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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.

Orientador: Eudes Borges de Araújo / Resumo: Polycrystalline thin films of Pb0.91La0.09Zr0.65Ti0.35O3 (PLZT9/65/35) and Sr0.75Ba0.25Nb2O6 (SBN75) were prepared by the chemical polymeric routine in order to investigate their physical properties at the macro- and nanoscale. X-ray diffraction (XRD), piezoresponse force microscopy (PFM), and scanning electron microscopy (SEM) were used as investigative tools. PLZT9/65/35 and SBN75 thin films have exhibited perovskite and tungsten bronze crystal structure at room temperature, as it was expected in this nominal composition for these relaxor ferroelectric materials. In addition, Rietveld method of the crystalline structure has revealed the thickness dependence of the crystallite size, grain size, and microstrain. The transition temperature of SBN thin film showed to shift to lower temperatures, suggesting the presence of a higher defect concentration, such as oxygen vacancies, chemical disorder, and lattice defects in this film. SEM has exhibited the porosity features in both thin films and has confirmed the existence of chemical elements (such as oxygen, niobium, lanthanum, strontium, platinum, silicon and barium) in film surface and near the substrate. Ferroelectric properties have been investigated by PFM and the results have suggested a thickness and crystallite size dependence of the piezoelectric response. Also in this work, the dynamic of ferroelectric domain switching and the induced domain relaxation were studied using the switching spectroscopy PFM (SS-PFM) in both r... (Resumo completo, clicar acesso eletrônico abaixo) / Doutor

Nanoscale ferroelectric materials have numerous possible applications such as actively tunable photonic crystals, terahertz emitters, ultrasound transducers, and energy harvesters. One of most technologically relevant ferroelectric materials is lead zirconate titanate (PZT) due to its large piezoelectric response. However, there are limited methods currently available for creating nanoscale PZT structures. Current top-down patterning methods include material removal via a high energy beam, which damages the piezoelectric's properties, and wet etching, which is an isotropic process that results in poor edge definition. Similarly, current bottom-up approaches such as hard template-growth and hydrothermal processing have limited control over the aspect ratio of the structures produced and lack site specific registry. In this work, a bottom-up approach for creating PbZr₀.₅₂Ti₀.₄₈O₃ nanotubes was developed using soft-template infiltration by a sol-gel solution. This method allows excellent control of the structures produced, overcoming current manufacturing limitations. PZT nanotubes were fabricated with diameters ranging from 100 to 200 nm, aspect ratios (height to diameter) from 1.25:1 to 5:1, and wall thicknesses from 5 to 25 nm. The piezoelectric and ferroelectric nature of the nanotubes was characterized via scanning probe microscopy in order to investigate nanoscale phenomena. Specifically, the effects of lateral constraint, substrate clamping, and critical size on the extrinsic contribution to the piezoelectric response were studied and the results are discussed.

Submitted by MICHAEL DE MELO null (michaeldemelo@hotmail.com) on 2017-09-28T20:19:34Z No. of bitstreams: 1 Tese_Versão de Correção_Final_6_ultima.pdf: 5448253 bytes, checksum: 719d0e92c6a574eea487ee70a3b68542 (MD5) / Approved for entry into archive by Monique Sasaki (sayumi_sasaki@hotmail.com) on 2017-09-29T18:01:11Z (GMT) No. of bitstreams: 1 melo_m_dr_ilha.pdf: 5511619 bytes, checksum: 89580a7f6e20d2c6d9a389aa1939e9e1 (MD5) / Made available in DSpace on 2017-09-29T18:01:11Z (GMT). No. of bitstreams: 1 melo_m_dr_ilha.pdf: 5511619 bytes, checksum: 89580a7f6e20d2c6d9a389aa1939e9e1 (MD5) Previous issue date: 2017-09-11 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Polycrystalline thin films of Pb0.91La0.09Zr0.65Ti0.35O3 (PLZT9/65/35) and Sr0.75Ba0.25Nb2O6 (SBN75) were prepared by the chemical polymeric routine in order to investigate their physical properties at the macro- and nanoscale. X-ray diffraction (XRD), piezoresponse force microscopy (PFM), and scanning electron microscopy (SEM) were used as investigative tools. PLZT9/65/35 and SBN75 thin films have exhibited perovskite and tungsten bronze crystal structure at room temperature, as it was expected in this nominal composition for these relaxor ferroelectric materials. In addition, Rietveld method of the crystalline structure has revealed the thickness dependence of the crystallite size, grain size, and microstrain. The transition temperature of SBN thin film showed to shift to lower temperatures, suggesting the presence of a higher defect concentration, such as oxygen vacancies, chemical disorder, and lattice defects in this film. SEM has exhibited the porosity features in both thin films and has confirmed the existence of chemical elements (such as oxygen, niobium, lanthanum, strontium, platinum, silicon and barium) in film surface and near the substrate. Ferroelectric properties have been investigated by PFM and the results have suggested a thickness and crystallite size dependence of the piezoelectric response. Also in this work, the dynamic of ferroelectric domain switching and the induced domain relaxation were studied using the switching spectroscopy PFM (SS-PFM) in both relaxor systems as a function of variable DC applied voltages and pulse durations. / Filmes policristalinos de Pb0,91La0,09Zr0,65Ti0,35O3 (PLZT9/65/35) e de Sr0,75Ba0,25Nb2O6 (SBN75) foram preparados por uma rotina química polimérica para investigarmos as suas propriedades em nano- e macroescala. Difração de raios-X (DRX), microscopia de força atômica de piezoresposta (PFM), e microscopia eletrônica de varredura (SEM), foram utilizados como ferramentas investigativas. Os filmes finos de PLZT9/65/35 e de SBN75 exibiram estrutura peroviskita e tungstênio bronze, respectivamente, conforme esperado à temperatura ambiente e na composição nominal para estes materiais ferroelétricos relaxores. Além disso, o refinamento de Rietveld da estrutura revelou a dependência do tamanho do cristalito e do microstrain com a espessura. A temperatura de transição de fase do filme de SBN mostrou um deslocamento para valores menores de temperatura, sugerindo a presença de concentração de defeitos, tais como vacâncias de oxigênio, desordem química e defeitos de rede, maior no filme de SBN. Microscopia eletrônica de varredura (SEM) exibiu o caráter poroso de ambos os filmes. Propriedades ferroelétricas desses filmes foram investigados por meio da técnica de PFM. A piezoresposta mostrou ter uma dependência em função do tamanho do cristalito e da espessura. Neste trabalho, a dinâmica de reversão de domínios ferroelétricos e a relaxação de domínios induzidos foram estudados por meio do uso da espectroscopia de chaveamento (SS-PFM) em ambos os sistemas em função da tensão DC e do tempo de duração do pulso. / CNPq: 232241/2014-7

No description available.

The integration of sensors, actuators, and control systems is an ongoing process in a wide range of applications covering automotive, medical, military, and consumer electronic markets. Four major families of ceramic and metallic actuators are under development: piezoelectrics, electrostrictors, magnetostrictors, and shape-memory alloys. All of these materials undergo at least two phase transformations with coupled thermodynamic order parameters. These transformations lead to complex domain wall behaviors, which are driven by electric fields (ferroelectrics), magnetic fields (ferromagnetics), or mechanical stress (ferroelastics) as they transform from nonferroic to ferroic states, contributing to the sensing and actuating capabilities. This research focuses on two multiferroic crystals, Pb(Mg1/3Nb2/3)O3-PbTiO3 and Fe-Ga, which are characterized by the co-existence and coupling of ferroelectric polarization and ferroelastic strain, or ferro-magnetization and ferroelastic strain. These materials break the conventional boundary between piezoelectric and electrostrictors, or magnetostrictors and shape-memory alloys. Upon applying field or in a poled condition, they yield not only a large strain but also a large strain over field ratio, which is desired and much benefits for advanced actuator and sensor applications. In this thesis, particular attention has been given to understand the structure-property relationships of these two types of materials from atomic to the nano/macro scale. X-ray and neutron diffraction were used to obtain the lattice structure and phase transformation characteristics. Piezoresponse and magnetic force microscopy were performed to establish the dependence of domain configurations on composition, thermal history and applied fields. It has been found that polar nano regions (PNRs) make significant contributions to the enhanced electromechanical properties of PMN-x%PT crystals via assisting intermediate phase transformation. With increasing PT concentration, an evolution of PNRï  PND (polar nano domains)-> micron-domains-> macro-domains was found. In addition, a domain hierarchy was observed for the compositions near a morphotropic phase boundary (MPB) on various length scales ranging from nanometer to millimeter. The existence of a domain hierarchy down to the nm scale fulfills the requirement of low domain wall energy, which is necessary for polarization rotation. Thus, upon applying an E-field along <001> direction(s) in a composition near the MPB, low symmetry phase transitions (monoclinic or orthorhombic) can easily be induced. For PMN-30%PT, a complete E-T (electric field vs temperature) diagram has been established. As for Fe-x at.% Ga alloys, short-range Ga-pairs serve as both magnetic and magnetoelastic defects, coupling magnetic domains with bulk elastic strain, and contributing to enhanced magnetostriction. Such short-range ordering was evidenced by a clear 2theta peak broadening on neutron scattering profiles near A2-DO3 phase boundary. In addition, a strong degree of preferred [100] orientation was found in the magnetic domains of Fe-12 at.%Ga and Fe-20 at.%Ga alloys with the A2 or A2+DO3 structures, which clearly indicates a deviation from cubic symmetry; however, no domain alignment was found in Fe-25 at.%Ga with the DO3 structure. Furthermore, an increasing degree of domain fluctuations was found during magnetization rotation, which may be related to short-range Ga-pairs cluster with a large local anisotropy constant, due to a lower-symmetry structure. / Ph. D.

Ferroelectric (piezoelectric) and ferromagnetic materials have extensively permeated in modern industry. (Na1/2Bi1/2)TiO3-BaTiO3 (NBT-x%BT) single crystals and K1/2Na1/2NbO3 (KNN) textured ceramics are top environment-friendly candidates which have potential to replace the commercial lead zirconate titanate or PZT. High magnetostrictive strain (up to 400 ppm) of Fe-xat.%Ga makes this alloys promising alternatives to existing magnetostrictive materials, which commonly either contain costly rare-earth elements or have undesirable mechanical properties for device applications. These systems have common characteristics: compositional/thermal/ electrical dependent structural heterogeneity and chemical disorder on sub-micron or nano scale, resulting in diverse local structures and different physical properties. In this work, I have investigated domain and local structures of NBT-x%BT crystals, KNN ceramics and Fe-xat.%Ga alloys under various conditions, mainly by scanning probe and electron transmission techniques. In NBT-x%BT single crystals, polarized light, piezo-response force (PFM) and transmission electron (TEM) microscopies were used to study domain structures and oxygen octahedral tiltings. Hierarchical domain structures were found in NBT: a high-temperature tetragonal ferroelastic domain structure is elastically inherited into a lower temperature rhombohedral ferroelectric phase. Nanoscale domain engineering mechanism was found to still work in NBT-x%BT system and a modified phase diagram was proposed based on domain observations. An increased intensity of octahedral in-phase tilted reflections and a decrease in the anti-phase ones was observed, with increasing x as the morphotropic phase boundary (MPB) is approached. It was also found that Mn substituents favor the formation of long range ordered micro-sized ferroelectric domains and octahedral in-phase tilted regions near the MPB. Nano-size heterogeneous regions were observed within submicron domain structure, indicating that the nanoscale polarization dynamics are not confined by domain boundaries, and the high piezoelectricity of NBT-x%BT is due to a polarization dynamics with high sensitivity to electric field and a broadened relaxation time distribution. In KNN textured ceramics, an aging effect was found to exist in the orthorhombic single phase field, not only in the orthorhombic and tetragonal two-phase field as previously reported. No variation of phase structure was revealed between before and after aging states. However, pronounced changes in domain morphology were observed by both PFM and TEM: more uniform and finer domain structures were then found with aging. These changes were even more pronounced after poling the aged state. A large number of sub-micron lamellar domains within micron-domains were observed: suggesting a domain origin for improved piezoelectric properties. In Fe-xat.%Ga alloys, an underlying inhomogeneity from Ga atoms embedded into the α-Fe matrix was believed to be the origin of giant magneostrictive properties. I have systematically investigated the phase structure and nano-size heterogeneity of Fe-xat.%Ga alloys subjected to different thermal treatments using standard TEM and high resolution TEM for 10<x<30. Nano-precipitates were observed in all specimens studied: A2, D03 and B2 phases were found depending on x. Nano-precipitates of D03 were observed to be dominant for compositions near the magnetostriction peaks in the phase diagram. Quenching was found to increase the volume fraction of nanoprecipitates for x=19, near the first magnetostriction peak. With increasing x to 22.5, nanoprecipitates were observed to undergo a D03 – B2 transformation. A high density of D03 precipitates of nanoscale size was found to be the critical factor for the first maximum in the magnetostriction. / Ph. D.

The increasing miniaturization of electric and mechanical components makes the synthesis and assembly of nanoscale structures an important step in modern technology. Functional materials, such as the ferroelectric perovskites, are vital to the integration and utility value of nanotechnology in the future. In the present work, chemical methods to synthesize one-dimensional (1D) nanostructures of ferroelectric perovskites have been studied. To successfully and controllably make 1D nanostructures by chemical methods it is very important to understand the growth mechanism of these nanostructures, in order to design the structures for use in various applications. For the integration of 1D nanostructures into devices it is also very important to be able to make arrays and large-area designed structures from the building blocks that single nanostructures constitute. As functional materials, it is of course also vital to study the properties of the nanostructures. The characterization of properties of single nanostructures is challenging, but essential to the use of such structures. The aim of this work has been to synthesize high quality single-crystalline 1D nanostructures of ferroelectric perovskites with emphasis on PbTiO3 , to make arrays or hierarchical nanostructures of 1D nanostructures on substrates, to understand the growth mechanisms of the 1D nanostructures, and to investigate the ferroelectric and piezoelectric properties of the 1D nanostructures. In Paper I, a molten salt synthesis route, previously reported to yield BaTiO3 , PbTiO3 and Na2Ti6O13 nanorods, was re-examined in order to elucidate the role of volatile chlorides. A precursor mixture containing barium (or lead) and titaniumwas annealed in the presence of NaCl at 760 °C or 820 °C. The main products were respectively isometric nanocrystalline BaTiO3 and PbTiO3. Nanorods were also detected, but electron diffraction revealed that the composition of the nanorods was respectively BaTi2O5/BaTi5O11 and Na2Ti6O13 for the two different systems, in contradiction to the previous studies. It was shown that NaCl reacted with BaO(PbO) resulting in loss of volatile BaCl2 (PbCl2 ) and formation and preferential growth of titanium oxide-rich nanorods instead of the target phase BaTiO3 (or PbTiO3 ). The molten salt synthesis route may therefore not necessarily yield nanorods of the target ternary oxide as reported previously. In addition, the importance of NaCl(g) for the growth of nanorods below the melting point of NaCl was demonstrated in a special experimental setup, where NaCl and the precursors were physically separated. In Paper II and III, a hydrothermal synthesis method to grow arrays and hierarchical nanostructures of PbTiO3 nanorods and platelets on substrates is presented. Hydrothermal treatment of an amorphous PbTiO3 precursor in the presence of a surfactant and PbTiO3 or SrTiO3 substrates resulted in the growth of PbTiO3 nanorods and platelets aligned in the crystallographic &lt;100&gt; orientations of the SrTiO3 substrates. PbTiO3 nanorods oriented perpendicular to the substrate surface could also be grown directly on the substrate by a modified synthesis method. The hydrothermal method described in Paper II and III was developed on the basis of the method described in Appendices I and II. In Paper IV, a template-assisted method to make PbTiO3 nanotubes is presented. An equimolar Pb-Ti sol was dropped onto porous alumina membranes and penetrated into the channels of the template. Single-phase PbTiO3 perovskite nanotubes were obtained by annealing at 700 °C for 6 h. The nanotubes haddiameters of 200 - 400 nm with a wall thickness of approximately 20 nm. Excess PbO or annealing in a Pb-containing atmosphere was not necessary in order to achieve single phase PbTiO3 nanotubes. The influence of the heating procedure and the sol concentration is discussed. In Paper V, a piezoresponse force microscopy study of single PbTiO3 nanorods is presented. The piezoelectric properties were studied in both vertical and lateral mode. Piezoelectric activity and polarization switching was observed in the vertical mode, demonstrating the ferroelectric nature of the nanorods. The nanorods decomposed after repeated cycling of the dc bias at one spot on the nanorod, which resulted in parts of the nanorod disappearing and/or accumulation of particles on the surface of the nanorod. In Paper VI, a method to contact single nanorods by electron beam induced deposition of platinum is presented. An organometallic compound, (trimethyl)-methylcyclopentadienylplatinum(IV), was used as precursor. A home-made apparatus was constructed for the purpose and was mounted onto a scanning electron microscope. Calculations based on apparatus geometry and molecular flow were used to estimate the deposition time and the height of the deposits. The location and height of the deposits were controlled so that single nanorods could be successfully contacted at the ends of the nanorods. Fabrication of a sample device for piezoresponse force microscopy studies of single nanorods using an axial dc bias setup is described in Appendix IV. A proposed experimental setup for such studies is also presented.

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