Orientador: Eudes Borges de Araújo / Banca: Rafael Zadorosny / Banca: Jesiel Freitas Carvalho / Resumo: O titanato zirconato de chumbo dopado com lantânio, dado convencionalmente pela fórmula estequiométrica Pb1− x Lax ( Zry ; Ti1− y ) 1− x / 4 O3 , com x = 0,09 e y = 0,65, também conhecido como PLZT 9/65/35, é um importante sistema ferroelétrico relaxor devido as suas propriedades dielétricas, elétricas e eletroóticas. Sendo um ferroelétrico, exibe, também, propriedades tais como piezo e piroeletricidade, dependendo apenas das proporções em que são preparados. Logo, esse sistema é bastante interessante para uma gama de aplicações tecnológicas. Na forma de filmes finos, a composição PLZT 9/65/35 tem sido amplamente estudada e preparada pelos mais diversos métodos. Neste trabalho propõe-se a síntese de filmes finos ferroelétricos da composição PLZT 9/65/35 pelo método dos precursores óxidos, a fim de se compreender a dinâmica dos processos de cristalização e, também, avaliar suas propriedades físicas, como permissividade elétrica e histerese ferroelétrica. A intenção, assim, é colaborar com as informações presentes na literatura sobre as propriedades de filmes finos de PLZT 9/65/35 / Abstract: The lead zirconate titanate doped with lanthanum, conventionally given by stoichiometric formula Pb1− x Lax ( Zry ; Ti1− y ) 1− x / 4 O3 , with x=0,09 and y=0,65, also known as PLZT 9/65/35, is an important relaxor ferroelectric system due to its dielectric, electrical and electrooptical properties. Being a ferroelectric material exhibits also properties such as piezo- and piroelectricity, depending upon the extent to which they are prepared. Therefore, this system is very interesting for a range of technological applications. In the thin films format, the composition PLZT 9/65/35 has been widely studied and prepared by several methods. In this project it is proposed the synthesis of thin films of such material by the oxide precursor method in order to understand the dynamics of crystallization process and also to evaluate their physical properties like electrical permittivity and ferroelectric hysteresis. The intention, thus, is collaborate with the information presented in the literature about the properties of PLZT 9/65/35 thin films / Mestre

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

Made available in DSpace on 2014-06-11T19:25:32Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-02-15Bitstream added on 2014-06-13T19:27:02Z : No. of bitstreams: 1 freire_rlh_me_ilha.pdf: 1499812 bytes, checksum: c68dc0f0c8070f1cf78c922fae42e2df (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O titanato zirconato de chumbo dopado com lantânio, dado convencionalmente pela fórmula estequiométrica Pb1− x Lax ( Zry ; Ti1− y ) 1− x / 4 O3 , com x = 0,09 e y = 0,65, também conhecido como PLZT 9/65/35, é um importante sistema ferroelétrico relaxor devido as suas propriedades dielétricas, elétricas e eletroóticas. Sendo um ferroelétrico, exibe, também, propriedades tais como piezo e piroeletricidade, dependendo apenas das proporções em que são preparados. Logo, esse sistema é bastante interessante para uma gama de aplicações tecnológicas. Na forma de filmes finos, a composição PLZT 9/65/35 tem sido amplamente estudada e preparada pelos mais diversos métodos. Neste trabalho propõe-se a síntese de filmes finos ferroelétricos da composição PLZT 9/65/35 pelo método dos precursores óxidos, a fim de se compreender a dinâmica dos processos de cristalização e, também, avaliar suas propriedades físicas, como permissividade elétrica e histerese ferroelétrica. A intenção, assim, é colaborar com as informações presentes na literatura sobre as propriedades de filmes finos de PLZT 9/65/35 / The lead zirconate titanate doped with lanthanum, conventionally given by stoichiometric formula Pb1− x Lax ( Zry ; Ti1− y ) 1− x / 4 O3 , with x=0,09 and y=0,65, also known as PLZT 9/65/35, is an important relaxor ferroelectric system due to its dielectric, electrical and electrooptical properties. Being a ferroelectric material exhibits also properties such as piezo- and piroelectricity, depending upon the extent to which they are prepared. Therefore, this system is very interesting for a range of technological applications. In the thin films format, the composition PLZT 9/65/35 has been widely studied and prepared by several methods. In this project it is proposed the synthesis of thin films of such material by the oxide precursor method in order to understand the dynamics of crystallization process and also to evaluate their physical properties like electrical permittivity and ferroelectric hysteresis. The intention, thus, is collaborate with the information presented in the literature about the properties of PLZT 9/65/35 thin films

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

Title: Lead-based relaxor ferroelectrics by Raman scattering Author: Iegor Rafalovskyi Institute: Institute of Physics of the Czech Academy of Sciences Supervisor: Ing. Jiří Hlinka, Ph.D., Department of Dielectrics, Institute of Physics of the Czech Academy of Sciences Abstract: The following work is dedicated to measurement and analysis of Raman scat- tering spectra of different perovskite ferroelectrics, mainly lead-based relaxors in the form of bulk and thin films. Investigation of single crystal MPB composition PMN-0.32PT has shown that procedure of zero-field heating of previously field-cooled sample leads to sta- bilization of heterophase pattern with 10-100 µm parallel stripes of alternating tetragonal and rhombohedral (rhombohedral-like) phases. Another point of interest investigated in PMN-0.32PT is rhombohedral to tetragonal phase transition induced by electric field. The domain structure with 90-degree domain walls has been observed in relaxor based composition PFN-0.38PT. Adjacent domains were investigated by polarized Raman scat- tering to confirm their structure and symmetry. Relaxor ferroelectric PSN has shown totally different behavior in polarized Raman spectra if studied in the form of single crystal or epitaxial thin film. The normalized cross-polarized intensity of 810 cm−1 band measured in...

The aim of doctoral dissertation „Grain Size Effect on Dielectric Properties of Ferroelectrics and Relaxors“ by Maksim Ivanov is to investigate, how grain size of ceramics and powders of a few ferroelectrics and relaxors influences macroscopic dielectric properties. The studied materials are powders of a relaxor PbMg⅓Nb⅔O3 (PMN), ceramics of a relaxor with a spontaneous phase transition PbSc½Nb½O3 (PSN), ceramics of a ferroelectric 0.36BiScO3-0.64PbTiO3, and ceramics of Ba2SnO4, which were compared to a better investigated BaSnO3. Investigations were performed in broad frequency (100 Hz – 55 GHz) and temperature (30 K – 1000 K) ranges. Experimental investigations and modelling showed, that bulk properties of relaxor materials are heavily influenced by polar nanoregions, but they do not fully determine them. Morphology of the material (i.e. grain size of ceramics) determines growth and interactions of the nanoregions, thus influencing bulk properties. Moreover, effective medium approximation can explain evolution of dielectric properties of ferroelectrics and relaxors only if dependence of bulk properties on grain size is known. The most interesting result is, that there exist polar entities in ferroelectrics, which are different from ferroelectric domains and are similar to polar nanoregions in relaxors. Their contribution to dielectric permittivity can be comparable to all other contributions. Dimensions of these entities depend on grain size in accordance with Kittel's law. / Maksimo Ivanovo daktaro disertacijos tema yra “Grūdų dydžio įtaka dielektrinėms feroelektrikų ir relaksorių savybėms”. Šio darbo tikslas yra ištirti, kaip keramikų ar miltelių grūdų dydis įtakoja makroskopiškai stebimas kelių feroelektrikų bei feroelektrinių relaksorių dielektrines savybes. Tirtos medžiagos yra klasikinio relaksoriuas PbMg⅓Nb⅔O3 (PMN) milteliai, relaksoriaus su savaiminiu feroelektriniu faziniu virsmu PbSc½Nb½O3 (PSN) keramikos, feroelektriko 0.36BiScO3-0.64PbTiO3 keramikos, bei Ba2SnO4 keramiką, kuri buvo palyginta su kiek labiau žinoma BaSnO3 keramika. Tyrimai buvo atlikti plačiame dažnių (100 Hz – 55 GHz) bei temperatūrų (30 K – 1000 K) intervaluose. Eksperimentiniai tyrimai bei modeliavimai parodė, kad polinės nanosritys labai stipriai įtakoja tūrines relaksorių savybes, tačiau jų neapsprendžia. Medžiagos morfologija (antai keramikų grūdų dydis) lemia nanosričių augimą bei tarpusavio sąveikas, tokiu būdų įtakojamos tūrinės savybės. Be to, efektyvios terpės aproksimacija gali paaiškinti feroelektrikų ir relaksorių dielektrinių savybių priklausomybę nuo grūdų dydžio tik, jei žinomas sąryšis tarp dydžio ir tūrinių savybių. Įdomiausia yra tai, kad feroelektrikuose yra objektų, kurie nėra feroelektriniai domenai ir yra panašūs į relaksorių polines nanosritis. Jų indėlis į dielektrinę skvarbą gali būti palyginamas su visų kitų procesų (pvz. domenų sienelių ir polinių modų) indėliais. Šių objektų dydis priklauso nuo grūdų dydžio pagal Kittel'io dėsnį.

Maksimo Ivanovo daktaro disertacijos tema yra “Grūdų dydžio įtaka dielektrinėms feroelektrikų ir relaksorių savybėms”. Šio darbo tikslas yra ištirti, kaip keramikų ar miltelių grūdų dydis įtakoja makroskopiškai stebimas kelių feroelektrikų bei feroelektrinių relaksorių dielektrines savybes. Tirtos medžiagos yra klasikinio relaksoriuas PbMg⅓Nb⅔O3 (PMN) milteliai, relaksoriaus su savaiminiu feroelektriniu faziniu virsmu PbSc½Nb½O3 (PSN) keramikos, feroelektriko 0.36BiScO3-0.64PbTiO3 keramikos, bei Ba2SnO4 keramiką, kuri buvo palyginta su kiek labiau žinoma BaSnO3 keramika. Tyrimai buvo atlikti plačiame dažnių (100 Hz – 55 GHz) bei temperatūrų (30 K – 1000 K) intervaluose. Eksperimentiniai tyrimai bei modeliavimai parodė, kad polinės nanosritys labai stipriai įtakoja tūrines relaksorių savybes, tačiau jų neapsprendžia. Medžiagos morfologija (antai keramikų grūdų dydis) lemia nanosričių augimą bei tarpusavio sąveikas, tokiu būdų įtakojamos tūrinės savybės. Be to, efektyvios terpės aproksimacija gali paaiškinti feroelektrikų ir relaksorių dielektrinių savybių priklausomybę nuo grūdų dydžio tik, jei žinomas sąryšis tarp dydžio ir tūrinių savybių. Įdomiausia yra tai, kad feroelektrikuose yra objektų, kurie nėra feroelektriniai domenai ir yra panašūs į relaksorių polines nanosritis. Jų indėlis į dielektrinę skvarbą gali būti palyginamas su visų kitų procesų (pvz. domenų sienelių ir polinių modų) indėliais. Šių objektų dydis priklauso nuo grūdų dydžio pagal Kittel'io dėsnį. / The aim of doctoral dissertation „Grain Size Effect on Dielectric Properties of Ferroelectrics and Relaxors“ by Maksim Ivanov is to investigate, how grain size of ceramics and powders of a few ferroelectrics and relaxors influences macroscopic dielectric properties. The studied materials are powders of a relaxor PbMg⅓Nb⅔O3 (PMN), ceramics of a relaxor with a spontaneous phase transition PbSc½Nb½O3 (PSN), ceramics of a ferroelectric 0.36BiScO3-0.64PbTiO3, and ceramics of Ba2SnO4, which were compared to a better investigated BaSnO3. Investigations were performed in broad frequency (100 Hz – 55 GHz) and temperature (30 K – 1000 K) ranges. Experimental investigations and modelling showed, that bulk properties of relaxor materials are heavily influenced by polar nanoregions, but they do not fully determine them. Morphology of the material (i.e. grain size of ceramics) determines growth and interactions of the nanoregions, thus influencing bulk properties. Moreover, effective medium approximation can explain evolution of dielectric properties of ferroelectrics and relaxors only if dependence of bulk properties on grain size is known. The most interesting result is, that there exist polar entities in ferroelectrics, which are different from ferroelectric domains and are similar to polar nanoregions in relaxors. Their contribution to dielectric permittivity can be comparable to all other contributions. Dimensions of these entities depend on grain size in accordance with Kittel's law.

Parmi les matériaux piézo-électriques, les pérovskites ferroélectriques à base de plomb sont connus pour avoir les meilleurs coefficients piézo-électriques et couplage électromécanique. Ils sont largement utilisés dans diverses applications industrielles et technologiques. Les "ferroélectrique relaxeurs" appartiennent à cette famille. Leur structure est caractérisée par la présence de nanorégions polaires orientées de façon aléatoire. Dans cette thèse, nous nous sommes intéressés à l'étude des propriétés structurales et dynamiques de matériaux ferroélectriques et relaxeurs tels que PbTiO3, PbZr0.52Ti0.48O3, PbMg1/3Nb2/3O3 (PMN), PbZn1/3Nb2/3O3, et PbMg1/3Ta2/3O3 (PMT). La structure à longue et courte portée a été étudiée par diffraction de neutrons et spectroscopie d'absorption des rayons X (XAFS), alors que la spectroscopie hyper-Raman (HR) est utilisée pour sonder les vibrations. L'analyse de la structure locale de matériaux pérovskites complexes AB'B''O3 montre que la pression diminue le désordre statique des gros cations occupant le site B, tandis que le champ électrique appliqué a un effet opposé. Cette distortion induite sous champ pourrait être à l'origine des forts coefficient piézoélectrique dans ces matériaux. La diffusion HR dans PMN et PMT a permis d'observer pour la première fois le "mode mou" responsable de la dépendance en température de la constante diélectrique. L'analyse des règles de sélection et la description en modes propres des vibrations actives en HR, permet de rendre compte de l'implication de chaque atome dans le comportement structural en température des ferroélectriques relaxeurs. / Among piezoelectric materials, lead-based ferroelectric perovskites are known to have the largest piezoelectric coefficients and electromechanical coupling. They are widely used in dfferent industrial and technological applications. The so-called "relaxors" belong to this family. Their structure is characterized by the presence of randomly oriented polar nanoregions. In this thesis, we are interested in studying the structural and dynamical properties of prototypical ferroelectric materials and relaxors such as PbTiO3, PbZr0.52Ti0.48O3, PbMg1/3Nb2/3O3 (PMN), PbZn1/3Nb2/3O3, and PbMg1/3Ta2/3O3 (PMT). The long and short range structure has been investigated by neutron diffraction and X-ray absorption fine structure (XAFS), while hyper-Raman scattering (HRS) is used to probe the vibrations. The local structure analysis of complex perovskite materials AB'B''O3 shows that pressure reduces the static disorder of the large cation occupying the B-site, while an applied electric field has an opposite effect. This field-induced distortion might relate to the large piezoelectric coefficient in such materials. HRS in PMN and PMT allows the first observation of the "primary" soft mode responsible for the temperature dependence of the dielectric constant. The selection rule analysis reveals the nature of the HRS active vibrational bands and enables us to get insights about the involvement of each atom in the structural modifications upon temperature.

Les multiferroïques sont des matériaux dans lesquels plusieurs propriétés ferroïques peuvent coexister, e. g. ferromagnétisme et ferroélectricité. La recherche de tels matériaux fait l'objet d'une activité croissante en raison de l’enjeu majeur qu’ils représentent dans de nombreux domaines (mémoires, spintronique…). Les matériaux qui possèdent les propriétés nécessaires pour des applications futures sont cependant peu nombreux. Des niobates de formule Ba2LnFeNb4O15 (Ln = lanthanide), de structure bronze quadratique (TTB) susceptibles de présenter un ordre ferroélectrique et un ordre magnétique ont été synthétisés. Les propriétés magnétiques des céramiques proviennent d'une phase secondaire, faisant d’eux des composites multiferroïques. Leur souplesse cristallochimique permet de contrôler les propriétés composites par substitutions cationiques dans la matrice TTB. Afin de compléter l'étude cristallochimique, la croissance de monocristaux de TTB a été entreprise avec succès. / Multiferroics are materials which possess several ferroic properties, e.g. ferroelectricity, ferromagnetism. The search for multiferroics arises a growing activity, due to their potential applications in memories, spintronic… Yet the materials displaying the adequate properties for future application are very few. Niobates with the formula Ba2LnFeNb4O15, potentially ferroelectric and ferromagnetic, have been synthesized. The magnetic properties of the ceramics are related to a secondary phase, thus making them composite multiferroics. Their crystal-chemical flexibility allows for the composites properties tuning by cationic substitutions into the TTB framework. To complete the crystal-chemical study, the growth of TTB single-crystals was successfully engaged.

Les travaux présentés dans ce manuscrit concernent des niobates de formulation Ba2LnNb4O15 (Ln = La ou Nd) et de structure "Tetragonal Tungsten Bronze" (TTB). Ces travaux se situent à la charnière de la chimie et de la physique des matériaux diélectriques et visent à mettre en relation structure cristalline et propriétés diélectriques. L'étude a été menée sur des TTB élaborés sous forme céramique et monocristalline. Après détermination de conditions optimales de croissance, par fusion de zone en four à image, des sections monocristallines ont été obtenues et caractérisées. Les résultats obtenus suggèrent des liens étroits entre composition, modulations structurales apériodiques et comportement diélectrique. Dans le même temps, deux nouvelles solutions solides céramiques ont été explorées, avec des schémas de substitution différents menant notamment à une réflexion très large sur les liens cristallochimie-ferroélectricité dans cette famille de TTB. Ces solutions solides présentent un crossover relaxeur-ferroélectrique, un comportement original et déjà observé dans d'autres solutions solides issues de cette famille de TTB. Des caractérisations avancées (mesures pyro- et piézoélectriques, cycles de polarisation) et des études structurales résolues en composition et en température ont permis d'établir des diagrammes de phases diélectriques montrant l'existence d'un état ferroélectrique métastable. Finalement, la présence d’une modulation structurale bidimensionnelle a pu être confirmée, dans les monocristaux et dans les céramiques, et l'ensemble des résultats obtenus pointent son implication dans les comportements cristallochimiques originaux rencontrés dans ces TTB. / The present work deals with Ba2LnNb4O15 (Ln = La ou Nd) niobates crystallizing with the "Tetragonal Tungsten Bronze" (TTB) structure. These researches, at the interface of chemistry and physics of dieletrics, aim at establishing structure / dielectric properties relationships. They were performed on TTB materials elaborated in ceramic and single crystal forms. Following optimization of growth parameters with an image furnace, single crystals were obtained and characterized. The results obtained suggest that composition, aperiodically modulated structure and dielectric behavior are closely tied in TTBs. Meanwhile, two new ceramic solid solutions with different substitutions schemes were investigated, deepening the insight on crystal-chemistry and ferroelectricity of TTBs. These solid solutions exhibit a relaxor-ferroelectric crossover, an original behaviour previously observed in solid solutions derived from the same family of TTB niobates. Advanced physical characterization (ferro-, pyro- and piezoelectric measurements, polarization loops), and composition/temperature resolved structural studies, allowed for the determination of a dielectric phase diagrams showing the presence of a metastable ferroelectric state. Finally, the existence of a two-dimensional structural modulation in single crystals and ceramics has been confirmed, and the whole set of experimental results points towards its implication in the original dielectric behavior observed in these TTBs.