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The aim of the current study is to develop an efficient model which can predict low-energy compatible microstructures in ferroelectric bulks and film devices and their dynamic behaviour. The results are expected to assist in the interpretation of microstructure observations and provide a knowledge of the possible domain arrangements that can be used to design future materials with optimum performance. Several recent models of ferroelectric crystals assume low energy domain configurations. They are mainly based on the idea of fine phase mixtures and average compatibility, and can require intensive computation resulting in complex domain configurations which rarely occur in nature. In this research, criteria for the exact compatibility of domain structure in the form of a periodic multi-rank laminate are developed. Exactly compatible structure is expected to be energetically favourable and does not require the concept of a fine mixture to eliminate incompatibilities. The resulting method is a rapid and systematic procedure for finding exactly compatible microstructures. This is then used to explore minimum rank compatible microstructure in various crystal systems and devices. The results reveal routes in polarization and strain spaces along which microstructure can continuously evolve, including poling paths for ferro- electric single crystals. Also, the method is capable to generate all possible exactly compatible laminate configurations for given boundary conditions. It is found that simple configurations are often energetically favourable in conditions where previous approaches would predict more complex domain patterns. Laminate domain patterns in ferroelectrics are classified and corre- lated with observations of domains in single crystals, showing good agreement. The evolution of microstructures under applied mechanical and electrical loads is studied. A variational method, which minimises the overall energy of the crystal is developed. A new concept of transitional “pivot states” is introduced which allows the model to capture the feature that the microstructure in ferroelectric crystal switches between possible domain patterns that are energetically favourable, rather than assuming one particular domain pattern throughout. This model is applied to study the hysteresis responses of barium titanate (BaTiO3) single crystals subjected to a variety of loads. The results have good agreement with experimental data in the literature. The relationship between domain patterns and ferroelectric hysteresis responses is discussed.

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This dissertation includes two parts. In the first part the study is focused on the fabrication of multifunctional thin films for photovoltaic applications. There is no doubt about the importance of transforming world reliance from traditional energy resources, mainly fossil fuel, into renewable energies. Photovoltaic section still owns very small portion of the production, despite its fast growth and vast research investments. New methods and concepts are proposed in order to improve the efficiency of traditional solar cells or introduce new platforms. Recently, ferroelectric photovoltaics have gained interest among researchers. First objective in application of ferroelectric material is to utilize its large electric field as a replacement for or improvement of built-in electric field in semiconductor p-n junctions which is responsible for the separation of generated electron-hole pairs. Increase in built in electric field will increase open-circuit voltage of the solar cell. In this regard, thin films of ferroelectric hafnium dioxide doped with silicon have been fabricated using physical vapor deposition techniques. Scanning probe microscopy techniques (PFM and KPFM) have been employed to analyze ferroelectric response and surface potential of the sample. The effects of poling direction of the ferroelectric film on the surface potential and current-voltage characteristics of the cell have been investigated. The results showed that the direction of poling affects photoresponse of the cell and based on the direction it can either improved or diminished. In the second part of this work, epitaxial thin films have been synthesized with physical vapor deposition techniques such as sputtering and electron beam evaporation for the ultimate goal of producing multifunctional three-dimensional structures. Three-dimensional structures have been used for applications such as magnetic sensors, filters, micro-robots and can be used for modification of the surface of solar cells in order to improve light absorption and efficiency. One of the important techniques for producing 3-D structures is using origami techniques. The effectiveness of this technique depends on the control of parameters which define direction of bending and rolling of the film or curvature of the structure based on the residual stress in the structure after film’s release and on the quality and uniformity of the film. In epitaxially grown films, the magnitude and direction of the stress are optimized, so the control over direction of rolling or bending of the film can be controlled more accurately. For this purpose, deposition conditions for epitaxy of Zn, Fe, Ru, Ti, NaCl and Cr on Si, Al2O3 or MgO substrates have been investigated and optimized. Crystallinity, composition and morphology of the films were characterized using reflective high energy diffraction (RHEED), Auger electron spectroscopy (AES), energy dispersive X-ray (EDX), and scanning electron microscopy (SEM).

Performance and reliability of solid state laser diodes in the IR region exceeds those in the visible and UV part of the light spectrum. Single frequency visible and UV laser diodes with higher than 500 mW power are not available commercially. However we successfully stabilized a multi-longitudinal mode IR laser to 860 mW single frequency. This means high efficiency harmonic generation using this laser can produce visible and UV laser light not available otherwise. In this study we examined three major leading nonlinear crystals: PPMgO:SLN, PPKTP and PPMgO:SLT to generate blue light by second harmonic generation. We achieved record high net conversion efficiencies 81.3% using PPMgO:SLT (~500 mW out), and 81.1% using PPKTP (~700 mW out). In both these cases an external resonance buildup cavity was used. We also studied a less complicated single pass waveguide configuration (guided waist size of ~ 5 um compared to ~60 um) to generate blue. With PPMgO:SLN we obtained net 40.4% and using PPKT net 6.8% (110mW and 10.1 mW respectively).

Ferroelectric materials have been extensively studied theoretically and experimentally for many decades. Their ferroelectric, piezoelectric, pyroelectric, dielectric and electro-optical properties offer great promise in various applications such as non-volatile random access memory devices, non linear optics, motion and thermal sensors, and tunable microwave devices. Advanced applications for high dielectric constant insulators and nonvolatile memories in semiconductor industry have led to a meteoric rise of interest in the ferroelectrics recently. As most studied and technically important ferroelectric materials, lead zirconate titanate (PZT) and barium strontium titanate (BST) are widely investigated to understand their properties for potential device applications. Using radio frequency magnetron sputtering, single crystalline PZT and BST thin films have been achieved on SrTiO3 substrates, and been characterized for their structural and electrical properties. Eyeing their different potential applications, ferroelectric, pyroelectric and dielectric properties of PZT and BST thin films were studied. In addition, the introduction of bridge layers (nucleation or buffer layers) grown by molecular beam epitaxy (MBE) has been employed to facilitate the heterostructure growth of PZT thin films on GaN and BST thin films on sapphire substrates. Highly (111)-oriented perovskite PZT thin films were achieved on silicon-doped GaN (0001)/c-sapphire with a PbTiO3/PbO oxide bridge layer. And (001)-oriented BST thin films were grown on a-plane sapphire with an MgO/ZnO bridge layer. This dissertation also discusses the realization of PZT ferroelectric field effect transistors (FeFET). Two different 1T FeFET structures were successfully fabricated and their electrical properties were examined. Ferroelectric behavior was observed in the plot of source-drain current versus gate voltage where it exhibited a large counterclockwise hysteresis with 50% current modulation.

Orientador: José de los Santos Guerra / Resumo: Os materiais vítreos a base de TeO2 têm sido amplamente estudados e suas potencialidades requerem particular atenção para o desenvolvimento de novos sistemas vitrocerâmicos. Neste trabalho, com o objetivo de formar nanocristais de BaTiO3 (na fase tetragonal) através da estequiometria do sistema xBaO–xTiO2–(100–2x)TeO2 (BTT), tratamentos isotérmicos foram realizados sob diferentes condições. Desse modo, foram investigadas as propriedades físicas do sistema BTT para as composições x = 7,5, 10,0 e 12,5 mol%, de nomenclaturas 85BTT, 80BTT e 75BTT, respectivamente. As amostras foram obtidas pelo método convencional de fusão, seguido de um rápido resfriamento (quenching). Particularmente, suas propriedades térmicas, estruturais e óticas foram analisadas a partir de Análise Térmica Diferencial (DTA), Difração de raios-X (DRX), Espectroscopia Raman (ER) e de Absorção Ótica (AO). Os resultados revelaram uma forte influência das concentrações de BaO-TiO2 nas propriedades estudadas, que pode ser associada à quebra de simetria da unidade estrutural elementar (TeO4), devido à variação estrutural TeO4TeO3+1TeO3, ao caráter covalente das ligações TeO, a presença do par de elétrons livres na camada de valência do TeO2 e, consequentemente, à formação de oxigênios não ligantes (NBO’s). As bandas de cortes no UV-Vis apresentaram absorção fundamental na região de 400-450nm, onde a rede mais polimerizada da composição 80BTT proporcionou os valores mais elevados do gap indireto (Ei = 2,87eV) e ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: TeO2-based glassy materials have been extensively studied and their potentialities require particular attention for the development of new ceramic-glass materials. In this work, viewing the formation of tetragonal BaTiO3 nanocrystals by considering the xBaO–xTiO2–(100–2x)TeO2 (BTT) stoichiometry formula, isothermal treatments were performed under different conditions. Thus, the physical properties of the BTT system were investigated for compositions with x = 7.5, 10.0 and 12.5 mol%, hereafter labeled as 85BTT, 80BTT and 75BTT, respectively. The samples were obtained by the conventional fusion method followed by rapid cooling (known as the quenching method). Particularly, the thermal, structural and optical properties were studied from Differential Thermal Analysis (DTA), X-ray Diffraction (XRD), Raman Spectroscopy and Optical Absorption (OA) analyses. The results showed a strong influence of the BaO-TiO2 concentrations on the studied properties, which could be related to the symmetry breaking of the elemental structural unit (TeO4), due to the TeO4→TeO3+1→TeO3 structural variation, the covalent character of the Te−O bonds, the presence of the lone-pair valence electrons in the TeO2 and, consequently, the formation of non-binding oxygen (NBO's). The UV-Vis cut-off bands revealed the fundamental absorption in the 400-450nm region, where the most polymerized network of the 80BTT samples has provided the highest indirect (Ei = 2.87eV) and direct (Ed = 2.96eV) gap values. The resu... (Complete abstract click electronic access below) / Doutor

Nas últimas décadas, o consumo de dispositivos eletrônicos e a alta demanda por armazenamento de dados tem mostrado grandes oportunidades para a criação de novas tecnologias que garantam as necessidades mundiais na área de computação e desenvolvimento. Alguns materiais multiferroicos tem sido amplamente estudados e o BiFeO3, considerado o único material multiferroico em temperatura ambiente, ganhou destaque como candidato para produção de dispositivos lógicos e de memória. O uso de técnicas de crescimento como a deposição por laser pulsado permitiu a produção de filmes finos de BiFeO3 com elevado controle de qualidade. Heteroestruturas de filmes multiferroicos de BiFeO3 e LaBiFeO3 foram crescidas com diferentes espessuras sobre substratos de SrTiO3(100), DyScO3(110) e SrTiO3/Si(100) para avaliação e teste de suas propriedades elétricas e magnéticas. Filmes ferromagnéticos de Co0,9Fe0,1 foram depositados por sputtering sobre os filmes multiferroicos para avaliação da interação interfacial entre ordenamentos magnéticos. Técnicas como fotolitografia foram utilizadas para padronização de microdispositivos gravados sobre as amostras. Tanto os filmes finos de BiFeO3 como os de LaBiFeO3 foram crescidos epitaxialmente sobre os substratos já cobertos com uma camada buffer de SrRuO3 usado como contato elétrico inferior. A estrutura cristalina romboédrica das ferritas de bismuto foi confirmada pelos dados de difração de raios X, bem como a manutenção de tensão estrutural causada pela rede cristalina do substrato para amostras de 20 nm. Os valores de coeficiente do tensor piezelétrico d33 foram da ordem de 0,15 V (∼ 60 kV.cm-2) para amostras com 20 nm de espessura enquanto que os valores de voltagem coerciva para as análises de histerese elétrica foram da ordem de 0,5 V para as mesmas amostras. A relação de coercividade elétrica com a espessura corresponde ao perfil encontrado na literatura pela relação E≈d-2/3. As amostras de CoFe/BFO e CoFe/LBFO depositadas em diferentes substratos apresentam acoplamento interfacial entre ordenamento ferromagnético e antiferromagnético com momento ferromagnético de rede. / For the last few decades, the consumption of electronic devices and the high demand for data storage have shown great opportunities to create modern technologies that assure the worldwide needs in computing and development. Some multiferroic materials have been extensively studied and BiFeO3, considered the only multiferroic material at room temperature, has received attention as a candidate to produce logic and memory devices. The use of growth techniques such as pulsed laser deposition allowed the production of thin films of BiFeO3 with high quality control. Multiferroic film heterostructures of BiFeO3 and LaBiFeO3 were grown with different thicknesses on SrTiO3 (100), DyScO3 (110) and SrTiO3/Si (100) substrates to evaluate and test their electrical and magnetic properties. The allow Co0.9Fe0.1 ferromagnetic films were deposited by sputtering on the multiferroic films to evaluate the interfacial interaction between magnetic ordering. Techniques such as photolithography were used to pattern microdevices on the samples. Both the BiFeO3 and LaBiFeO3 thin films were grown epitaxially on the substrates already covered with a SrRuO3 buffer layer used as the lower electrical contact. The rhombohedral crystalline structure of the bismuth ferrites was confirmed by the X-ray diffraction data as well as the strain maintenance caused by the crystal lattice of the substrate for 20 nm samples. The coefficient values of the piezoelectric tensor d33 were around 0.15 V (∼ 60 kV.cm-2) for 20 nm thick samples whereas the coercive voltage values for the electrical hysteresis analyzes were about 0.5 V for the same samples. The relation between electric coercivity and the thickness corresponds to the profile found in the literature by the relation E≈d-2/3. The samples of CoFe/BFO and CoFe/LBFO deposited in different substrates present interfacial coupling between ferromagnetic and antiferromagnetic arrangement with net ferromagnetic moment.

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