together with their electric polarization dipole. The complete vector determination of the dipole orientation is a prerequisite to important applications including ferroelectric nano-domain orientation, membrane potential imaging and rotation dynamics of single biomolecules, especially by using a new low-cost non-invasive imaging method with a low intensity illumination beam.The ferroelectric domain pattern of periodically poled KTiOPO4 and of a two-dimensional decagonal quasi-periodic LiNbO3 nonlinear crystal was determined by local measurement of their electro-optically induced phase retardation. Owing to the sign reversal of the electrooptic coefficients upon domain inversion, a 180 degree (pi) phase shift is observed across domain barriers between domains with opposed orientations. PLEOM allows to reveal the nonlinear and electrooptic spatially modulated patterns in ferroelectric crystals in a non-destructive manner and to determine their poling period, duty cycle and short-range order as well as to detect local defects in the domain structure, such due to incomplete poling.In addition, we have also proposed and demonstrated a new method, based on the voltage dependence of the electrooptic dephasing, to mimic the membrane potential in cells, working at this stage on nonlinear dye containing phospholipidic membranes, grown in a microfluidic set-up.

Durant ce travail de thèse, nous avons étudié l’effet d’un champ électrique intense (>3 kV.cm-1) sur des matériaux à structures pérovskites, le ferroélastique CaTiO3 et le ferroélectrique BaTiO3. Un tel champ agit comme une force extérieure dans la sélection, l’orientation et la distribution des domaines. Son application durant la croissance modifie la nucléation, le coefficient de partage des espèces et la possible modification du diagramme de phase du matériau considéré. En effet les ions dans un champ électrique voient leur énergie changer ce qui implique un nouvel équilibre thermodynamique. La première partie est dédiée à la croissance cristalline de CaTiO3 lorsque plusieurs paramètres de croissance sont modifiés (vitesse de croissance vG et potentiel électrique V). En faisant varier ces paramètres, nous montrons que nous pouvons contrôler la morphologie du cristal et ainsi altérer l’orientation cristalline des domaines. Des résultats similaires sont retrouvés avec BaTiO3.Plusieurs techniques expérimentales ont été employées dans le but d’étudier la microstructure des composés notamment la microscopie électronique miroir (MEM) et la microscopie électronique à faible énergie (LEEM) afin de caractériser les domaines et parois de domaines à la surface du titanate de calcium. La polarité de ces parois ayant été récemment prouvée, nous avons étudié et comparé le potentiel de surface entre les échantillons qui ont été élaborés sous et sans champ électrique. / In this work, we investigate electric field effect (>3 kV.cm-1) on perovskite compound, CaTiO3 (ferroelastic) and BaTiO3 (ferroelectric). This electric field acts like an external force in selection, orientation and distribution of piezoelectric/ferroelastic domains. The electric field can act on nucleation, the partition coefficient of species and the possible modification phases diagrams of a material during its growth. Indeed ions within an electric field see their energy changing which implies a new thermodynamic equilibrium.In the first part, we discuss about crystal growth of CaTiO3 with different growth parameters (velocity of cristal growth vG, electric potential V). By varying this parameters, we can control crystal shape and can alter the crystalline orientation of domains. Same results are found with BaTiO3.In a second step, we used Mirror Electron Micrsocopy (MEM) and Low Energy Electron Microscopy (LEEM) to caracterize domains walls at the surface of calcium titanate. Polarity of domains walls have been prooved recently, and so we have investigated surface potential between samples grown under or without electric field.

Ce travail de thèse porte sur les propriétés structurales et électroniques des parois de domaines ferroïques ; il a pour objectif une meilleure compréhension des mécanismes de conduction dans les parois de domaines du niobate de lithium d’une part, et de la polarité des parois de domaine dans le titanate de calcium d’autre part. La première partie est consacrée aux interactions entre les défauts et les parois de domaine dans le niobate de lithium. L’observation d’une relaxation diélectrique de faible énergie d’activation et l’analyse de son comportement sous l’effet d’un recuit dans des échantillons avec et sans parois nous conduisent à proposer que les parois de domaines stabilisent des états polaroniques. Nous rapportons aussi l'évolution de modes Raman dans des échantillons congruents de niobate de lithium dopés de manière croissante en magnésium. Nous identifions des décalages en fréquence spécifiques aux parois de domaines. Les parois de domaines apparaissent alors comme des lieux de stabilisation des défauts polaires. Nous utilisons la microscopie électronique miroir (MEM) et la microscopie électronique de faible énergie (LEEM) pour caractériser les domaines et parois de domaines à la surface du niobate de lithium dopé magnésium. Nous démontrons que les réglages de la distance focale peuvent être utilisés pour déterminer la polarisation du domaine. Aux parois de domaines, un champ électrique latéral, provenant de différents états de charge de surface, est mis en évidence. Dans une seconde partie, nous étudions la polarité des parois de domaine dans le titanate de calcium. Nous utilisons la spectroscopie de résonance piézo-électrique pour mettre en évidence l’excitation de résonances élastiques par un signal électrique, ce qui est interprété comme une réponse piézoélectrique des parois de domaines. Une image directe des parois de domaine du titanate de calcium est obtenue par LEEM, et montre une différence de potentiel de surface entre domaines et parois. Ce contraste peut être modifié sous l’effet d’injection d’électrons, par un effet d’écrantage des charges de polarisation aux parois. / We investigate the structural and electronic properties of domain walls to achieve a better understanding of the conduction mechanisms in domain walls of lithium niobate and the polarity of domain walls in calcium titanate. In a first part, we discuss the interaction between defects and domain walls in lithium niobate. A dielectric resonance with a low activation energy is observed, which vanishes under thermal annealing in monodomain samples while it remains stable in periodically poled samples. Therefore we propose that domain walls stabilize polaronic states. We also report the evolution of Raman modes with increasing amount of magnesium in congruent lithium niobate. We identified specific frequency shifts of the modes at the domain walls. The domains walls appear then as spaces where polar defects are stabilized. In a second step, we use mirror electron microscopy (MEM) and low energy electron microscopy (LEEM) to characterize the domains and domain walls at the surface of magnesium-doped lithium niobate. We demonstrate that out of focus settings can be used to determine the domain polarization. At domain walls, a local stray, lateral electric field arising from different surface charge states is observed. In a second part, we investigate the polarity of domain walls in calcium titanate. We use resonant piezoelectric spectroscopy to detect elastic resonances induced by an electric field, which is interpreted as a piezoelectric response of the walls. A direct image of the domain walls in calcium titanate is also obtained by LEEM, showing a clear contrast in surface potential between domains and walls. This contrast is observed to change reversibly upon electron irradiation due to the screening of polarization charges at domain walls.

The polarization response such as ferroelectric and ferroelastic switching in ferroelectrics is the important feature for ferroelectric and electromechanical applications. In polycrystalline form ferroelectrics, effects of the microstructural parameters such as texture, grain size, and residual stress are there and have not fully been understood. Among these effects, (1) the origin of grain size effects on ferroelastic switching, (2) mechanical stress effects on polarization switching, and (3) ferroelectric switching kinetics and the relationship to grain boundaries are investigated.<br>Firstly, the microscopic origin of ferroelastic switching suppression in smaller grains is discovered using a microscopic probing technique (piezoresponse force microscopy). It is demonstrated that there is no independent grain size effect on ferroelastic switching; the grain size affects the domain structure in a grain, and the domain structure plays an important role in the ferroelastic switching suppression. This result suggests that the grain size is not an independent critical parameter for the electromechanical property degradation in a grain < 1 m as the ferroelastic switching is a dominant component for the electromechanical property.<br>The study about the mechanical stress effects on the electric field induced polarization switching rationalizes the emergence of the electric field induced low-symmetry phases observed in tetragonal Pb(Zr,Ti)O3 and BaTiO3 ceramics after poling. It is demonstrated that a shear stress plays an important role in stabilizing the monoclinic phase in Pb(Zr,Ti)O3 whereas a normal stress along the polarization axis is a key for the monoclinic phase in BaTiO3 with a thermodynamic approach. It is suggested that the fraction of the low-symmetry phase, which is important for the large electromechanical property, can be engineered by applying an appropriate stress.<br>For the work about ferroelectric switching kinetics, the first direct Barkhausen noise associated with ferroelectric switching is measured. The domain switching time is quantified by the frequency of the Barkhausen noise. It is discovered that the dominant domain wall pinning site is grain boundaries based on the domain wall jump distance between pinning sites calculated from the switching time. This result suggests that the technique is a good tool for understanding the relationship between microstructure – domain wall kinetics.<br>In sum, the mechanisms of the polarization switching suppression due to domain structure and grain boundaries, and the emergence of the low symmetry phases due to stresses are revealed. These discoveries facilitate further improvements of the device performances with engineering the domain structure, grain boundaries and residual stress.<br>