<p>I want delay publication of my dissertation until April 30 2013. Thanks.</p> / <p>Strontium titanate (SrTiO₃) has a wide range of applications in the electronic industry and attracts growing world-widely interest recently because of novel discoveries at its surfaces, interfaces and with selected dopants. The understanding of some of the structural properties of SrTiO₃ and its optical properties have been lagging due to limited characterization techniques available to study single monolayers and dopants in this material.</p> <p>In the present thesis, pure SrTiO₃ single crystals with (2x1) and c(4x2) surface patterns were synthesized and samples (Pr, Al) doped SrTiO₃ were prepared through ion implantation. The atomic and electronic structures of these samples were investigated by various high-resolution imaging and spectroscopic techniques available in an aberration-corrected transmission electron microscope. Particularly, the direct imaging of individual light atoms and vacancies within a bulk material containing heavier elements was demonstrated for the first time via the STEM-annular dark-field (ADF)/annular bright-field (ABF) images. In addition, the first electron energy-loss spectroscopy (EELS) 2-dimensional maps of dopants located in a lattice were obtained. These results provided a solid foundation regarding the mechanism of red light emission in doped SrTiO₃. More importantly, a new experimental approach allowing the effective extraction of weak EELS signals from low-dimensional defects was developed and successfully applied to understand the chemical state and coordination of Ti cations within a single monolayer on a reconstructured SrTiO₃surface and the local defect configurations of injected Pr⁺ and Al⁺ ions within SrTiO₃ single crystals.</p> / Doctor of Philosophy (PhD)

abstract: Non-stoichiometric oxides play a critical role in many catalytic, energy, and sensing technologies, providing the ability to reversibly exchange oxygen with the ambient environment through the creation and annihilation of surface oxygen vacancies. Oxygen exchange at the surfaces of these materials is strongly influenced by atomic structure, which varies significantly across nanoparticle surfaces. The studies presented herein elucidate the relationship between surface structure behaviors and oxygen exchange reactions on ceria (CeO2) catalyst materials. In situ aberration-corrected transmission electron microscopy (AC-TEM) techniques were developed and employed to correlate dynamic atomic-level structural heterogeneities to local oxygen vacancy activity. A model Ni/CeO2 catalyst was used to probe the role of a ceria support during hydrocarbon reforming reactions, and it was revealed that carbon formation was inhibited on Ni metal nanoparticles due to the removal of lattice oxygen from the ceria support and subsequent oxidation of adsorbed decomposed hydrocarbon products. Atomic resolution observations of surface oxygen vacancy creation and annihilation were performed on CeO2 nanoparticle surfaces using a novel time-resolved in situ AC-TEM approach. Cation displacements were found to be related to oxygen vacancy creation and annihilation, and the most reactive surface oxygen sites were identified by monitoring the frequency of cation displacements. In addition, the dynamic evolution of CeO2 surface structures was characterized with high temporal resolution AC-TEM imaging, which resulted in atomic column positions and occupancies to be determined with a combination of spatial precision and temporal resolution that had not previously been achieved. As a result, local lattice expansions and contractions were observed on ceria surfaces, which were likely related to cyclic oxygen vacancy activity. Finally, local strain fields on CeO2 surfaces were quantified, and it was determined that local strain enhanced the ability of a surface site to create oxygen vacancies. Through the characterization of dynamic surface structures with advanced AC-TEM techniques, an improvement in the fundamental understanding of how ceria surfaces influence and control oxygen exchange reactions was obtained. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2019