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

With recent trends in miniaturization in the electronics sector, ferroelectrics have gained popularity due to their applications in non-volatile RAM. Taking one step further researchers are now exploring multiferroic devices that overcome the drawbacks of ferroelectric (FE) and ferromagnetic (FM) RAM’s while retaining the advantages of both. The work presented in this dissertation focuses on the growth of FE and FM thin film structures. The primary goals of this work include, (1) optimization of the parameters in the pulsed laser deposition (PLD) of FE and FM films and their heterostructures, (2) development of a structure-property relation that leads to enhancements in electric and magnetic polarizations of these structures, (3) investigation of doping on further enhancement of polarizations and coupling between the FE and FM layers. The materials of choice are La0.7Sr0.3MnO3 (LSMO) as the ferromagnetic and PbZr0.52Ti0.48O3 (PZT) as the ferroelectric component. Epitaxial thin film capacitors were grown using PLD. The work starts with the establishment of the optimum deposition conditions for PZT and goes on to describe results of attempts at performance enhancement and tuning using two methods. It is demonstrated that ferroelectric and ferromagnetic properties can be tuned by inserting a ferromagnetic buffer layer of CoFe2O4 (CFO) between PZT and LSMO. One of the key findings of this work was the anomalously high ferroelectric polarizations produced by lanthanum (La) doped PZT films. This work attempts to shine light on a possible mechanism that leads to such high enhancements in polarization.

With the overriding goal of developing functional multiferroic systems with technological potential, this thesis focuses on the role of orbital and charge ordering in coupling magnetism and ferroelectricity in synthetic quadruple perovskites. Using x-ray diffraction as the primary characterisation tool, modulations to crystal ordering have been interpreted in terms of orbital occupation and charge variation. Expanding on previous magnetic structure studies and polarisation measurements, structural analysis of CaMn₇O₁₂ has led to the experimental realisation of a new mechanism for multiferroicity, resulting from a "magneto-orbital helix". Motivated by the idea of tuning multiferroic properties through varying manganese valence, the doped system CaCu_xMn_7-xO₁₂ has been studied. Structural models considering the possibility of domain formation and multiple coexisting modulations have been tested against x-ray diffraction data. Finally, motivated by theoretical predictions of ferroelectric phases and multiferroicity in doped, simple, manganite perovskites, a structural model for the low temperature phase of NaMn₇O₁₂ has been developed, based upon theoretical predictions for orbital ordering and the experimentally determined magnetic structure. This model has been tested against previously measured neutron diffraction data. The importance of understanding crystal formation and domain structures when applying theoretical models has been highlighted, and has prompted the consideration of future work involving viewing and manipulating twin formation.

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...

Ferroelectrics are a group of advanced electronic materialswith a wide variety of properties useful in applications suchas memory devices, resonators and filters, infrared sensors,microelectromechanical systems, and optical waveguides andmodulators. Among the oxide perovskite-structured ferroelectricthin film materials sodium potassium niobate or Na0.5K0.5NbO3(NKN) has recently emerged as one of the most promisingmaterials in microwave applications due to high dielectrictunability and low dielectric loss. This licentiate thesispresents results on growth and structural, optical, andelectrical characterization of Na0.5K0.5NbO3 thin films. Thefilms were deposited by rf-magnetron sputtering of astoichiometric, high density, ceramic Na0.5K0.5NbO3 target ontosingle crystal LaAlO3 and Al2O3, and polycrystalline Pt80Ir20substrates. By x-ray diffractometry, NKN films on c-axisoriented LaAlO3 substrates were found to grow epitaxially,whereas films on hexagonal sapphire and polycrystallinePt80Ir20 substrates were found to be preferentially (00l)oriented. Optical and waveguiding properties of theNa0.5K0.5NbO3/Al2O3 heterostructure were characterized using aprism-coupling technique. Sharp and distinguishable transversemagnetic (TM) and electric (TE) propagation modes wereobserved. The extraordinary and ordinary refractive indiceswere calculated to ne = 2.216±0.003 and no =2.247±0.002 for a 2.0 μm thick film at λ = 632.8nm. This implies a birefringence Δn = ne - no =-0.031±0.003 in the film. The ferroelectric state inNKN/Pt80Ir20 films at room temperature was indicated by apolarization loop with polarization as high as 33.4 μC/cm2at 700 kV/cm, remnant polarization of 9.9 μC/cm2 andcoercive field of 91 kV/cm. Current-voltage characteristics ofvertical Au/NKN/Pt80Ir20 capacitive cells and planar Au/NKN/LaAlO3 interdigital capacitors (IDCs) showed very goodinsulating properties, with the leakage current density for anNKN IDC on the order of 30 nA/cm2 at 400 kV/cm. Rf dielectricspectroscopy demonstrated low loss, low frequency dispersion,and high voltage tunability. At 1 MHz NKN/LaAlO3 showed adissipation factor tan δ of 0.010 and a tunability of 16.5% at 200 kV/cm. For the same structure the frequencydispersion, Δεr, between 1 kHz and 1 MHz was 8.5%. <b>Key words:</b>ferroelectrics, sodium potassium niobates,thin films, rf-magnetron sputtering, waveguiding, refractiveindex, prism coupling, dielectric tunability / NR 20140805

Title: PFM and Raman spectroscopy of selected dielectric materials Author: Fedir Borodavka Institute: Department of Dielectrics, Institute of Physics of the Academy of Sciences, Na Slovance 2, 182 21, Prague 8, Czech Republic Supervisor: Ing. Ivan Gregora, CSc. Training institute: Department of Dielectrics, Institute of Physics of the Academy of Sciences, Na Slovance 2, 182 21, Prague 8, Czech Republic Consultants: RNDr. Stanislav Kamba, CSc. and RNDr. Vladimír Vorlíček, CSc. Abstract: The thesis is devoted to a detailed investigation of dielectric materials using Raman spectroscopy and PFM microscopy techniques. Phonon properties of a newly synthesized guanylurea(1+) hydrogen phosphite single crystals have been studied. A tentative assignment of the observed Raman peaks has been done and the sets of A′ MIX, A′ TO and A′′ TO mode frequencies have been determined. Phonon behaviour of BiMnO3 ceramics, obtained from Raman spectra, has been char- acterized. After comparing the factor group analysis with the Raman spectra it has been concluded that the material has a centrosymmetric C2/c structure and is not ferroelectric. Lattice modes of the complex La1/2Na1/2TiO3 single crystal have been investigated. We have numerically analysed the intensity behaviour of the sharp peak at 455 cm−1 on heating and...

Il y a un besoin de nouvelles technologies photovoltaïques avec une efficacité de conversion lumière-électricité augmentée, qui puissent être des alternatives aux dispositifs plus traditionnels d’efficacité limitée et couteux à base de jonctions p-n. Dans ce contexte, la recherche sur les pérovskites ferroélectriques inorganiques ouvre des possibilités pour le développement de nouvelles approches pour augmenter l’efficacité, par exemple grâce à leur aptitude à séparer les charges électriques photoexcitées par le champ électrique intrinsèque (associé à leur polarisation) qui existe dans chaque maille élémentaire de ces matériaux. Pour profiter de cet avantage, un matériau doit posséder plusieurs propriétés comme la ferroélectricité, une bande interdite d’énergie relativement petite pour pouvoir absorber la lumière et une mobilité des porteurs de charges élevée. Ici, on a synthétisé et étudié des solutions solides Ba(Sn,Ti)O3, qui ont comme composants parents un ferroélectrique BaTiO3 et un paraélectrique BaSnO3. Les transitions de phases cristallographiques et la modification des états des dipôles sont caractérisées par les méthodes de diffraction et la spectroscopie diélectrique. La spectrométrie des photoélectrons X montre une corrélation entre l’évolution non-linéaire de la bande interdite pour les différentes compositions et entre l’évolution des charges locales dynamiques. Les propriétés optiques en température sont dominées par l’arrangement des dipôles dans les compositions ferroélectriques. Pour les autres compositions les propriétés sont plutôt guidées par les défauts. Il a été possible de déterminer les températures critiques des différents mécanismes à partir des caractérisations optiques. Dans ce système Ba(Sn,Ti)O3, les propriétés optiques et le photocourant sont fortement reliés à la structure locale particulière et la nature de la liaison chimique, comme nous avons mis en évidence par la spectroscopie Raman et la spectrophotométrie photoélectronique X. / There is an active search for new photovoltaic technologies with improved efficiency, since the traditional p-n junctions have either the limited efficiency or the increased cost. The research on inorganic ferroelectric perovskites offers opportunities to develop new approaches and increase photovoltaic efficiency, for instance due to capability of these materials to more efficiently separate the photoexcited charges due to the existence of an internal electric field within their unit cell. To profit from this advantage, the material must combine properties like ferroelectricity, relatively small band gap and high charge mobility. In this work, we have synthesized and studied compounds from Ba(Sn,Ti)O3 solid solution, having as end members ferroelectric BaTiO3 and paraelectric BaSnO3. Crystallographic phase transitions and changes of the polar states were characterized by diffraction techniques and dielectric spectroscopy. The non-linear evolution of the band gap for different compounds has been correlated to arise from evolution of the local dynamic charge existing in these compounds, as deduced from X-ray photoelectron spectroscopy. The temperature-dependent optical properties are dominated by polar order in ferroelectric compositions, while for the other compositions the defect-related mechanisms prevail. The critical temperatures for different mechanisms can be determined from optical characterization. In these compounds, the optical properties and photocurrent are strongly related to particularities of the local structure and chemical bonding deduced from Raman and X-ray photoelectron spectroscopies.

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