The correlation of structure and electronic properties near the surface of transition metal oxides

The strong couplings between different degrees of freedom are believed to be responsible for novel and complex phenomena discovered in transition metal oxides (TMOs). The physical complexity is directly responsible for their tunability. Creating surfaces/interfaces add an additional ' man-made' twist, approaching the quantum phenomena of correlated materials. ^ The dissertation focused on the structural and electronic properties in proximity of surface of three prototype TMO compounds by using three complementary techniques: scanning tunneling microscopy, angle-resolved photoelectron spectroscopy and low energy electron diffraction, particularly emphasized the effects of broken symmetry and imperfections like defects on the coupling between charge and lattice degrees of freedom. ^ Ca1.5Sr0.5RuO4 is a layered ruthenate with square lattice and at the boundary of magnetic/orbital instability in Ca2-xSrxRuO4. That the substitution of Sr 2+ with Ca2+ causing RuO6 rotation narrows the dxy band width and changes the Fermi surface topology. Particularly, the γ(dxy) Fermi surface sheet exhibited hole-like in Ca1.5Sr0.5RuO4 in contrast to electron-like in Sr2RuO4, showing a strong charge-lattice coupling. ^ Na0.75CoO2 is a layered cobaltite with triangular lattice exhibiting extraordinary thermoelectric properties. The well-ordered CoO2-terminated surface with random Na distribution was observed. However, lattice constants of the surface are smaller than that in bulk. The surface density of states (DOS) showed strong temperature dependence. Especially, an unusual shift of the minimum DOS occurs below 230 K, clearly indicating a local charging effect on the surface. ^ Cd2Re2O7 is the first known pyrochlore oxide superconductor (Tc ∼ 1K). It exhibited an unusual second-order phase transition occurring at TS1 = 200 K and a controversial first-order transition at TS2 = 120 K. While bulk properties display large anomalies at TS1 but rather subtle and sample-dependent changes at TS2, the surface DOS near the EF show no change at T s1 but a substantial increase below TS2---a complete reversal as the signature for the transitions. We argued that crystal imperfections, mainly defects, which were considerably enhanced at the surface, resulted in the transition at TS2. ^

Evidence of Recent Phosphorus Enrichment in Surface Soils of Taylor Slough and Northeast Everglades National Park

Everglades National Park (ENP) is the last hydrologic unit in the series of impounded marsh units that make up the present-day Everglades. The ENP receives water from upstream Water Conservation Areas via canals and water control structures that are highly regulated for flood control, water supply, wildlife management, concerns about poor water quality and the potential for downstream ecosystem degradation. Recent surveys of surface soils in ENP, designed for random sampling for spatial analysis of soil nutrients, did not sample proximate to inflow structures and thus did not detect increased soil phosphorus associated with these water conveyances. This study specifically addressed these areas in a focused sampling effort at three key inflow points in northeast ENP which revealed elevated soil TP proximate to inflows. Two transects extending down Shark River Slough and one down Taylor Slough (a natural watershed of particular ecological value) were found to have soil TP levels in excess of 500 mg kg−1—a threshold above which P enrichment is indicated. These findings suggest the negative impact of elevated water (P) from surface flows and support the assertion that significant soil TP enrichment is occurring in Taylor Slough and other areas of northeastern ENP.