Made available in DSpace on 2014-06-11T19:32:11Z (GMT). No. of bitstreams: 0 Previous issue date: 2006-03-22Bitstream added on 2014-06-13T19:42:34Z : No. of bitstreams: 1 souza_ia_dr_araiq.pdf: 3152207 bytes, checksum: f9e6c24958aaba1d137ed39fcf9d1179 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / 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. / 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.

Ferroelectric and antiferroelectric ultrathin films have attracted a lot of attention recently due to their remarkable properties and their potential to allow for device miniaturization in numerous applications. However, when the ferroelectric films are scaled down, it brings about an unavoidable depolarizing field. A partial surface charge compensation allows to control the residual depolarizing field and manipulate the properties of ultrathin ferroelectric films. In this dissertation we take advantage of atomistic first-principles-based simulations to expand our understanding of the role of the partial surface charge compensation in the properties of ferroelectric and antiferroelectric ultrathin films. The application of our computational methodology to study the effect of the partial surface charge compensation in ferroelectric ultrathin films led to the prediction that, depending on the quality of the surface charge compensation, ferroelectric thin films respond to an electric field in a qualitatively different manner. They can be tuned to behave like a linear dielectric, a ferroelectric or even an antiferroelectric. This effect was shown to exist in films with different mechanical boundary conditions and different crystal symmetries. There are a number of potential applications where such properties of ferroelectric thin films can be used. One of these potential applications is energy storage. We will show that, in the antiferroelectric regime, ferroelectric thin films exhibit drastic enhancement of energy storage density which is a desirable property. One of the most promising applications of ferroelectric ultrathin films that emerged only recently is the harvesting of the giant electrocaloric effect. Interestingly, despite numerous studies of the electrocaloric effect in ferroelectric thin films, it is presently unknown how a residual depolarizing field affects the electrocaloric properties of such films. Application of state-of-the-art computational methods to investigate the electrocaloric effect in ferroelectric films with partial surface charge compensation led to the prediction that the residual depolarizing field can perform a dual role in the electrocaloric effect in these films. When the depolarizing field creates competition between the monodomain and nanodomain states, we predict an enhancement of the electrocaloric effect due to the frustration that increases the entropy of the state and therefore the electrocaloric temperature change. On the other hand, when the depolarizing field leads to a formation of nanodomains, thin films either exhibit a small electrocaloric effect or lose their electrocaloric properties altogether to the irreversible nanodomain motion. When the residual depolarizing field is weak enough to permit the formation of monodomain phases, the electrocaloric effect is significantly reduced as compared to bulk. We believe that our findings could potentially reveal additional opportunities to optimize solid state cooling technology. While the electrocaloric effect has been a popular topic of interest in recent years [12], there still exists numerous gaps in the fundamental understanding of the effect. In particular, it is presently unknown whether the scaling laws, known to exist for magnetocaloric materials, can be applied to ferroelectric and antiferroelectric electrocalorics. We predict the existence of scaling laws for low-field electrocaloric temperature change in antiferroelectric and ferroelectric materials. With the help of first-principles-based simulations, we showed computationally that the scaling laws exist for antiferroelectric PbZrO3 along with ferroelectrics PbTiO3, BaTiO3 and KNbO3. Additional evidence of the scaling laws existence are provided using experimental data from the literature. Interestingly, our studies on ferroelectric films predicted the existence of antiferroelectric behavior in ultrathin films with partial surface charge compensation. One may wonder whether it is possible to stabilize the ferroelectric phase in antiferroelectric films and what role the surface charge screening would play in such a transition. Motivated to address these fundamental questions, we used computational experiments to study antiferroelectric ultrathin films with a residual depolarizing field. Our studies led to the following predictions. We found that PbZrO3 thin films exhibit the ferroelectric phase upon scaling down and under the condition of efficient surface charge compensation. We also found a strong competition between the antiferroelectric and ferroelectric phases for the thin films of the critical size associated with antiferroelectric-ferroelectric phase transition. This finding motivated us to study the electrocaloric effect in PbZrO3 thin films with antiferroelectric-ferroelectric phase competition. We found that high tunability of the phase transition by the electric field leads to a wide range of temperatures associated with a strong electrocaloric effect. In addition, we found that epitaxial strain provides further tunability to the electrocaloric properties. In summary, our studies led to a broader and deeper understanding of the abundantly many roles surface charge compensation plays in ultrathin ferroelectrics and antiferroelectrics.

Perovskite ferroelectrics and antiferroelectrics have attracted a lot of attention owing to their potential for device applications including THz sensors, solid state cooling, ultra high density computer memory, and electromechanical actuators to name a few. The discovery of ferroelectricity at the nanoscale provides not only new and exciting possibilities for device miniaturization, but also a way to study the fundamental physics of nanoscale phenomena in these materials. Ferroelectric nanowires show a rich variety of physical characteristics which are advantageous to the design of nanoscale ferroelectric devices such as exotic dipole patterns, a strong dependence of the polarization and phonon frequencies on the electrical and mechanical boundary conditions, as well as a dependence of the transition temperatures on the diameter of the nanowire. Antiferroelectricity also exists at the nanoscale and, due to the proximity in energy of the ferroelectric and antiferroelectric phases, a phase transition from the ferroelectric to the antiferroelectric phase can be facilitated through the application of the appropriate mechanical and electrical boundary conditions. While much progress has been made over the past several decades to understand the nature of ferroelectricity/antiferroelectricity in nanowires, many questions remain unanswered. In particular, little is known about how the truncated dimensions affect the soft mode frequency dynamics or how various electrical and mechanical boundary conditions might change the nature of the phase transitions in these ferroelectric nanowires. Could nanowires offer a distinct advantage for solid state cooling applications? Few studies have been done to elucidate the fundamental physics of antiferroelectric nanowires. How the polarization in ferroelectric nanowires responds to a THz electric field remains relatively underexplored as well. In this work, the aim is to to develop and use computational tools that allow first-principles-based modeling of electric-field-induced phenomena in ferroelectric/antiferroelectric nanowires in order to address the aforementioned questions. The effective Hamiltonian approach is a well validated model which reliably reproduces many static and dynamic properties of perovskite ferroelectric and antiferroelectrics. We begin by developing an effective Hamiltonian for the prototypical ferroelectric potassium niobate, a lead-free material which undergoes multiple structural phase transitions. Density functional theory calculations within the LDA and GGA are used to determine the effective Hamiltonian parameters for KNbO3 . By simulating an annealing within an NPT ensemble, we find that the KNbO3 parameters found from first principles underestimate the experimental transition temperatures. We apply a universal scaling technique to all of the first-principles derived parameters and are thus able to more accurately reproduce the transition temperatures predicted by experiment as well as a number of other static and dynamic properties of potassium niobate. Having determined the parameters of the effective Hamiltonian for KNbO3 , we use this as well as previously determined effective Hamiltonian parameters for PbTiO3 and BaTiO3 to study the electrocaloric effect in nanowires made of these materials. We determined that, in general, the electrocaloric effect in ferroelectric nanowires is diminished due to the reduced correlation length resulting from the finite lateral dimensions. However, certain temperature ranges were identified near ambient temperature where the electrocaloric response is enhanced with respect to bulk. The effective Hamiltonian model was also employed to study the response of the spontaneous polarization and temperature to tailored electric fields. We identified a novel means of reversing the polarization in ferroelectric nanowires which could potentially be used in the design of nanoscale THz sensors of ultra high density ferroelectric memory devices. While the soft mode frequency dynamics of bulk ferroelectrics under various mechanical boundary conditions have been studied extensively, the effects of different mechanical boundary conditions on the soft mode dynamics in ferroelectric nanowires remains relatively under-explored. We conduct a comprehensive study on PbTiO3 nanowires which explores the effects of hydrostatic pressure, applied uniaxial stress, and biaxial strain on the structural properties, transition temperatures, and soft mode dynamics. We found that depending on the particular type of mechanical boundary condition, the nanowire can exhibit either monodomain or polydomain vortex phases, drastically different from what is found for PbTiO3 bulk and originates from the critical role of the depolarizing field. We found a rich variety of dipole patterns, particularly for the polydomain states with the dipoles arranged in single and double polarization vortices depending on the type and strength of the mechanical boundary conditions. The soft mode frequency dynamics are also strongly affected by the mechanical boundary conditions. In particular we find that the frequency of the E mode in the P4mm phase is significantly larger than the A 1 mode which is in contrast with bulk PbTiO3 . This striking finding is attributed to the presence of the depolarizing field along the truncated directions which leads to mode hardening. In the last chapter, we identify the emergence of a ferroelectric state in antiferroelectric PbZrO3 nanowires and describe possible ways to stabilize the ferroelectric phase. Finally, we explore how our findings could potentially be used to improve existing technologies such as energy storage devices and electromechanical actuators as well as future technologies like solid state cooling devices.

Advancements in electronics research triggered a vision of a more connected world, touching new unprecedented fields to improve the quality of our lives. This vision has been fueled by electronic giants showcasing flexible displays for the first time in consumer electronics symposiums. Since then, the scientific and research communities partook on exploring possibilities for making flexible electronics. Decades of research have revealed many routes to flexible electronics, lots of opportunities and challenges. In this work, we focus on our contributions towards realizing a complimentary approach to flexible inorganic high performance electronic memories on silicon. This approach provides a straight forward method for capitalizing on the existing well-established semiconductor infrastructure, standard processes and procedures, and collective knowledge. Ultimately, we focus on understanding the reliability and functionality anomalies in flexible electronics and flexible solid state memory built using the flexible silicon platform. The results of the presented studies show that: (i) flexible devices fabricated using etch-protect-release approach (with trenches included in the active area) exhibit ~19% lower safe operating voltage compared to their bulk counterparts, (ii) they can withstand prolonged bending duration (static stress) but are prone to failure under dynamic stress as in repeated bending and re-flattening, (iii) flexible 3D FinFETs exhibit ~10% variation in key properties when exposed to out-of-plane bending stress and out-of-plane stress does not resemble the well-studied in-plane stress used in strain engineering, (iv) resistive memories can be achieved on flexible silicon and their basic resistive property is preserved but other memory functionalities (retention, endurance, speed, memory window) requires further investigations, (v) flexible silicon based PZT ferroelectric capacitors exhibit record polarization, capacitance, and endurance (1 billion write-erase cycles) values for flexible FeRAMs, uncompromised retention ability under varying dynamic stress, and a minimum bending radius of 5 mm, and (vi) the combined effect of 225 °C, 260 MPa tensile stress, 55% humidity under ambient conditions (21% oxygen), led to 48% reduction in switching coercive fields, 45% reduction in remnant polarization, an expected increase of 22% in relative permittivity and normalized capacitance, and reduced memory window (20% difference between switching and non-switching currents at 225 °C).

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The nuclear magnetic resonance spectrum of the protons in rubidium hydrogen sulfate, and the spin-lattice relaxation time for the protons in lithium hydrazinium sulfate have been examined as a function of temperature, in order to obtain information about the motions of the protons in the different states of these substances. Rubidium hydrogen sulfate becomes ferroelectric below -15°C, and the possibility of a change in the proton resonance linewidth associated with this transition was investigated. The free-precession (spin echo) NMR technique was used to obtain the proton spin-lattice relaxation time in lithium hydrazinium sulfate, over a wide temperature range. The observed changes in relaxation time gave further data on the hydrazinium ion motions that were inferred from proton NMR studies by Cuthbert and Petch in 1963. / Thesis / Master of Science (MSc)

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