Les matériaux ferroélectriques suscitent beaucoup d’intérêt du fait de leurs propriétés physiques telles que la piézoélectricité, la ferroélectricité ou encore leur permittivité élevée. Ainsi, on cherche à les intégrer dans les micro- et nano-systèmes dans lesquels on les retrouve généralement sous forme de couche mince dans une configuration de type capacité plane. En particulier, l’oxyde de plomb, titane et zirconium (PZT) est un matériau très attractif pour les applications RF capacitives du fait de sa grande permittivité. Son intégration sur des électrodes métalliques, i.e. les lignes coplanaires constituant le guide d’onde, implique de maîtriser sa croissance en film mince. L’application d’une tension dans un dispositif RF actif impose également de contrôler les propriétés électriques : nature des courants de fuite et comportement ferroélectrique du PZT. Dans ce contexte, les couches minces de PZT sont déposées par ablation laser (PLD) sur un empilement La₀.₆₇Sr₀.₃₃MnO₃ (LSMO) / Pt (111) déposé sur un substrat monocristallin de saphir. La couche d’accroche conductrice LSMO est nécessaire afin d’éviter la formation d’une phase pyrochlore paraélectrique. Le contrôle de l’orientation cristalline de la couche de LSMO permet de contrôler la texturation de la couche de PZT. Les courants de fuite au travers de l’empilement Pt/PZT/LSMO/Pt ont ensuite été étudiés dans l’intervalle de température 220-330K de façon à déterminer les mécanismes de conduction. Une transition a été mise en évidence entre, autour de la température ambiante, un mécanisme contrôlé par la diffusion des charges en volume et, à basse température, un mécanisme contrôlé par l’injection des charges aux interfaces électrode/PZT. Un mécanisme par sauts a été identifié au-dessus de 280K en cohérence avec la présence de défauts étendus et la structure colonnaire du PZT. Afin de contrôler ces courants de fuite, différentes stratégies ont été utilisées. La première consiste à insérer une couche d’oxyde isolante à l’interface supérieure Pt/PZT modifiant ainsi l’injection des charges et permettant de réduire les courants de fuite. La seconde stratégie consiste, quant à elle, à modifier la structure de la couche de PZT en volume en élaborant des composites diélectrique/PZT multicouches ou colonnaires. Ainsi, une couche d’oxyde isolante a été insérée au milieu de la couche de PZT et a permis de réduire les courants de fuite. Le contrôle de la nucléation du PZT a également permis par nanofabrication d’élaborer un composite colonnaire pérovskite PZT/pyrochlore. La densité de piliers de pyrochlore dans la phase ferroélectrique permet de moduler la densité de courant dans la structure. Le PZT et les hétérostructures permettant de réduire les courants de fuite ont ensuite été intégrés dans une structure RF capacitive avec des lignes coplanaires d’or. Les performances RF en termes d’isolation et de pertes par insertion ainsi que la compatibilité de ces différents matériaux ont été étudiées et ont montré que les solutions développées dans le cadre du contrôle des courants de fuite sont prometteuses pour être intégrées dans les dispositifs RF capacitifs. En outre, on a cherché à extraire la permittivité à haute fréquence du PZT lorsque celui-ci est inséré dans une structure capacitive. Cette étude a notamment permis de mettre en évidence les points techniques à modifier concernant la structure du dispositif afin de parvenir à exploiter les propriétés physiques du PZT à haute fréquence. / Ferroelectric materials are raising a lot of interest due to their physical properties such as piezoelectricity, ferroelectricity or high dielectric constant. Thus, they are generally integrated in micro- and nano-systems as thin films in a capacitive configuration. Especially, the lead zirconate titanate oxide (PZT) is an attractive material for capacitive RF applications due to its high dielectric constant. The growth of the PZT thin film has to be controlled on metallic electrodes for its integration on coplanar transmission lines. Moreover, electrical properties such as leakage current and ferroelectric behavior of PZT have to be monitored upon application of a dc voltage bias for RF device operation. In this context, PZT thin films were grown by the pulsed laser deposition technique (PLD) on a La₀.₆₇Sr₀.₃₃MnO₃ (LSMO) / Pt (111) electrode on a monocrystalline sapphire substrate. The LSMO buffer layer is mandatory to avoid the formation of the paraelectric pyrochlore phase. The control of the crystalline orientation of the LSMO layer allows for the control of the PZT layer texture. Leakage currents through the Pt/PZT/LSMO/Pt stack were then studied in the 220-330K temperature range to determine the conduction mechanisms. A transition is evidenced between a bulk-controlled mechanism near room temperature and an interface-controlled mechanism at low temperature. A hopping mechanism is identified above 280K in line with the presence of extended defects and the columnar structure of the PZT layer. Several strategies were tested to control leakage currents. The first one consists in inserting an insulating oxide layer at the top Pt/PZT interface. In this way, charge injection was modified and leakage currents were reduced. The second strategy consists in changing the PZT layer bulk structure by elaborating a layered or columnar dielectric/PZT composite. Thus, an insulating oxide layer was inserted in the middle of the PZT layer and permitted to reduce leakage currents. Moreover, the control of the PZT nucleation allowed for the elaboration of a columnar PZT/pyrochlore composite. The leakage currents in this composite can be tuned through the pyrochlore pillars density among the ferroelectric matrix. Then, PZT and the heterostructures for leakage current control were integrated in a capacitive RF structure with gold coplanar transmission lines. RF performances in terms of isolation and insertion loss of these materials were studied and gave good results. In particular the heterostructures developed to control the leakage currents are promising for their integration in capacitive RF devices. Besides, I tried to extract the permittivity of PZT at high frequency with the PZT layer in a capacitive configuration. This study highlighted the essential modifications of the capacitive structure that have to be made in order to be able to exploit PZT properties at high frequency.

Les matériaux ferroélectriques sont caractérisés par l'existence d'une polarisation électrique spontanée, dont l'orientation peut être inversée par l'application d'un champ électrique adéquat. Permettant de coder l'information sous la forme d'un domaine ferroélectrique, i.e. une région du matériau avec une certaine orientation de la polarisation, les ferroélectriques ouvrent la voie au stockage de masse de très haute densité (>10 Tbit/in ²). Dans ce contexte, nous avons employé la Piezoresponse Force Microscopy (PFM), un mode particulier de Microscope à Force Atomique (AFM), permettant la manipulation et la détection des domaines ferroélectriques à l'échelle du nanomètre. Avec pour objectif d'étudier les mécanismes de formation des domaines par l'intermédiaire d'une pointe AFM, nos travaux ont mis en valeur la cinétique de croissance des domaines dans des films minces monocristallins de LiTaO3, avec une approche complémentaire de celle thermodynamique, dépendante du champ électrique et soulignant le rôle de l'humidité dans une possible conduction de surface. En parallèle, les films de LiTaO3 ont permis d'appréhender davantage la nature électro-mécanique de la réponse PFM, pour notamment relier l'amplitude du signal mesuré à la géométrie du domaine sous pointe. PFM et domaines ferroélectriques se sont en effet révélés tour à tour, objet d'étude et outil de caractérisation. / Ferroelectric materials are characterized by their spontaneous polarization, whose direction can be reversed by the application of a suitable electric field. Using domains, i.e. regions of uniform polarization orientation, as information bits, ferroelectrics opens the pathway towards ultrahigh storage densities (>10 Tbit/in²). In this respect, Piezoresponse Force Microscopy (PFM), a technique derived from Atomic Force Microscopy (AFM), was used to manipulate and detect ferroelectric domains on the nanometer scale. Our study was focused on the domains formation mechanism in the local electric field of a nanosized tip. Within an approach complementary to the thermodynamic one, we underlined the kinetics of domains growth in single-crystal LiTaO3 thin films, and the role of humidity in a possible surface conduction. In parallel, the LiTaO3 thin films were used to better understand the PFM response, in particular the relation between the measured signal and the geometry of the domain below the tip. This way, PFM and ferroelectrics domains alternately appeared as object of study and characterization tool.

Die Ferroelektrische Lithografie ist ein im letzten Jahrzehnt entwickeltes Verfahren zur gezielten Steuerung des Aufbaus von Nanostrukturen auf ferroelektrischen Oberflächen. Hierbei wird ausgenutzt, dass die unterschiedlich orientierte Spontanpolarisation des Materials in den einzelnen Domänen zu einer charakteristischen Variation der Oberflächenchemie führt. Die vorliegende Dissertation behandelt die Umsetzung dieses Ansatzes zur gezielten und steuerbaren Deposition von Nanostrukturen aus Edelmetallen oder organischen Molekülen. Diese Deposition erfolgte mittels einer nasschemischen Prozessierung unter UV-Beleuchtung auf magnesiumdotierten, einkristallinen Lithiumniobat-Substraten. Als typisches Ergebnis zeigte sich sowohl für in Wasser gelöste Silber-, Gold- und Platinsalze als auch für wässrige Lösungen des organischen Fluoreszenzfarbstoffs Rhodamin 6G eine bevorzugte Abscheidung des Materials an den 180°-Domänenwänden auf der Substratoberfläche. Dabei beginnt die Abscheidung in Form einzelner Nanopartikel innerhalb eines 150−500 nm breiten Streifens parallel zur Domänenwand. Bei fortgesetzter Beleuchtung erfolgt ein weiteres Wachstum der Kristallite bis zur ihrer gegenseitigen Berührung. Damit ermöglicht dieser Abscheideprozess den Aufbau organischer oder metallisch polykristalliner Nanodrähte mit Abmessungen um 100 nm in Breite und Höhe. Die Länge ist lediglich durch die Probenabmessungen begrenzt. Die so erzeugten Strukturen wurden im Rahmen der experimentellen Arbeiten topografisch, elektrisch und optisch charakterisiert. Am Beispiel einzeln kontaktierter Platindrähte konnte dabei deren annähernd ohmsches Leitfähigkeitsverhalten nachgewiesen werden. Zudem reagiert der Widerstand eines solchen Platin-Nanodrahtes sehr sensitiv auf Änderungen des umgebenden Gasmediums, was die Eignung solcher Strukturen für die Integration in künftige Sensorbauelemente unterstreicht. Weitergehende Untersuchungen beschäftigten sich mit der Klärung der Ursachen dieser sogenannten Domänenwanddekoration. Hierzu wurde die Lage der abgeschiedenen Strukturen mit dem zu Grunde liegenden Domänenmuster verglichen. Bis auf wenige Ausnahmen wurde dabei eine auf die Domänengrenze zentrierte, symmetrische Bedeckung nachgewiesen. Als Erklärungsansatz wird die Trennung der photoinduzierten Elektron-Loch-Paare durch das elektrostatische Feld der Polarisations- und Abschirmladungen diskutiert. Diese führt zur Ladungsträgerakkumulation und erhöhten chemischen Reaktivität an den Domänengrenzen. / Ferroelectric lithography is a method for a controlled assembly of nanostructures on ferroelectric surfaces, which has has been established throughout the last decade. It exploits the characteristic variations in surface chemistry arising from the different orientations of the spontaneous polarisation within the separate domains. The scope of this thesis is the application of that approach for the directed and controlled deposition of nanostructures consisting of noble metals or organic molecules. For this deposition, a wet chemical processing under UV illumination was carried out on magnesium doped lithium niobate single crystals. As a typical result, the decoration of 180° domain walls was observed for aqueous solutions of silver, gold and platinum salts as well as for the dissolved organic fluorescent dye Rhodamine 6G. The deposition starts within a stripe of 150−500 nm in width parallel to the domain wall. Under continuing illumination, the crystallites grow further until they finally touch each other. Using this technique, organic or metallic polycrystalline nanowires with dimensions in the range of 100nm in width and height can be assembled. Their length is only limited by the sample size. These nanostructures were characterised in respect of their topographical, electrical and optical properties. In the case of contacted single platinum wires an electrical conduction was measured, which showed approximately ohmic behaviour. It was also shown that the resistance of such a platinum nanowire is very sensitive to changes in the surrounding gas medium. This emphasises the suitability of such structures for integration in future sensor devices. Further experiments were carried out to investigate the physical background of the observed domain wall decoration. For this, the positions of the deposited structures were compared with the underlying domain structure. Apart from few exceptions, a symmetric deposition centered at the domain wall was observed. As a starting point for explanation, the separation of electron-hole-pairs by the electrostatic field from polarisation and screening charges is discussed. This process leads to charge carrier accumulation at the domain boundaries, thus enhancing the local chemical reactivity.

Semiconductor quantum dots (QDs) are fascinating systems for potential applications in quantum information processing and communication, since they can emit single photons and polarisation entangled photons pairs on demand. The asymmetry and inhomogeneity of real QDs has driven the development of a universal and fine post-growth tuning technique. In parallel, new growth methods are desired to create QDs with high emission efficiency and to control combinations of closely-spaced QDs, so-called "QD molecules" (QDMs). These systems are crucial for the realisation of a scalable information processing device after a tuning of their interaction energies. In this work, GaAs/AlGaAs QDs with low surface densities, high optical quality and widely tuneable emission wavelength are demonstrated, by infilling nanoholes fabricated by droplet etching epitaxy with different GaAs amounts. A tuning over a spectral range exceeding 10 meV is obtained by inducing strain in the dot layer. These results allow a fine tuning of the QD emission to the rubidium absorption lines, increasing the yield of single photons that can be used as hybrid semiconductor-atomic-interface. By embedding InGaAs/GaAs QDs into diode-like nanomembranes integrated onto piezoelectric actuators, the first device allowing the QD emission properties to be engineered by large electroelastic fields is presented. The two external fields reshape the QD electronic properties and allow the universal recovery of the QD symmetry and the generation of entangled photons, featuring the highest degree of entanglement reported to date for QD-based photon sources. A method for controlling the lateral QDM formation over randomly distributed nanoholes, created by droplet etching epitaxy, is demonstrated by depositing a thin GaAs buffer over the nanoholes. The effect on the nanohole occupancy of the growth parameters, such as InAs amount, substrate temperature and arsenic overpressure, is investigated as well. The QD pairs show good optical quality and selective etching post-growth is used for a better characterisation of the system. For the first time, the active tuning of the hole tunnelling rates in vertically aligned InGaAs/GaAs QDM is demonstrated, by the simultaneous application of electric and strain fields, optimising the device concept developed for the single QDs. This result is relevant for the creation and control of entangled states in optically active QDs. The modification of the electronic properties of QDMs, obtained by the combination of the two external fields, may enable controlled quantum operations.

Ferroic materials play an increasingly important role in novel (nano-)electronic applications. Recently, research on domain walls (DWs) received a big boost by the discovery of DW conductivity in bismuth ferrite (BiFeO3 ) and lead zirconate titanate (Pb(Zrx Ti1−x )O3) ferroic thin films. These achievements open a realistic and unique perspective to reproducibly engineer conductive paths and nanocontacts of sub-nanometer dimensions into wide-bandgap materials. The possibility to control and induce conductive DWs in insulating templates is a key step towards future innovative nanoelectronic devices [1]. This work focuses on the investigation of the charge transport along conductive DWs in ferroelectric single crystals. In the first part, the photo-induced electronic DC and AC charge transport along such DWs in lithium niobate (LNO) single crystals is examined. The DC conductivity of the bulk and DWs is investigated locally using piezoresponse force microscopy (PFM) and conductive AFM (c-AFM). It is shown that super-bandgap illumination (λ ≤ 310 nm) in combination with (partially) charged 180° DWs increases the DC conductivity of the DWs up to three orders of magnitude compared to the bulk. The DW conductivity is proportional to the charge of the DW given by its inclination angle α with respect to the polar axis. The latter can be increased by doping the crystal with magnesium (0 to 7 mol %) or reduced by sample annealing. The AC conductivity is investigated locally utilizing nanoimpedance microscopy (NIM) and macroscopic impedance measurements. Again, super-bandgap illumination increases the AC conductivity of the DWs. Frequency-dependent measurements are performed to determine an equivalent circuit describing the domains and DWs in a model system. The mixed conduction model for hopping transport in LNO is used to analyze the frequency-dependent complex permittivity. Both, the AC and DC results are then used to establish a model describing the transport along the conductive DW through the insulating domain matrix material. In the last part, the knowledge obtained for LNO is applied to study DWs in lithium tantalate (LTO), barium titanate (BTO) and barium calcium titanate (BCT) single crystals. Under super-bandgap illumination, conductive DWs are found in LTO and BCT as well, whereas a domain-specific conductivity is observed in BTO.

Si l'utilisation des transformateurs piézoélectriques se bornait jusqu'alors à l'alimentation ou la protection de dispositifs électriques, ils sont aujourd'hui envisagés pour la génération de décharges plasma directement à leur surface. Les propriétés remarquables de ces générateurs piézoélectriques en font une alternative intéressante aux dispositifs conventionnels, notamment par la simplicité de mise en œuvre. La surface du transformateur constitue à la fois le support de décharge et l'élément élévateur de tension réduisant significativement l'encombrement des dispositifs. En outre les gains en tension de ces transformateurs sont remarquablement élevés et permettent d'obtenir des décharges pour des tensions d'alimentation n'excédant pas quelques volts. Ces avantages peuvent répondre avantageusement à certains problèmes rencontrés dans les procédés plasmas dont l'implantation dans les processus industriels, bien qu'elle soit en constante amélioration, est parfois confrontée à des problèmes de mise en œuvre d'enceintes complexes, rendant le procédé couteux ou inadapté aux conditions opératoires. L'objet de cette thèse porte sur l'étude fondamentale d'un transformateur piézoélectrique de type Rosen dédié à la génération de décharges électriques. Plus particulièrement, ce travail s'attèle au développement d'un modèle analytique permettant de mieux appréhender les limites de ce procédé innovant, ainsi qu'une meilleure compréhension du comportement des décharges plasma face aux spécificités de ce transformateur et de son matériau. Pour ce faire l'étude se consacre en première partie à la caractérisation du transformateur piézoélectrique hors décharge à partir de ses bornes, puis à l'extension d'un modèle analytique afin d'appréhender la distribution du potentiel électrique à sa surface. Le développement d'un dispositif expérimental permettra la mesure du potentiel ainsi que la discussion du modèle. Dans un second temps l'étude s'attache au comportement du transformateur piézoélectrique en décharge. La distribution de potentiel à présent connue constitue une donnée d'entrée nécessaire à l'étude de la dynamique de décharges dans ces différentes configurations. Les phénomènes à l'œuvre dans ce processus de génération étant complexes, l'étude est conduite suivant différentes étapes. Tout d'abord en passant par l'étude des propriétés des céramiques ferroélectriques au travers d'une décharge à barrière diélectrique plan-plan. Ensuite la dynamique des décharges est abordée par modélisation numérique suivant trois configurations différentes. Ces cas d'études conduisent à des régimes de décharges différents pouvant faire l'objet de mise en application future. Bien que le problème soit sous l'hypothèse d'un couplage faible, les résultats ont corroborés les observations expérimentales et ont permis de mieux comprendre l'influence des hautes permittivités et de la distribution du potentiel sur l'évolution spatio-temporelle de ce procédé. / Nowadays piezoelectric transformers are not only used to supply or protect electrical devices, but also to generate plasma discharges directly on their surface. The remarkable properties of these piezoelectric generators make them an interesting alternative to conventional devices, especially the simple implementation. The surface of the transformer constitutes both the discharge support and the voltage elevator component reducing significantly the bulk of the devices. Besides the transformers' gain voltage are remarkably high and permit to generate discharges for low voltage supply not exceeding a few volts. These advantages respond to some problems met in the plasma processes of which the establishment in industrial processes - in constant improvement - is sometimes confronted to problems of chambers implementations, making this process expensive and not adequate to the operating conditions. The purpose of this thesis focuses on the fundamental studies of a Rosen piezoelectric transformer dedicated to the generation of electrical discharges. In particular, this work tackles the development of an analytical model allowing to improve the understanding of the limits of this innovating process, as well as a better comprehension of the plasma discharges behavior face with transformer and material features. In order to do this the first part of the study is devoted to the characterization of the piezoelectric transformer without discharge, then the extension of the analytical modeling in order to comprehend the distribution of surface electrical potential. The development of an experimental device will allow the potential measurement and the discussion of the model. In a second part the study focuses on behavior of the piezoelectric transformer in discharge. The potential distribution known today constitutes a necessary input data for the study of the discharge dynamic in different configurations. The complexity of the phenomena implemented in this process of generation requires to conduct the study following different steps. First of all, by the study of ferroelectric ceramic features through a dielectric-barrier discharge. Then the discharges dynamic is approached by numerical modeling following three different configurations. This cases conduct to different discharge regimes that can be the subject of future application. Even if the problem is under the hypothesis of a weak coupling, the results confirmed the experimental observations and permitted to understand better the influence of high permittivity and of the potential distribution on the saptio-temporal evolution of this process.

Made available in DSpace on 2016-06-02T20:16:51Z (GMT). No. of bitstreams: 1 5339.pdf: 3033412 bytes, checksum: 3e684081236853aacfacccef70bd4635 (MD5) Previous issue date: 2009-10-02 / Financiadora de Estudos e Projetos / Lead titanate zirconate modified with lanthanum, or PLZT, is one the most ferroelectric compounds utilized in electronic devices, due to its versatility and low production costs in comparison with single-crystalline materials. When adequately prepared, this system presents good optical (high optical transmission) properties, in the visible and near infrared range, and can be electro-optically characterized. Recently, in the end of 90 s, it was verified its high potential as host of photoluminescent ions, as the lanthanide (rare-earth) family. The possibility to use its electro-optic properties (due to its ferroelectric characteristics) and its photoluminescent properties (achieved by the doping process) together ,enlarges the range of application of this system. In this way, the electro-optical characterization of doped PLZT ceramics becomes essential, besides the photonic characterization. In this work, the Senarmont compensator method for electro-optical characterization, or dynamic method, was instrumented, and the values of the induced (due to the quadratic electrooptic effect, Kerr) and permanent (due to the linear electro-optic effect, Pockels) birefringence were determined as a function of the temperature, wave-length and electric-field frequency, of the rare-earth (Nd2O3, Ho2O3, Er2O3, Tm2O3 e Yb2O3) doped PLZT, with La/Zr/Ti=9/65/35, ceramics. The results shown a relationship between of the electro-optic (electro-optic coefficients, or birefringence values) and the dielectric, ferroelectric and structural properties (studied in others works) of the ceramics, that were related with the site occupancy and the structural defects due to the aliovalent dopant. It also can be identified two distinct birefringence dependence as a function of the electric field, for the same electro-optic effect (Kerr, or Pockels), identified as a function of the doping process. In the case of electro-optical characterizations in function of the variable frequency, was observed an agreement with the characterization ferroelectric results made in other works in GCFerr, being evidenced the reduction of electro-optical properties with increasing frequency, where if it observed the occurrence of anomalies in the Pockels response with direct influence on the response Kerr. The characterization as a function of wavelength showed the occurrence of two types of behavior depending on the dopant ion used, being one of them the reduction of the values of birefringence with increasing wavelength (the samples pure and doped ions neodymium (Nd) and ytterbium (Yb)), with a tendency to expected behavior in the literature, however, in the second was seen irregular increase birefringence with increase wavelength (for samples doped with ions holmio ( Ho), erbium (Er) and thulium (Tm),not existing relation with to the theoretical models adopted. In relation the characterization as a function of temperature, this was carried through in a temperature interval that understood the characteristic temperatures of systems relaxores (freezing temperature (TF), the maximum dielectric permittivity (TM (e)) and Burns (TB)), except for the sample doped with neodymium ions, whose freezing temperature is below interval worked. By the curve of birefringence (Δn) as a function of temperature was possible to determine the temperature of maximum birefringence for each of the samples, correlated them with each other. Through the curve (d Δn / dt) vs. T was possible to identify a relationship between the maximum variations, positive and negative birefringence with the temperature characteristics TF and TB. / Entre os sistemas ferroelétricos, o sistema titanato zirconato de chumbo modificado com lantânio (PLZT) é um dos mais amplamente utilizados em dispositivos eletrônicos, dada sua versatilidade em aplicações e relação de custo quando comparado aos materiais monocristalinos utilizados nessa mesma área. Quando preparado pelo devido método de síntese, apresenta excelentes propriedades óticas (altos valores de transmissão ótica) desde a região do visível ao infravermelho próximo, possibilitando uma adequada caracterização de suas propriedades óticas e eletro-óticas. Recentemente, a partir do final da década de 90, foi verificada sua alta potencialidade como matriz hospedeira para íons fotoluminescentes, como os da família dos lantanídeos (ou terras-raras). A possibilidade do uso conjunto das propriedades eletro-óticas (dado seu caráter ferroelétrico) e de suas propriedades luminescentes (devido à incorporação de dopantes laser-ativos) aumentou ainda mais a possibilidade de aplicação desses materiais. Desse modo, a caracterização eletro-ótica das cerâmicas de PLZT dopado torna-se indispensável, além de sua caracterização fotônica. Sendo assim, neste trabalho foi instrumentado um sistema de caracterização eletro-ótica, utilizando o método do compensador Senarmont, também conhecido como método dinâmico, para determinar os valores da birrefringência induzida (devido ao efeito eletro-ótico quadrático, Kerr) e a permanente (devido ao efeito eletro-ótico linear, Pockels) em função da temperatura, comprimento de onda e frequência do campo elétrico de prova para composições cerâmicas de PLZT na razão La/Zr/Ti=9/65/35, dopadas com os óxidos terras-raras Nd2O3, Ho2O3, Er2O3, Tm2O3 e Yb2O3, na quantidade de 1,0% em peso. Os resultados mostraram que há uma relação entre as propriedades eletro-óticas encontradas (seja na forma de valores dos coeficientes eletro-óticos, ou na variação da birrefringência) com as propriedades dielétricas, ferroelétricas e estruturais (já observadas em outros trabalhos do grupo de pesquisa no qual esta dissertação foi realizada) das cerâmicas que, por sua vez, foram relacionadas com o tipo de ocupação e de defeitos gerados devido à incorporação dos dopantes. Além disso, foi possível observar que para uma mesma composição pode ocorrer a presença dos dois tipos de efeitos eletro-óticos - Kerr e Pockels - com proporções distintas em função do tipo de dopante. Através desse método, para esse conjunto de amostras, também foi possível identificar dois tipos distintos de variações da birrefringência em função do campo elétrico para um mesmo efeito eletro-ótico (Kerr, ou Pockels), que também puderam ser associados com o tipo de ocupação dos dopantes. Em se tratando das caracterizações eletro-óticas em função da variável frequência, foi observada uma concordância com os resultados da caracterização ferroelétrica, realizada em outros trabalhos no GCFErr, sendo evidenciada a redução das propriedades eletro-óticas com o aumento da frequência, em que se observou a ocorrência de anomalias na resposta Pockels com influência direta na resposta Kerr. A caracterização como uma função do comprimento de onda mostrou a ocorrência de dois tipos de comportamentos, dependendo do íon dopante utilizado, sendo um deles a redução dos valores da birrefringência com o aumento do comprimento de onda (caso das amostras pura e dopadas com os íons neodímio (Nd) e itérbio (Yb)), havendo certa tendência ao comportamento previsto em literatura, no entanto, no segundo caso foi constatado o aumento irregular da birrefringência com o aumento do comprimento de onda (caso das amostras dopadas com os íons holmio (Ho), érbio (Er) e túlio (Tm), não havendo relação com os modelos teóricos adotados. Quanto à caracterização em função da temperatura, esta foi realizada em um range de que compreendeu as temperaturas características de sistemas relaxores (de freezing (TF(e)), máxima permissividade dielétrica (TM(e)) e Burns (TB(e))), exceto para a amostra dopada com o íon neodímio, cuja TF(e) estava abaixo do intervalo considerado. Através da curva de birrefringência (Δn) em função da temperatura foi possível determinar a temperatura de máxima birrefringência para cada uma das amostras, correlacionado-as entre si. Através da curva de (dΔn/dt) vs. T, foi possível constatar uma relação entre as máximas variações, positiva e negativa, da birrefringência com as temperaturas características TF e TB.

Bismuth layer-structured ferroelectrics have received significant attention recently due to their fairly high TC and good fatigue endurance which make them important candidates for non-volatile ferroelectric random access memories (Fe-RAMs) as well as for the piezoelectric device applications at high temperatures. Structure of these compounds is generally described as the pseudo-perovskite block (An-1BnO3n+1)2- sandwiched between the bismuth oxide layers (Bi2O2)2+ along the c-axis, where n represents the number of corner sharing BO6 octahedra forming the perovskite-like slabs. Only a few compounds belonging to this family show relaxor behavior (frequency dependent diffuse phase transition). Relaxor ferroelectrics are very attractive for a variety of applications, such as capacitors, sensors, actuators, and integrated electromechanical systems. The present work attempts to understand the mechanism of relaxor behavior in Aurivillius oxides as well as to improve the piezoelectric and ferroelectric properties of some of the known phases. Details pertaining to the fabrication and characterization of BaBi4Ti4O15 (n = 4 member of Aurivillius family of oxides) ceramics are presented. X-ray diffraction, Raman spectroscopy, Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to probe the structural and microstructural details. The contribution of irreversible domain wall movement to the room temperature dielectric constant and polarization was quantitatively evaluated using the nonlinear dielectric response. Dielectric dispersion and conduction mechanism of these ceramics are also explicated using the complex impedance spectroscopy. The effects of La3+ and Ca2+ doping on the phase transition behavior and other properties of BaBi4Ti4O15 are investigated. La3+ doping for Bi3+ was found to strengthen the relaxor behavior. New compounds such as CaNaBi2Nb3O12, SrNaBi2Nb3O12, Na0.5La0.5Bi4Ti4O12, etc. belonging to the Aurivillius family of oxides have been synthesized and investigations concerning their structural, dielectric and ferroelectric properties are presented. Rietveld refinement of room temperature X-ray powder data suggested that CaNaBi2Nb3O12 and SrNaBi2Nb3O12crystallize in the orthorhombic space group B2cb. SrNaBi2Nb3O12 ceramics exhibited frequency-dependent Tm which follows the Vogel-Fulcher relation implying a relaxor nature. No frequency dependence of Tm was observed for CaNaBi2Nb3O12 ceramics. Polarization - electric field hysteresis loops recorded well above Tm confirmed the coexistence of polar and non-polar domains in SrNaBi2Nb3O12 ceramics. Dielectric anomaly observed around 675 K for CNBN corresponds to the ferroelectric to paraelectric phase transition which is accompanied by the change in crystal structure from orthorhombic to tetragonal. Fe and Nb co-doped Bi4Ti3O12 ceramics were fabricated and characterized for their structural, electrical and magnetic properties.

FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / Uma forte demanda por materiais mais compactados, de baixo custo e de fÃcil fabricaÃÃo sÃo necessÃrios para diversas aplicaÃÃes tecnolÃgicas, neste sentido diversos materiais cerÃmicos sÃo candidatos por suas propriedades dielÃtricas e Ãpticas. Neste presente trabalho, foram investigadas as propriedades estruturais, dielÃtricas e Ãpticas da fase ortorrÃmbica da matriz cerÃmica ferroelÃtrica CaBi4Ti4O15, uma pseudo-perosviskita de estrutura de camada de bismuto (BLSFs) do grupo espacial A21am da famÃlia aurivillius, preparada pelo mÃtodo do estado sÃlido e sinterizada em baixas temperaturas. A preparaÃÃo das amostras para anÃlise estrutural e dielÃtrica, tiveram a adiÃÃo de pentÃxido de vanÃdio (V2O5) à fase CaBi4Ti4O15 calcinada, em proporÃÃes de 0.5, 1.0, 1.5, 2.0 e 5.0 % em massa. Para obtenÃÃo das propriedades Ãpticas, a matriz cerÃmica pura foi dopada com os Ãons terras raras Ãrbio III (Er2O3) e Ãxido de itÃrbio III (Yb2O3). O estudo da estrutura e composiÃÃo das amostras foi feito atravÃs de difraÃÃo de raios-X e a confirmaÃÃo da fase Ãnica foi feita pelo Refinamento Rietveld. A caracterizaÃÃo vibracional foi obtida atravÃs da Espectroscopia Raman (SR). O estudo da morfologia, para anÃlise de grÃo e contorno de grÃo, foi realizado atravÃs de Microscopia EletrÃnica de Varredura. A caracterizaÃÃo dielÃtrica em radio freqÃÃncia foi realizada por Espectroscopia em ImpedÃncia a qual se verificou dois mecanismos de condutividade para todas as amostras analisadas, um em baixa freqÃÃncia e outro em alta freqÃÃncia. Os modelos de relaxaÃÃo dielÃtrica se aproximam do modelo do tipo Cole-Cole. As medidas na faixa de microondas foram obtidas utilizando-se o mÃtodo hakki-coleman e monopolo, chegou-se a um coeficiente de temperatura da frequÃncia de ressonÃncia (tAU f) prÃximo de zero com adiÃÃo de V2O5. As medidas de permissividade dielÃtrica em radiofreqÃÃncia e microondas, realizadas em temperatura ambiente, tiveram um alto valor constante (εr ≈ 150) com a adiÃÃo de 1% de V2O5, e um valor da tangente de perda relativamente baixa em relaÃÃo à famÃlia de Aurivillus (tan[δ] ≈10-2 ) em 2 GHz.. Uma simulaÃÃo numÃrica foi realizada com cada amostra verificando-se aproximaÃÃo com os dados experimentais. Nas amostras dopadas com terras raras foi verificado o fenÃmeno de conversÃo ascendente de energia com a presenÃa de bandas intensas amostras de emissÃo de luz visÃvel na regiÃo do verde e de bandas de menor intensidade na regiÃo do vermelho. O Material investigado tem potencial para aplicaÃÃo em memÃrias volÃteis, filtros capacitivos e componentes Ãpticos, como sensores, cÃlulas fotoelÃtricas e leds. / A strong demand for compressed materials, low cost and easy to manufacture are needed for various technological applications, in this sense many ceramics are candidates for its dielectric and optical properties .In this work, structural, dielectric and optical phase of the orthorhombic ferroelectric ceramic matrixCaBi4Ti4O15were investigated, one pseudo-perovskite bismuth layer structure (BLSFs) of space group A21am of the aurivillius family, prepared by the solid state method and sintered in low temperatures. Sample preparation for structural analysis and dielectric, had the addition of vanadium pentÃxido (V2O5) to the phase CaBi4Ti4O15 calcined in ratios of 0.5, 1.0, 1.5, 2.0 and 5.0% by mass. To obtain optical properties of the ceramic matrix doped with rare earth ions erbiumIII (Er2O3) and III ytterbium oxide (Yb2O3). The study of the structure and composition of the samples was done by X-ray diffraction and confirmation was made by single stage rietveld refinement. The vibrational characteristics was obtained by Raman spectroscopy (RS). The morphology study off or analysis of grain and grain boundary, was performed by scanning electron microscopy. The dielectric characterization of radio frequency spectroscopy was performed in impedance which occurred two conductivity mechanisms for all samples, one at low frequency and the on the rat high frequency. Models of dielectric relaxation approach the Cole-Cole type model. Measures in the microwave range were obtained using the hakki-coleman method and monopole, which gave a temperature coefficient of resonant frequency (f) close to zero with the addition of V2O5. The dielectric permittivity measurements in radiofrequency and microwave, performe dat room temperature, had a high constant value (εr≈150) with the addition of 1%V2O5, and a value of relatively low loss tangent for family aurivillus (tan[δ]≈10-2) at 2 GHz. A numerical simulation was performed with each sample verifying approach with the experimental data. In rare earth doped samples was checked energy up-conversion phenomenon with the presence of intense bands samples of visible light emission in the green region and a less intense bands in thered region.The investigated material has potential for application in volatile memories, capacitive filters and optical components such as sensors, solar cells and LEDs.

Avec l’usage intensif de dispositifs microélectroniques modernes, il existe un besoin croissant de mémoires non volatiles. La FeRAM (mémoire ferroélectrique à accès aléatoire) est une des mémoires de nouvelle génération les plus prometteuses en raison de sa faible consommation et de sa vitesse élevé de lecture/écriture. Parmi les différents matériaux ferroélectriques, le PZT (Pb (Zr1-x,Tix)O3) présente une polarisation rémanente élevée et un faible champ coercitif qui en font un candidat de choix pour les FeRAM.Dans cette thèse, la croissance épitaxiale de couches de PZT (52/48) d’épaisseurs variables (33 à 200 nm), sur un substrat de SrTiO3 et une électrode inférieure interfaciale de SrRuO3, a été réalisé par deux méthodes pour comparaison : pulvérisation cathodique et sol – gel. Trois matériaux conducteurs différents (SrRuO3, Pt et ITO) ont été utilisés comme électrode supérieure. L’objectif a été une étude détaillée des propriétés électriques et ferroélectriques de ces structures MFM (métal-ferroélectrique-métal), avec une attention particulière sur l’influence des conditions d’élaboration et de la nature des électrodes sur le courant de fuite et la dynamique de basculement de domaines.Les capacités élaborées par pulvérisation ou sol-gel présentent des caractéristiques semblables : Au-delà d’une épaisseur minimum d’environ 100 nm, pour une structure capacitive à base de PZT de 100 × 100 μm2, elles montrent un faible courant de fuite, une permittivité relative maximale élevée (600 - 1300) et une polarisation rémanente élevée (30 - 40 μC/cm2). Les mécanismes dominants dans le courant de fuite ont été identifiés par un fit des résultats, manifestant différentes contributions en fonction du champ électrique. Des caractérisations par PFM (microscopie à force piézoélectrique) confirme l’existence de domaines ferroélectriques de directions opposées. Il est aussi montré que le champ coercitif dépend fortement de la fréquence de travail. D’autre part, les propriétés d’impression dépendent de l’électrode supérieure, de la nature du recuit et de l’épaisseur de l’électrode inférieure. / With the intensive use of modern microelectronic devices in numerous areas, there is an increasing demand for non-volatile memories. FeRAM (ferroelectric random access memory) is one of the most potential next-generation memories for its ultra-low power consumption and high read/write rate. Among various ferroelectrics, PZT (Pb(Zr1-x,Tix)O3) exhibits high remnant polarization and low coercive field, which make it a promising candidate for FeRAM.In this dissertation, PZT(52/48) layers of various thicknesses (from 33 nm to 200 nm) have been epitaxially grown on SrTiO3 substrate, with a SrRuO3 interlayer as bottom electrode, using two deposition methods for comparison: sol-gel and sputtering. Three different conductive materials (SrRuO3, Pt and ITO) have been deposited as top electrode. The objective was a detailed study of the electrical and ferroelectric properties of these MFM (metal-ferroelectric-metal) capacitors, with a particular investigation of the influence of elaboration conditions and electrode material on leakage currents and domain switching dynamics.Sputtered and sol-gel-derived PZT capacitors showed similar properties: Above a minimum workable thickness of about 100 nm for a 100 × 100 μm2 PZT capacitor, they showed low leakage current, high maximum relative permittivity (600 - 1300) and high remnant polarization (30 - 40 μC/cm2). The dominant leakage current mechanisms were identified by fitting the results, showing different contributions as a function of electric field. PFM (piezoresponse force microscopy) characterizations confirmed the existence of ferroelectric domains of opposite directions. Coercive field was found to be highly dependent on work frequency. Besides, imprint properties were found to be dependent on top electrode, annealing procedure and bottom electrode thickness.