Electronic patterns found on Pb quantum islands can serve as a template to grow nanoclusters spontaneously. Nanoclusters of different materials display various growth behaviors. Compared to Pb adatoms, Ag nanoclusters can be fabricated in a perfectly ordered form. In the work, using density-functional theory, we demonstrate that how the interaction between adatom and substrate affects the atomic motion on the Pb quantum islands of electronic origin.

Single Wall Carbon Nanotubes (SWCNTs) are often synthesized as bundles and are chemically modified via either covalent or non-covalent approaches to prevent aggregation, improve their dispersability and tune their physical properties for a potential application. The spatial distribution and effect of covalent addends on the electronic properties of SWCNTs was characterized using a Scanning Tunneling Microscope but with limited success. The effect of sample preparation was questioned as it often involves sonicating the SWCNTs in either an organic or an aqueous medium. Sonication of SWCNTs in certain common solvents was found to alter their electronic properties. The solvent molecules are broken down via a radical pathway during sonicating leading to the formation of new species that interact with the SWCNTs and in some cases with the catalytic material present. New species such as iron chlorides and oxygen, which were formed for example in o-dichlorobenzene and water respectively, caused p-type doping. Doping was characterized by Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). A blue shift in the D* mode along with a shift to lower binding energy in the C1s peak was observed from Raman spectroscopy and XPS respectively. The reactivity of the radicals (formed during sonication) towards the structure of the SWCNTs was also investigated. Radicals formed during sonication of certain chlorinated aromatic solvents lead to the formation of sonochemical polymers, which interacted heavily with the SWCNTs. These interactions, which can be the source of features commonly associated with covalent functionalization, were thwarted by a washing protocol and were found to be non-covalent in nature. The observations are of relevance towards understanding an inadvertent chemical modification during chemical processing, which can impact reproducibility of results that involve wet-chemical processes. However, with such knowledge of the chemistry involved during sample preparation the occurrence of doping can be either circumvented or appropriately used. / Thesis / Doctor of Philosophy (PhD)

Rechargeable lithium-ion batteries are a staple of modern society, providing power to a significant portion of the world's electronics and rapidly replacing older power sources. The advent of widely available electric cars with batteries of up to 200 kWh, with an increasing emphasis on fast charging, has only increased their importance. Lithium-ion battery electronic and ionic properties are largely determined by the microstructure of the battery electrode film and can be heavily influenced by relatively small variations in film makeup, including the formation of voids or distribution of carbon and binder. Prior to this research, electrical properties, which are some of the most important characteristics to battery cost, performance, and safety, were either difficult or, in the case of contact resistance, impossible to directly measure. This dissertation focuses on the development and use of a micro-surface probe for measurement and mapping of lithium-ion battery film electronic characteristics. The measurement apparatus, inversion and mapping routines, and experimental data presented provide manufacturers and researchers with a better understanding of battery heterogeneity and the influence of microstructure on electrical properties. The micro-surface probe was used to map spatial variation on both a macro and micro scale; compare physical, electrical, and ionic properties; and validate tests that were previously used to estimate electronic parameters. Experiments on commercial-quality battery electrode films showed higher micro-heterogeneity than was previously assumed by a significant margin. Additionally, electronic and ionic properties were shown to not always be inversely related and some physical explanations for observed variation were explored. Macro-variations were measured and shown to exist across electrode films which were previously assumed to be uniform. Finally a comparison to the mechanical peel test, a common test used in industry as a proxy measurement of electrical contact resistance, proved the peel test to be inconclusive and showed that it will not always accurately reflect electrical properties of films. Direct measurements of both electrical conductivity and contact resistance provide a new and important tool to advance understanding and development of lithium-ion batteries. The magnitude of the measured resistivities and their significant variation demonstrates that a better understanding of film properties is needed and will significantly influence our understanding of modern battery parameters and the effects of manufacturing techniques on battery performance.

Unlike the binary compound, where the simple charge transfer between cation and anion, or the ternary compound, which is composed of two binary compound semiconductors with a common cation or anion and whose electronic structures usually can be derived from those of the two constituent binary compounds with some modifications, the electronic property of quaternary compound is quiet complicated and interesting because of its complex charge transfer due to the electronegativity differences of its composed atoms. In this thesis, the first-principles pseudofunction (PSF) method and the first-principles molecular dynamics (MD) method are used to investigate the complicated variations of the electronic properties of three kinds of quaternary compounds, namely titanates [Ba1-xSrxTiO3 (BSTO) and Pb1-xSrxTiO3 (PSTO)], manganites [La1-xSrxMnO3 (LSMO) and La1-xCaxMnO3 (LCMO)], and (SiC)1-x(AlN)x. First, for BSTO and PSTO titanates, the first-principles calculation results and O K-edge x-ray absorption near edge structure (XANES) measurements are used to study their electronic structures. Because the valence band maximum (VBM) and conduction band minimum (CBM) are composed of O-p and Ti-d partial densities of states (PDOS), respectively, the bowing upward of calculated band gaps are related to the bowing downward of the Ti-O bond lengths for both of BSTO and PSTO, though for PSTO Pb-p PDOS also contributes to states near CBM. The substitutions of Sr by Ba in BSTO and by Pb in PSTO are quiet different, and it is because Pb atom has two extra valence electrons and a larger electronegativity than other cations. Second, we provide a new interpretation of the insulator-like to metal-like and anti-ferromagnetic to ferromagnetic transitions with Sr and Ca doping concentrations of La1-xSrxMnO3 and La1-xCaxMnO3, which is based on the variations of the Sr and Ca induced delocalization of the Mn majority-spin eg subband and the lowering of the Mn minority-spin t2g subband down to the Fermi energy (EF). Moreover, this study also suggests that the magnetic properties of manganites result from a detailed balancing between the O-mediated super-exchange mechanism that favors anti-ferromagnetism and the delocalized-state mediated Mn-spin coupling that favors ferromagnetism. Third, for (SiC)1-x(AlN)x superlattice, where SiC and AlN layers arranged alternatively along a common c-axis, our analysis shows subtle charge transfer among Si, C, Al and N ions and the band gap is not linear but bows downwards with respect to x. The calculated results suggest that the direct band gap of (SiC)1-x(AlN)x can be tuned over a wide range from 2.97eV to 6.28eV. Thus, (SiC)1-x(AlN)x is potentially useful for optoelectronic applications. It can be inferred from the calculated electronic properties of the above three kinds of quaternary compounds, the subtle charge transfer is because of differing electronegativities of constituent atoms, especially cations, and the relative valence state of the dopant with respect to the host cation. The subtle charge transfer also influences the magnetic properties of these hole-doped manganites. Moreover, the quaternary compounds have four kinds of atoms with different electronegativities and relative orbital energies, the complicated competition and balancing between the occupation of orbitals and charge transfer render the electronic properties of these material unable to be predicted from constituent binary oxides/semiconductors or even ternary compounds. For example, even though Pb substitutes Sr only in Pb1-xSrxTiO3, the effective charges of Ti and O are significantly altered.