Phase-transformation-induced microstructures, including twin domains, anti-phase domains and inversion domains have been analyzed using the scanning and transmission electron microscopy for BaTiO3, BaCeO3 and CaTiO3 of the perovskite structure. Differential etching rate was taken to identify the ferroelectric domains in tetragonal (t-) BaTiO3. Space group Pbnm (No. 62) usually adopted for the orthorhombic crystals by materials scientists is assumed throughout this research to avoid confusion of the plane and direction indices. Traditional contrast analysis was adopted for determining dislocation Burgers vectors (b) and fault vectors (R) in deformed and phase-transformed perovskites, synthetic ceramics (BaTiO3, BaCeO3 and CaTiO3) as well as natural minerals (CaTiO3), polycrystalline (BaTiO3, BaCeO3 and CaTiO3) as well as single crystal (CaTiO3). Atomic images for the structures of twin boundaries and anti-phase boundaries were taken by high resolution technique and image contrast enhancement was performed using fast Fourier transform. Failure of Friedel¡¦s law is adopted for determining if the crystal belongs to non-centrosymmetric point groups. Whether the twins are £_-, £\- or £k-type (i.e. anti-phase domain boundaries) is analysed from the contrast of extreme fringe patterns. Tilting experiments were performed on selected area diffraction patterns containing un-split row of reflections to ensure that the twin boundaries are the reflection or rotation type. Transformation twinning in all perovskites studied here follows the prediction by the relation of point group symmetries between the high- and low-symmetry phases, assuming continuous, diffusionless, second-order transitions that obey the restrictions imposed by the Landau theory of phase transition. Although such predictions of transformation-induced twinning are only permitted when crystallographic group-subgroup relationship exists and structural coherence retains between the high- and low-symmetry phases, experimental observations for r (rhombohedral) ¡÷ o-BaCeO3 and t ¡÷ o in CaTiO3 that are not related by group-subgroup, c (cubic) ¡÷ t (tetragonal) in CaTiO3 and and c (cubic) ¡÷ t (tetragonal) in BaTiO3 that are related by group-subgroup, are all consistent with the predictions from loss of point group symmetry elements and change of unit cell volume. In order that the Landau theory is conformed, however, an intermediate phase of either the lowest common supergroup (cubic Pm m) or highest common subgroup (monoclinic C2/c), with phase transition experiencing multistage pathways suggested by Christy and assumption of non-disruption conditions proposed by Guymont, was identified to bridge between two structures, such as rhombohedral and orthorhombic that are not group-subgroup related. Both the 90o and 180o ferroelectric twin domains in t-BaTiO3 are the reflection type and have been identified in pressureless-sintered ceramics. Further, fault vectors (R = £`<110]) for such domain boundaries were determined, boundary planes of {110) for the former, {100) and {220) for the latter deduced accordingly. The polar c-direction between adjacent domains was determined by differential etching rate across domain boundaries, convergent beam electron diffraction was also adopted for identification and confirmation of the c-axis for two types of domains in t-BaTiO3. Plastic deformation resulting from the thermodynamic driving force for sintering (?p) intensified by a multiplication factor £p) was evidenced microstructurally from analysing dislocations in pressureless-sintered BaTiO3 where a Frank-Read source was observed. Slip systems are activated for the effective stress acting on the slip plane along the slip direction has exceeded the critical value of resolved shear stress (£nCRSS) and yielding occurs. It has contributed to densification, i.e. the overall system shrinkage of a green powder compact, although if such contribution is at all significant requires studies of sintering kinetics to ascertain. Dislocation dissociation into the scallop-shaped half partials according to the following reactions is determined from analysing corresponding Burgers vectors. [010] + [001] ¡÷ [011] [001] + [10 ] ¡÷ [100] [001] + [110] ¡÷ [111] Both transformation twins lying in {110) and {112) and anti-phase domain boundaries with R = 1/2<111> are detected in o-BaCeO3. For orthorhombic (o-) BaCeO3, fault vectors of the latter R = 1/2<111> determined by contrast analysis was confirmed by high-resolution imaging, but on the contrary, fault vectors the former R = £`<110] and £`<021], respectively, could not be determined from such images. Utilizing the technique of large-angle convergent beam electron diffraction, such fault vectors and dislocation Burgers vectors determined by traditional contrast analysis have been confirmed. Both twinning and dislocations were observed in hot-pressed CaTiO3 prepared in a multi-anvil apparatus. Such twins are deformation twins since hot-pressing was conducted in the orthorhombic stable phase field at 1000oC under 8 GPa. Since fault vectors R = £`<110] determined for {112) and {110) twins are different from the transformation-induced twins in o-CaTiO3, R = £`<021] determined for the {112) twinning in natural perovskite may serve as a diagnostic feature for the deformation twins. Plastic deformation in hot-pressured sample was contributed by both slip and twinning. Slip occurred via slip systems with dislocations of b = [110] gliding in (110) is therefore {110}o <1 0>o (equivalent to {100}pc <001>pc, where pc for pseudo-cubic) often found in perovskites deformed at high temperatures. Another set of dislocations with b = [001] in screw orientation was also determined. APB with R = 1/2<111> detected in natural minerals suggests that the phase transition sequence in CaTiO3 is better described by: (c) ¡÷ t (I4/mcm) ¡÷ o (Pbnm) and such APB are generated from loss of the lattice point at I-centre (1/2,1/2,1/2) in the absence of a second orthorhombic Cmcm between t-I4/mcm and o-Pbnm reported before from neutron and X-ray powder diffraction studies.

Thesis (Ph. D.)--University of Washington, 2003. / Vita. Includes bibliographical references (p. 232-243).

Thesis (Ph. D.)--University of Texas at Austin, 2001. / Vita. Includes bibliographical references (leaves 206-210). Available also in a digital version from Dissertation Abstracts.

Inside your microelectronic devices there are up to a billion transistors working in flawless operation. Silicon has been the workhorse semiconductor used for the transistor; however, there must be a transition to materials other than silicon, such as germanium, with future device sizes. In addition, new dielectric oxide materials are needed. My research has examined a type of crystalline oxide, known as a perovskite, which is selected for its ability to bond chemically to Si and Ge, and eliminate the electrical defects that affect performance. Many perovskite oxides are lattice-matched to the Si (001) and Ge (001) surface spacing, enabling heteroepitaxy. To date, the majority of research on crystalline oxides integrated with semiconductors has been based on strontium titanate, SrTiO3, epitaxially grown on Si (001) by molecular beam epitaxy. Alternative low-temperature growth methods, such as atomic layer deposition (ALD), offer both practical and economic benefits for the integration of crystalline oxides on semiconductors. My initial research informed the broader community that four unit cells (~1.5 nm) of SrTiO3 are required to enable heteroepitaxy on Si. The research has also shown that heteroepitaxial layers can be monolithically integrated with Si (001) without the formation of a SiOx interlayer between the Si (001) surface and the SrTiO3 layer because ALD is performed at lower temperatures than are typical for MBE. Thus, a combined MBE-ALD growth technique creates possible advantages in device designs that require the crystalline oxide to be in contact with the Si (001) surface. In recent work, I have demonstrated a method for integrating crystalline oxides directly on Ge by ALD. Germanium is being explored as an alternative channel material due to its higher hole and electron mobilities than Si, potentially enabling device operation at higher speed. This all-chemical growth process is expected to be scalable, is inherently less costly from a manufacturing cost of ownership, and is based on current manufacturing tool infrastructure. The impact of my research will be in continued scaling of device dimensions with novel materials that will provide faster speed and lower power consumption for microelectronic devices. / text

Not available / text

This dissertation is divided into two parts. In the first, the general paradigm of scanned probe microscopy is outlined with a focus on atomic force microscopy and a few of its variations. Magnetic force microscopy is covered in detail as it forms the basis of the second part of this dissertation. The core elements and extra features of the instrument are described with attention paid to the upgrades made by the author. In the second part of this dissertation, background information on perovskite oxides and the inverse spinel system, magnetite, is given. Magnetic force microscopy studies were done on three thin film systems and are detailed. In the first study, ferromagnetic manganite films were subjected to discontinuous changes in strain due to structural transitions in their barium titanate substrates. The resulting effect on the magnetic domains was observed. In the second study, the ferromagnetism of a tensile-strained LaCoO₃ film was studied across temperatures from 4.3 K to 90 K and applied fields up to [mu]₀H=1.1 T. Finally, the properties of antiphase domains in magnetite films of varying film strain due to transition metal buffer layers was probed by imaging the magnetic domains which are pinned to the antiphase boundaries. / text

Not available / text

No description available.

Our understanding of the nature of Earth’s D” region was changed significantly by a recent finding by Murakami et al. (2004), who revealed a phase transition from perovskite to post-perovskite structure in MgSiO3 at about 125 GPa and 2500 K, corresponding to conditions of the lowermost mantle. A perovskite to post-perovskite phase transition accounts for many unusual features of the D” region, including its notable seismic anisotropy, and also accounts for the unusual topology of the D” discontinuity. However, the experimentally synthesised post-perovskite phase of MgSiO3 is not quenchable to ambient conditions, which means that many of its physical properties remain difficult to determine. On the other hand, there are several post-perovskite oxides, CaIrO3, CaPtO3, CaRhO3 and CaRuO3, which can be quenched to ambient conditions, maintaining their structure. High pressure synthesis of CaIr1-xPtxO3 solid solutions (x = 0, 0.3, 0.5, 0.7) and CaIr0.5Rh0.5O3 was conducted at the University of Edinburgh and Geodynamics Research Center, Ehime University, and structures and physical properties of these novel post-perovskite materials determined. Substantial [100] grain growth was observed in all solid solutions leading to pronounced texture even in powdered materials. Temperature-independent paramagnetism above 150 K and small magnetic entropy observed in heat capacity measurements suggest that CaIrO3 is an intrinsically weak itinerant ferromagnetic metal, while electrical resistivity measurements show that it is a narrow bandgap semiconductor, possibly due to grain boundary effects. CaIrO3 undergoes a magnetic transition at 108K and possesses a saturated magnetic moment of 0.04 μB. Doping with Pt or Rh induces Curie-Weiss paramagnetism and suppresses the magnetic transition. The anisotropic structure and morphology of CaIrO3 combined with the Ir4+ spin-orbit coupling results in a large magnetic anisotropy constant of 1.77 x 106 Jm-3, comparable to values for permanent magnet materials. A new high-pressure phase of CaIr0.5Pt0.5O3 was synthesised at 60GPa, 1900K using a laser-heated DAC (diamond anvil cell) at GRC, Ehime University. Its Raman spectra resemble those of perovskite phases of CaIrO3 and CaMnO3, implying that CaIr0.5Pt0.5O3 undergoes a post-perovskite to perovskite phase transition with increasing pressure. I estimate an increase in thermodynamic Grüneisen parameter γth across the post-perovskite to perovskite transition of 34 %, with similar magnitude to (Mg,Fe)SiO3 and MgGeO3, suggesting that CaIr0.5Pt0.5O3 is a promising analogue for experimentally simulating the competitive stability between perovskite and post-perovskite phase of magnesium silicates in Earth’s lowermost mantle. Such estimation is reliable since the estimated and directly calculated thermodynamic Grüneisen parameter γth from heat capacity show consistent values. The marked effect that Pt has on stabilising the post-perovskite structure in CaIr1-xPtxO3 solid solutions explains why the post-perovskite to perovskite phase transition has not been observed for CaPtO3 in contrast to other quenchable post-perovskite oxides: CaIrO3, CaRhO3 and CaRuO3.Work presented here demonstrates that CaIrO3 solid solutions can be used to provide new insight into factors stabilising post-perovskite structures in Earth’s lowermost mantle.

This work focused on the study of three independent projects involving perovskite oxide materials and their applications as solid oxide fuel cell (SOFC) anodes and electrochemical oxygen sensors. The underlying theme is the versatility and tune-ability of the perovskite structure. Reactivity and conductivity (ionic as well as electronic) are modified to optimize performance in a specific application. The effect of Ce doping on the structure and the conductivity of BaFeO3 perovskite materials is investigated and the resulting materials are applied as oxygen sensors. The new perovskite family, Ba1-xCexFeO3-δ (x=0, 0.01, 0.03, and 0.05), was prepared via a sol-gel method. Powder XRD indicates a hexagonal structure for BaFeO3 with a change to a cubic perovskite upon Cerium doping at the A site. The solubility limit of Ce at the A site was experimentally determined to be between 5-7 mol %. Bulk, electronic and ionic conductivities of BaFeO3-δ and Ba0.95Ce0.05FeO3-δ were measured in air at temperatures up to 1000˚C. Cerium doping increases the conductivity throughout the entire temperature range with a more pronounced effect at higher temperatures. At 800˚C the conductivity of Ba0.95Ce.05FeO3-δ reaches 3.3 S/cm. Pellets of Ba0.95Ce.05FeO3-δ were tested as gas sensors at 500 and 700˚C and show a linear, reproducible response to O2. Promising perovskite anodes have been tested in high sulfur fuel feeds. A series of perovskite solid oxide fuel cell (SOFC) anode materials: Sm0.95Ce0.05FeO3-δ, Sm0.95Ce0.05Fe0.97Ni0.03O3-δ and Sm0.95Ce0.05Fe0.97Co0.03O3-δ have been tested for sulfur tolerance at 500°C. The introduction of the extreme 5% H2S enhances the performance of these anodes, verified by EIS and CA experiments. Post mortem analyses indicate that the performance XII enhancement arises from the partial sulfidation of the anode, leading to the formation of FeS2, Sm3S4 and S on the perovskite surface. Testing in lower concentrations of sulfur, more common in sour fuels, 0.5% H2S, also enhances the performance of these materials. The SCF-Co anode shows promising stability and an increase in exchange current density, io, from 13.72 to 127.02 mA/cm2 when switching from H2 to 0.5% H2S/99.5% H2 fuel composition. Recovery tests performed on the SCF-Co anode conclude that the open cell voltage (OCV) and power density of these cells recover within 4 hours of H2S removal. We conclude that the formation of metal sulfide species is only partially reversible, yielding an anode material with an overall lower Rct upon switching back to pure H2. Combining their performance in sulfur containing fuels with their previously reported coke tolerance makes these perovskites especially attractive as low temperature SOFC anodes in sour fuels. A new perovskite family Ba1-xYxMoO3 (x=0-0.05) has been investigated in regards to electrical conductivity and performance as IT-SOFC anode materials for the oxidation of H2. Refinement of p-XRD spectra as well as SEM imaging conclude that the solubility limit of Y doping at the A site is 5 mol%, beyond which Y2O3 segregation occurs. The undoped BaMoO3 sample has a colossal room temperature conductivity of 2500 S/cm in dry H2. All materials maintain metallic conductivity in the temperature range of 25-1000°C with resistance increasing with Y doping. The Ba1-xYxMoO3 (x=0, 0.05) materials exhibit good performance as SOFC anode materials between 500-800°C, with Rct values at 500°C in dry H2 of 3.15 and 6.33 ohm*cm2 respectively. The catalytic performance of these perovskite anodes is directly related to electronic conductivity, as concluded from composite anode performance.