Made available in DSpace on 2014-06-11T19:32:10Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-04-24Bitstream added on 2014-06-13T19:47:11Z : No. of bitstreams: 1 reis_rn_dr_bauru.pdf: 4426846 bytes, checksum: 0832ad71536929474c2efea40b48c449 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Materiais ferroelétricos do sistema Pb('Mg IND. 1/3''Nb IND.2/3')'O IND. 3'-xPbTi'O IND. 3'(PMN-xPT), possuem potencial efetivo para aplicações em dispositivos eletromecânicos, tais como, transdutores e sensores. Porém, a obtenção de cerâmica de PMN-xPT livre de fase pirocloro (paraelétrica) exige rigoroso controle durante a síntese. Neste trabalho, as condições destinadas a supressão de fase pirocloro em cerâmicas de PMN e PMN-xPT (para x = 0,33, 0,35 e 0,37), foram estudadas a partir de uma nova rota de preparação em função do excesso de MgO e PbO. Paralelamente, cerâmicas de PMN e PMN-PT obtidas pela rota convencional de mistura de óxidos, foram preparadas e os resultados comparados. Os resultados obtidos revelaram valores mais elevados de permissividade para as cerâmicas preparadas pela nova rota. Os valores da polarização remanescente das cerâmicas de PMN-xPT mostraram-se comparáveis com monocristais. Medidas dielétricas realizadas nas cerâmicas de PMN-xPT apontam um significante aumento nos valores de permissividade dielétrica em função do aumento do campo elétrico AC. Condutividade AC e impedância nas cerâmicas de PMN-xT foram estudadaas na região de frequência de 100Hz-1MHz e temperatura 325 - 50ºC. Uma anomalia no espectro de condutividade foi observada para todas as composições, próximo ao ponto de transição de fase ferroelétrica-paraelétrica. / Ferroelectric materials of Pb('Mg IND. 1/3''Nb IND.2/3')'O IND. 3'-xPbTi'O IND. 3'(PMN-xPT) system have effective potential for applications in electromechanical devices such as transducers and sensors. However, to obtain free pyrochlore phase (paraelectric) ceramics of PMN-xPT requires control during the synthesis. In this work, the conditions for the removal of pyrochlore phase of PMN and PMN-xPT (for x = 0.33, 0,35 and 0.37) ceramics, were studied using a new route of preparation with the excess MgO and PbO. The obtained results were compared with the ceramics of PMN and PMN-xPT prepared by the conventional route of mixed oxides. The results showed higher values of permittivity for the ceramics prepared by the new route. The remnant polarization values of PMN-xPT ceramics shown to be comparable with single crystal. Dielectric of PMN-xPT ceramics showed a significant increase in the values of dielectric permittivity due to the increase of the AC electric field. Conductivity AC and impedance of PMN-xPT ceramics were studied in the frequency range of 100Hz - 1MHz and temperature 325 - 50ºC. An anomaly was observed in the spectrum of conductivity for all the compositions, which is close to the point of ferroelectric-paraelectric phase transition.

Orientador: Eudes Borges de Araújo / Banca: Victor Ciro Solano Reynoso / Banca: Sebastião William da Silva / Resumo: O presente trabalho tem como objetivo estudar, através de investigações de espectros no infravermelho (FTIR), as transições de fases estruturais do sistema ferroelétrico titanato zirconato de chumbo, PbZr1-xTixO3 (PZT) no Contorno de Fase Morfotrópico (Morphotropic Phase Boundary, conhecido como MPB), região em que as propriedades elétricas desse material são máximas. Foram analisadas as soluções sólidas PbZr0,53Ti0,47O3 e PbZr0,54Ti0,46O3, que à temperatura ambiente encontram-se no interior do MPB e PbZr0,55Ti0,45O3, composição no limite da região do MPB, entre a fase monoclínica e a fase romboédrica, região ainda não bem definida e sob intensa investigação. Estudos estão centrados na freqüência e na meia largura dos modos stretching nos octaedros (BO6) da estrutura perovskita (ABO3) em função da temperatura. Anomalias encontradas para amostras com 47 e 46 mol % de PbTiO3 sugerem as transições da fase monoclínica de baixa para alta temperatura ( LT M F ? HT M F ), da fase monoclínica de alta temperatura para a coexistência da fase monoclínica com a fase tetragonal ( M F ? M F + T F ), e da coexistência da fase monoclínica com a tetragonal para a fase cúbica ( M F + T F ? C F ). Na amostra com 45 mol % de PbTiO3 foram encontradas anomalias que podem também estar associadas às transições de fases, mas que não foram possíveis de serem identificadas nas fases envolvidas. / Abstract: The present work studies, through investigations of the spectra in infrared (FTIR), the transitions of structural phases of the ferroelectric system lead zirconate titanate, PbZr1- xTixO3 (PZT), in the Morphotropic Phase Boundary (MPB), region where the electrical properties of this material are at its maxiumun. We analyzed the solid solutions PbZr0,53Ti0,47O3 and PbZr0,54Ti0,46O3, which at room temperature are found within the MPB and also the composition PbZr0,55Ti0,45O3, that is located on the limit of the MPB - between the monoclinic and the rhombohedral phases - a not-yet defined region under intense investigation. Studies are concentrating on frequency and half width of the stretching modes in octahedrons (BO6) of the perovskite structure (ABO3) regarding temperature. Anomalies found in samples with 47 and 46 mol % of PbTiO3 suggest transitions in the monoclinic phase from low to high temperature ( LT M F ? HT M F ), from monoclinic phase of high temperature to the coexistence between the monoclinic phase with the tetragonal phase ( M F ? M F + T F ), and the coexistence between the monoclinic phase with tetragonal for the cubic phase ( M F + T F ? C F ). In the sample with 45 % mol of PbTiO3 we have found anomalies that can also be associated with phase transitions. Such transitions have not been possible to identify during the stages of this work. / Mestre

Resumo: Materiais cerâmicos à base de titanato de estrôncio e bário puro (BST) e dopado com estanho (BST:Sn), apresentam propriedades ferroelétricas e ópticas com importantes aplicações tecnológicas. Essas propriedades dependem da estequiometria do material, rota de síntese e processamento e dopagem. No presente trabalho foi desenvolvido o estudo das propriedades ferroelétricas, microestruturais e ópticas do sistema Ba0,5Sr0,5(Ti1-ySny)O3, em variadas porcentagens molares (mol %), para pós e filmes sintetizados pelo método dos precursores poliméricos (MPP). Neste método foram utilizados, como principais fontes de cátions, carbonato de bário, carbonato de estrôncio e isopropóxido de titânio. Como agente complexante foi utilizado o ácido cítrico e como agente polimerizante o etilenoglicol. Os resultados experimentais e os cálculos mecânico-quânticos, realizados utilizando-se métodos de cálculos "ab inítio" com o programa CRISTAL98, indicaram que a PL pode estar associada com defeitos presentes na estrutura desordenada do BST e BST:Sn. As medidas de absorbância associadas com a caracterização fotoluminescente sugerem um "band gap" não uniforme com níveis de energia localizados dentro da região do "gap", os quais atuam como centro de absorção óptica e isto é a principal razão pela PL visível em temperatura ambiente. / Abstract: Ceramic materials based on strontium and barium titanate (BST) pure or doped with Sn (BST:Sn), posses ferroelectric and optical properties which important technological applications. Those properties are affected by sthoichiometry of material, synthesis and processing route and dopants. In our case the ferroelectric and optical properties and microstructure of system Ba0,5Sr0,5(Ti1-xSnx)O3 were investigated, considering various molar percentages (mol %) for powders and films synthesized by polymeric precursor method (MPP). In this method it was utilized, as a main source of cations, barium carbonate, strontium carbonate and titanium isopropoxide. For reaction of complexation was used cytric acid and for polymerization was used ethylene glycol. The experimental results and quantum-mechanical calculations using "ab initio" calculation method with program CRISTAL98, pointed to that PL could be associated with defects present in disordered structure of BST and BST:Sn. The measurement of absorbance associated with the photoluminescence characterization suggests that "band gap" is not uniform due to energy levels localized inside the "gap" region, which act as a center of optical absorption and it is the main reason for PL visible at room temperature. / Orientador: Elson Longo da Silva / Coorientador: Mario Cilense / Banca: Carlos de Oliveira Paiva Santos / Banca: Júlio Ricardo Sambrano / Banca: Valmor Roberto Mastelaro / Banca: Paulo Sérgio Pizani / Doutor

Compósitos cerâmicos planares de titanato zirconato de bário, BaTi1-xZrxO3, foram produzidos e os efeitos da quantidade de Zr4+ em suas propriedades funcionais foram estudados. As amostras foram fabricadas pelo método convencional de processamento cerâmico e pela técnica de deposição de fitas cerâmicas a partir de BaTi1-xZrxO3 com x=0, 0,05, 0,1, 0,15 e 0,2 sintetizados pelo método hidrotermal e pelo método dos precursores poliméricos. Foram realizadas caracterizações estrutural (difração de Raios X pelo método do pó e espectroscopia Raman), composicional (espectroscopia por dispersão de energia), microestrutural (microscopia eletrônica de varredura, ensaios de dilatometria) e funcional (permissividade elétrica, coeficiente piezoelétrico d33, coeficiente piroelétrico e histerese ferroelétrica). Além disso, a regra da mistura de fase foi utilizada para prever a permissividade elétrica dos compósitos e as tensões mecânicas internas e seus efeitos na permissividade elétrica e na temperatura de Curie de policristais de BaTiO3 foram simulados. As análises dos dados e as discussões foram realizadas considerando o modelo fenomenológico de Devonshire, a modificação de Forsbergh deste modelo para incluir efeitos de tensões mecânicas bidimensionais e o modelo de policristal tetragonal de BaTiO3 sugerido por Buessem. Os resultados mostram a existência de tensões residuais bidimensionais que surgem após o resfriamento dos compósitos devido às diferenças nos coeficientes de expansão térmica das fases constituintes. Os métodos de obtenção das amostras afetaram o tamanho final dos grãos e as espessuras das interfaces dos compósitos, sendo que, em geral, eles são menores e mais finos nas fitas cerâmicas homogêneas do que nas correspondentes cerâmicas homogêneas. Os compósitos apresentaram deslocamento da Tc para maiores temperaturas e aumento do grau de difusividade da transição. A presença das tensões mecânicas residuais e as características microestruturais, juntamente com os modelos utilizados, explicam qualitativamente a permissividade elétrica obtida. Concluí-se que a quantidade de Zr4+ modifica o comportamento das camadas durante a sinterização e altera o coeficiente de dilatação. Estas mudanças geram tensões mecânicas residuais que afetam a microestrutura e as propriedades funcionais dos compósitos. Portanto, a produção de compósitos cerâmicos ferroelétricos deve considerar a correlação existente entre microestrutura e tensões residuais para que suas propriedades sejam otimizadas. / Planar BaTi1-xZrxO3 ceramic composites had their functional properties investigated. These composites were obtained by the conventional ceramic processing technique and by tape casting technique. Furthermore, BaTi1-xZrxO3 x=0, 0.05, 0.1, 0.15 and 0.2 were synthesized by the polymeric precursors method and by the hydrothermal synthesis to study the synthesis influences and to study the effect of Zr4+ on the functional properties of the composites. Structural characterization (X-Ray powder diffraction and Raman spectroscopy), compositional analysis (energy dispersive X-Ray spectroscopy), microestrutural evaluation (scanning electron microscopy, dilatometry measurements) and functional properties characterization (electrical permittivity, piezoelectric coefficient d33, pyroelectric coefficient and ferroelectric hysteresis) were performed. Furthermore, the composites electrical permittivity was predicted by the simple mixture and the internal mechanical stress distribution and it´s effects on both, electrical permittivity and Curie´s temperature (Tc) of BaTiO3 polycrystals, were simulated. The analyses and discussions were supported by 1- Devonshire´s phenomenological theory, 2- Forsbergh´s modification to Devonshire´s theory to include the two-dimensional stress effects on Tc and 3- Buessem´s BaTiO3 tetragonal polycrystal model. The results show that the sintered composites present two-dimensional residual stresses after cooling due to the constrained sintering of the layers and their thermal expansion coefficient mismatch. The methods of sample preparation led to differences in grain size and interface thickness, with the homogeneous ceramic tapes presenting smaller grain sizes and thinner thickness than the conventional homogeneous ceramics. On the other hand, the composites showed a Tc shift to higher temperatures, a more diffuse phase transition and residual mechanical stresses. Concluding, the Zr4+ substitution of Ti4+ modifies the layer´s sintering behavior and their thermal expansion coefficient. These changes lead to microstructure modifications that affect the functional properties of planar BaTi1-xZrxO3 composites. Thus, the design of ferroelectric composites should take into consideration the correlations between microstructure and residual stresses in order to optimize their functional properties.

Abstract Nd-modified lead-zirconate-titanate (PNZT) thin films were deposited on MgO(100), Si(100) and Al2O3(1102) single-crystal substrates using the pulsed-laser-ablation technique with a XeCl excimer laser. The post-annealing heat-treatment technique was used for the crystallisation of the films. The structural characterization, microstructure and the chemical composition of the thin films and of the ceramic Pb0.97Nd0.02(Zr0.55Ti0.45)O3 targets after ablation were studied using x-ray diffraction, scanning electron microscopy and energy-dispersive x-ray spectroscopy, respectively. The formation of the particulates on the target surface during the ablation process and the effect of the particulates on the quality of the thin films were studied. Typically, the ferroelectric PNZT thin films for the capacitor structures were deposited at the laser-beam fluence of around 1.0 J/cm2 and annealed at the temperatures from 600 to 700 °C. The dielectric and, especially, the polarization properties and the residual macroscopic stress state of the PNZT thin films were studied. The relationship between the electrical properties of the films and the nature of the stress state was also investigated. The average growth rate of the PNZT films increased linearly with increasing laser-beam fluence above the threshold value of around 0.4 J/cm2. The composition of the PNZT films varied strongly with the deposition laser-beam fluence and annealing temperature. The phase structure of PNZT films ablated from Pb0.97Nd0.02(Zr0.55Ti0.45)O3 targets could be adjusted between tetragonal and rhombohedral structures by changing the incident laser-beam fluence on the target surface. The surface of the target after ablation was covered by the laser-cone structure and the topmost layer of the target was amorphous having TiO2 and ZrO2 structures with separate segregated lead droplets. On MgO substrates, values of the relative dielectric constant er from 430 to 560 and of the remanent polarization εr of the order of 18 μC/cm2 were achieved in PNZT films which were under a compressive stress of the order of 300 MPa. On silicon substrates, εr was around 100 and the polarization properties of the films were modest due to a strong tensile stress of the order of 400 MPa. The Poole-Frenkel conduction mechanism with the activation energy of around 0.2 eV was found responsible for the leakage conductivity in the capacitor structures with PNZT films.

Abstract The thesis describes electrically tunable microwave devices utilising low sintering temperature, screen printable Barium Strontium Titanate (BST) thick films. The work has been divided into two parts. In the first section, the fabrication and microwave characterisation of BST material based structures compatible with Low Temperature Cofired Ceramic technology (BST-LTCC) are presented. Three different fabrication techniques, namely: direct writing, screen printing and via filling techniques, were used for the realisation of the structures. A detailed description of these fabrication techniques is presented. The dielectric properties such as relative permittivity, static electric field dependent tunability and loss tangent of BST-LTCC structures at microwave frequencies were characterised using coplanar waveguide transmission line and capacitive element techniques. The measured dielectric properties of BST-LTCC structures realised with the different fabrication methods are presented, compared and discussed. The second section describes tunable microwave devices based on BST-LTCC structures. A frequency tunable folded slot antenna (FSA) with a screen printed, integrated BST varactor is presented. The resonant frequency of the FSA was tuned by 3.2% with the application of 200 V external bias voltage. The impact of the BST varactor on the total efficiency of the antenna was studied through comparison with a reference antenna not incorporating the BST varactor. A compact, frequency tunable ceramic planar inverted-F antenna (PIFA) utilising an integrated BST varactor for mobile terminal application is presented. The antenna's resonant frequency was tuned by 3% with an application of 200 V bias voltage. Frequency tunable antennas with a completely integrated electrically tunable BST varactor with silver metallisation are introduced in this work for the first time. The integration techniques which are described in this thesis have not been previously reported in scientific literature. The last part of the thesis presents a microwave delay line phase shifter operating at 3 GHz based on BST-LTCC structures. The figure of merit (FOM) of the phase shifter was measured to be 14.6 °/dB at 3 GHz and and the device employs a novel structure for its realisation that enabled the required bias voltage to be decreased, while still maintaining compliance with standard screen printing technology. The performance of the phase shifter is compared and discussed with other phase shifters realised with the BST thick film process. The applications of BST-LTCC structures were demonstrated through frequency tuning of antennas, varactors, and phase shifters. The low sintering temperature BST paste not only enables the use of highly conductive silver metallisation, but also makes the devices more compact and monolithic.

No description available.

Organic ferroelectrics polymers have recently received much interest for use in nonvolatile memory devices. The ferroelectric copolymer poly(vinylidene fluoride- trifluoroethylene) , P(VDF-TrFE), is a promising candidate due to its relatively high remnant polarization, low coercive field, fast switching times, easy processability, and low Curie transition. However, no detailed study of charge injection and current transport properties in P(VDF-TrFE) have been reported in the literature yet. Charge injection and transport are believed to affect various properties of ferroelectric films such as remnant polarization values and polarization fatigue behavior.. Thus, this thesis aims to study charge injection in P(VDF-TrFE) and its transport properties as a function of electrode material. Injection was studied for Al, Ag, Au and Pt electrodes. Higher work function metals such as Pt have shown less leakage current compared to lower work function metals such as Al for more than an order of magnitude. That implied n-type conduction behavior for P(VDF-TrFE), as well as electrons being the dominant injected carrier type. Charge transport was also studied as a function of temperature, and two major transport regimes were identified: 1) Thermionic emission over a Schottky barrier for low fields (E < 25 MV/m). 2) Space-Charge-Limited regime at higher fields (25 < E <120 MV/m). We have also studied the optical imprint phenomenon, the polarization fatigue resulting from a combination of broad band optical illumination and DC bias near the switching field. A setup was designed for the experiment, and validated by reproducing the reported effect in polycrystalline Pb(Zr,Ti)O3 , PZT, film. On the other hand, P(VDF-TrFE) film showed no polarization fatigue as a result of optical imprint test, which could be attributed to the large band gap of the material, and the low intensity of the UV portion of the arc lamp white light used for the experiment. Results suggest using high work function metals for a memory application, as lower leakage would enhance fatigue endurance for P(VDF-TrFE) film.

Indiana University-Purdue University Indianapolis (IUPUI) / Thermal constraints and the quantum limit will soon put a boundary on the scale of new micro and nano magnetoelectronic devices. This necessitates a push into the limits of harnessable natural phenomena to facilitate a post-Moore’s era of design. Requirements for thermodynamic stability at room temperature, fast (Ghz) switching, and low energy cost narrow the list of candidates. Here we show voltage controllable, room temperature, stable locking of the spin state, and the corresponding conductivity change, when molecular spin crossover thin films are deposited on a ferroelectric substrate. This opens the door to the creation of a non-volatile, room temperature, molecular multiferroic gated voltage controlled device.

Ferroelectric non-volatile memories have gained momentous importance in the recent years. Significant research is being done on different device structures with several ferroelectric films for better data retention, lower power dissipation and higher density of integration. Metal - ferroelectric insulator – semiconductor (MIS) capacitor structures with Poly Vinylidene Fluoride(80%) - trifluoroethylene (20%) (PVDF – TrFE) copolymer are observed to demonstrate consistent dielectric properties and retainable memory action under selected operating conditions. Prior research was done on devices with MFeOS structure with an oxide buffer layer. The presence of a buffer oxide reduces the field acting on the film for memory state switching, which in effect requires the devices to be operated at higher voltages. In this work, MFeS devices with lower ferroelectric film thickness; with, and without a very thin buffer oxide have been studied. The dielectric behavior of PVDF thin film, when deposited directly on Si, is observed to exhibit reliable memory properties without significant charge injection under certain operating conditions. Electrical characteristics such as capacitance-voltage(C-V) and polarization-electric field (P-E) hysteresis with the direction of measurement and conduction properties through the junction have been comprehensively studied to establish the behavior of the MIS device for possible use in MIS FETs for high density ferroelectric memories.