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<p>The traditional semiconductor device scaling based on Moore’s law is reaching its physical limits. New materials hosting rich physical phenomena such as correlated electronic behavior may be essential to identify novel approaches for information processing. The tunable band structures in such systems enables the design of hardware for neuromorphic computing. Strongly correlated perovskite nickelates (ReNiO3) represent a class of quantum materials that possess exotic electronic properties such as metal-to-insulator transitions. In this thesis, detailed studies of NdNiO3 thin films from wafer-scale synthesis to structure characterization and to electronic device demonstration will be discussed.</p> <p>Atomic layer deposition (ALD) of correlated oxide thin films is essential for emerging electronic technologies and industry. We reported the scalable ALD growth of neodymium nickelate (NdNiO3) with high crystal quality using Nd(iPrCp)3, Ni(tBu2-amd)2 and ozone (O3) as precursors. By controlling various growth parameters such as precursor dose time and reactor temperature, we have optimized ALD condition for perovskite phase of NdNiO3­. We studied the structure and electrical properties of ALD NdNiO3 films epitaxially grown on LaAlO3 and confirmed their properties were comparable to those synthesized by physical vapor deposition methods. </p> <p>ReNiO3 undergoes a dramatic phase transition by hydrogen doping with catalytic electrodes independent of temperature. The electrons from hydrogen occupy Ni 3<em>d</em> orbitals and create strongly correlated insulating state with resistance changes up to eight orders of magnitudes. At room temperature, protons remain in the lattice locally near catalytic electrodes and can move by electrical fields due to its charge. The effect of high-speed voltage pulses on the migration of protons in NdNiO3 devices is discussed. After voltage pulses were applied with changing the voltage magnitude in nanosecond time scale, the resistance changes of the nickelate device were investigated. </p> <p>Reconfigurable perovskite nickelate devices were demonstrated and a single device can switch between multiple electronic functions such as neuron, synapse, resistor, and capacitor controlled by a single electrical pulse. Raman spectroscopy showed that differences in local proton distributions near the Pd electrode leads to different functions. This body of results motivates the search for novel materials where subtle compositional or structural differences can enable different gaps that can host neuromorphic functions.</p>

Grasslands provide fundamental ecosystem services in many arid and semi-arid regions of the world, but are experiencing rapid increases in fire activity making them highly susceptible to post-fire accelerated soil erosion by wind. A quantitative assessment that integrates fire-wind erosion feedbacks is therefore needed to account for vegetation change, soil biogeochemical cycling, air quality, and landscape evolution. We investigated the applicability of a novel tracer technique – the use of multiple rare earth elements (REE) - to quantify aeolian soil erosion and to identify sources and sinks of wind-blown sediments in a burned and unburned shrub-grass transition zone in the Chihuahuan desert, NM, USA. Results indicate that the horizontal mass flux of wind-borne sediment increased approximately three times following the fire. The REE-tracer analysis of aeolian sediments shows that an average 88% of the horizontal mass flux in the control area was derived from bare microsites, whereas at the burned site it was derived from shrub and bare microsites, 42% and 39% respectively. The vegetated microsites, which were predominantly sinks of aeolian sediments in the unburned areas, became sediment sources following the fire. The burned areas exhibited a spatial homogenization of sediment tracers, highlighting a potential negative feedback on landscape heterogeneity induced by shrub encroachment into grasslands. Though fires are known to increase aeolian sediment transport, accompanying changes in the sources and sinks of wind-borne sediments likely influence biogeochemical cycling and land degradation dynamics. Our experiment demonstrated that REEs can be used as reliable tracers for field-scale aeolian studies. / Geology / Accompanied by one compressed .zip file: MET_Tower_Data.zip

Magnets play a major role in our rapidly developing world of technology. Electric motors and generators, transformers, data storage devices, MRI machines, cellphones, and NMR are some of the many applications for magnets. However, almost all the magnets currently being used have rare-earth heavy metals in them. Despite their high-energy product, the presence of rare-earth metals increases the cost significantly. Also, the processes involved in the mining of rare-earth metals are hazardous to the environment, and to all life forms. In the past few decades, oxide based magnets have gained a lot of attention as potential replacements for the rare-earth magnets. Oxide based magnetic nanocrystals are attracting a lot of attention as a potential replacement for rare-earth magnets. They are stable in ambient condition and their manufacturing cost is very low when compared to the rare-earth magnets. My work deals with the synthesis of core-shell magnetic structure for high frequency applications (Chapter 1) and the synthesis of high energy product magnetic nanocrystals (Chapter 2) and the synthesis of soft magnetic nanocrystals for high frequency measurement. NiZn ferrite, a soft oxide based magnet cannot be directly implied at high frequencies as they fail at the frequency which over the MHz range. On the other hand, BaZn ferrite is a Y-type magnets, which is robust at higher frequencies. Therefore, using the latter magnet as a protective shell for core material, made of former magnet, enables us to manufacture a cheap solution to the rare-earth magnets used in our cell phones and other devices that work on high frequency signals. On the other hand, successful coating of a very soft magnetic material on a hard-magnetic core increases the total energy product of the magnetic composite, which enhances its versatility. / Mechanical Engineering

Karst aquifers are dynamic hydrologic systems which are sensitive to short-term recharge events (storms) and heterogeneous recharge characteristics (point recharge at sinks, irregular soil thicknesses). These aquifers are highly productive yet also vulnerable to contamination, in large part because the conduit network is a significant unknown for predicting karst flow paths. To address these uncertainties, two adjacent karst springs, Tippery Spring and Near Tippery Spring, were monitored to better understand flow and source mixing characteristics. The two springs in central Pennsylvania’s Nittany Valley have similar discharges and are only 65 meters apart, yet they show unique behaviors in terms of water chemistry and discharge response to storms. First examined for flow characterization in 1971 by Shuster and White, the springs were analyzed in this study using high-resolution logging and new tracers such as rare earth element (REEs) and Ca/Zr ratios. This research contributes to the field of karst hydrology through innovative water sampling and monitoring techniques to investigate karst recharge and flow behavior along with conduit flow models incorporating multiple calibration target datasets such as water temperature and dye tracing. Stable isotope signatures (δD & δ18O) of storm water samples at the two springs varied based on storm intensity, but also due to their unique recharge behaviors. Increased spring discharge preceded the arrival of storm water as conduits were purged of pre-storm water, indicated by no change in isotopic composition on the rising limb. The isotopic signature then became progressively more enriched at both springs, indicating storm water recharge. At Tippery, this enrichment began around peak flow, sooner than at Near Tippery where enrichment began during the descending limb. Thus, isotopes indicated a stronger surface connection at Tippery Spring. Storm intensity also affected the relative contribution of recharging water reaching both springs, with a larger storm producing a larger recharge signature compared to a smaller storm. At Tippery Spring, for a short time the majority of emerging water was storm water, which may indicate a reversal in water exchange between the conduits and the surrounding matrix, an important consideration in karst contaminant transport. Two natural tracers were applied in new ways for this study: Ca/Zr ratios and REE patterns. Both tracers provided additional information about flow paths and recharge sources as they varied during the storm hydrograph. Ca/Zr ratios changed in timing and intensity with storm intensity, and both springs exhibited a decline in Ca/Zr ratios as calcium-rich carbonate matrix water was displaced by zirconium-rich storm recharge water from sinking streams off the clastic upland ridges. Being a storm water arrival indicator in clastic-ridge-fed Valley and Ridge springs, this relationship made Ca/Zr ratios a useful substitute for stable water isotopes while also providing information on source area. In response to storm water recharge, REE concentrations increased with the arrival of storm water. The timing and magnitude of concentration increases were influenced both by the degree of surface connectivity intrinsic to each spring and the intensity of the recharge event. Elevated REE concentrations persisted after other parameters recovered to pre-storm levels, suggesting water which has interacted with either the local carbonate matrix or the upland siliciclastics. These slower flow paths recharging the two springs were not apparent from other geochemical parameters. This study illustrated the relationships among multiple tracers to understand source waters in different periods of storm hydrographs. A flow and transport model using the Finite Element Subsurface Flow Model (FEFLOW) was calibrated using quantitative dye trace and high resolution temperature data to simulate the connection between a sinking stream and Tippery Spring. Dye was injected at the sink and monitored at the spring while temperature data was collected using loggers at both the sink and the spring. FEFLOW was used to simulate the connection between sink and spring through varying conduit geometries, sink and spring discharges, conduit conductivity, conduit cross-sectional area, matrix transmissivity, matrix porosity, and dispersivity. Single conduit models reproduced larger peak and recession concentrations than observed. A forked conduit model diverted flow from the main conduit, reducing the concentration of dye reaching the spring, provided a better match. Latin Hypercube sensitivity analysis indicated that dye concentration breakthrough curves were most sensitive to conduit conductivity and less sensitive to other model parameters. Temperature data from high-resolution loggers at the sink and spring were then incorporated into the model scenarios to reproduce seasonal spring temperature using the conduit configuration fit to the dye trace. Simulated temperature signals at the spring were sensitive to parameters in addition to conduit conductivity, most notably matrix transmissivity and inflow rates at the sink. The dual approach to karst model calibration using a temperature model set up from an initial dye trace results in greater model confidence due to a limited possible range in conduit conductivity. This study improved conceptual and numerical models for karst by examining how data from storm events and tracers can be used to better understand recharge and flow paths. / Geoscience

Many grasslands in arid and semi-arid regions are undergoing rapid changes in vegetation, including encroachment of woody plants and invasive grasses, which can alter the rates and patterns of fire and sediment transport in these landscapes. We investigated the spatial distribution of sediments at the scale of vegetated microsites for three years following a prescribed fire using a multiple rare earth element (REE) tracer-based approach in a shrub-grass transition zone in the northern Chihuahuan desert (New Mexico, USA). To this end, we applied REE tracers – holmium, europium, and ytterbium on shrub, grass, and bare microsites, respectively in March 2016. Soil samples were collected from both burned and control (not burned) sites before (March) and after (June) the annual windy season, from 2016 through 2018. Results indicate that although the horizontal mass flux (HMF) of wind-borne sediment increased approximately threefold in the first windy season following the fire, and the HMF of both plots were not significantly different after three windy seasons. Comparing REE concentrations in sediments from both plots over the three years and three annual windy seasons, we observed a post-fire shift in source and sink dynamics of sediments. The tracer analysis of wind-borne sediments indicated that the source of the HMF in the burned site was mostly derived from shrub microsites following the fire, whereas the bare microsites were the major contributors for aeolian sediment in control areas. The shift in sources and sinks, and the spatial homogenization of REEs indicate that the removal of shrub vegetation resulted in sediment redistribution to the bare microsites even three years after the prescribed fire. The findings of this study will improve our understanding of post-fire geomorphic processes at a microsite scale in a grassland ecosystem undergoing land degradation induced by shrub encroachment. / Geology

The synthesis and electropositive metal (Y, Lu, La, Zr, Hf) chemistry of two rigid dianionic xanthene-based ligands, 4,5-bis(2,4,6-triisopropylanilido)- -2,7-di-tert-butyl-9,9-dimethylxanthene (XN2) and 4,5-bis(2,4,6-triisopropylphenylphosphido)- 2,7-di-tert-butyl-9,9-dimethylxanthene (XP2) have been explored. The reaction of the pro-ligand H2XN2 with [Y(CH2SiMe2R)3(THF)2] (R = Me or Ph) produced the monoalkyl yttrium complexes [(XN2)Y(CH2SiMe3)- (THF)].(O(SiMe3)2)x (3, x = 1-1.5) and [(XN2)Y(CH2SiMe2Ph)(THF)].(O- (SiMe3)2) (4). Neutral 3 reacted with excess AlMe3 to yield [(XN2)Y{(m- Me)2AlMe2}(THF)].O(SiMe3)2 (5.O(SiMe3)2), which is thermally robust, and transfer of the XN2 ligand to aluminum was not observed. However, [(XN2)- AlMe].(O(SiMe3)2)0.5 (6.(O(SiMe3)2)0.5) was synthesized via the reaction of H2XN2 with AlMe3. Compounds 3, 5 and 6 were characterized by X-ray crystallography, and neutral 3, while being poorly active for ethylene polymerization, was highly active for both intra- and inter-molecular hydroamination with a variety of substrates. The synthesis of the pro-ligand H2XP2 was achieved via reduction of 4,5-bis(2,4,6-triisopropylphenylchlorophosphino)-2,7-di-tert-butyl-9,9-dimethylxanthene (XP2Cl2; 7). Double deprotonation of H2XP2 (8) with excess KH yielded the potassium salt, [K2XP2(DME)2.5] (9), which when stirred in THF followed by recrystallization from hexanes, produced the tetrametallic complex, [K4(XP2)2(THF)4] (10) featuring a central K4P4 cage. The reaction of [K2XP2(DME)2.5] (9) with [YI3(THF)3.5] yielded a mixture of products including [(XP2)YI(THF)2] (11) and tris(2,4,6-triisopropylphenylphosphinidene) (P3Tripp3); pure 11 could be isolated in low yield by extraction with a minimum volume of hexanes or O(SiMe3)2. In the solid state, complex 11 reveals a face-capped trigonal bipyramidal geometry at yttrium, in which the xanthene backbone is planar and adopts a large angle (85 degrees) between the P(1)/C(4)/C(5)/P(2) and P(1)/Y/P(2) planes. Due to the successful synthesis and hydroamination catalysis achieved with the XN2 ligand in combination with yttrium, the chemistry of XN2 was further explored using both smaller (Lu) and larger (La) rare earth elements. The alkane elimination reaction of H2XN2 with [Lu(CH2SiMe3)3(THF)2], followed by crystallization from O(SiMe3)2, yielded [(XN2)Lu(CH2SiMe3)(THF)].(O- (SiMe3)2)1.5 (12.(O(SiMe3)2)1.5). By contrast, lanthanum complexes of the XN2 dianion were prepared by salt metathesis; treatment of H2XN2 with excess KH in DME produced the dipotassium salt, [K2(XN2)(DME)x] (2; x = 2-2.5), and subsequent reaction with [LaCl3(THF)3] afforded [{(XN2)LaCl- (THF)}x].(O(SiMe3)2)0.25x (13.(O(SiMe3)2)0.25x; x = 1 or 2) after crystallization from O(SiMe3)2. Compound 13.(O(SiMe3)2)0.25x reacted with two equivalents of LiCH2SiMe3, to form the dialkyl-`ate' complex, [Li(THF)x][(XN2)- La(CH2SiMe3)2].Toluene.LiCl (14.Toluene.LiCl; x = 3). Both 12 and 14 (x = 4) were structurally characterized by X-ray crystallography, and were evaluated as catalysts for intramolecular hydroamination. While compound 14 showed poor activity, the neutral lutetium alkyl complex, 12, is highly active for both intramolecular hydroamination and more challenging intermolecular hydroamination. Like the yttrium analogue, 3, reactions with unsymmetrical alkenes yielded Markovnikov products. Additionally, it is noteworthy that the activity of 12 surpassed that of 3 in the reaction of diphenylacetylene with 4-tert-butylbenzylamine. The reaction of H2XN2 with [Zr(NMe2)4], followed by crystallization from O(SiMe3)2, yielded [(XN2)Zr(NMe2)2].(O(SiMe3)2)0.5 (15.(O(SiMe3)2)0.5). The zirconium dimethyl complex [(XN2)ZrMe2] (16) was accessed via two routes; either by treatment of 15.(O(SiMe3)2)0.5 with excess AlMe3, or by reaction of 15.(O(SiMe3)2)0.5 with excess Me3SiCl, affording [(XN2)ZrCl2] (17), followed by the subsequent reaction of 17 with 2 equivalents of MeLi. The reaction of 16 with one equivalent of B(C6F5)3 or [CPh3][B(C6F5)4] yielded cationic [(XN2)- ZrMe][MeB(C6F5)3] (18) and [(XN2)ZrMe(arene)][B(C6F5)4] (19; arene = n6-benzene, n6-toluene or bromobenzene), respectively. Both 18 and 19 are active for ethylene polymerization under 1 atm of ethylene at 24 and 80 degree Celcius in toluene, with activities ranging from 23.5{883 kg/(mol.atm.h), yielding polymers with weight average molecular weights (Mw) of 71{88 kg/mol and polydispersities (Mw/Mn) of 3.94-4.67. / Thesis / Doctor of Philosophy (PhD) / Pincer ligands are defined as meridionally-coordinating tridentate ligands, and are typically mono-, di- or tri-anionic. This thesis is focused on the synthesis and reactivity of rigid dianionic pincer ligands with an NON- or POP-donor array, with particular emphasis on rare earth and group 4 transition metal complexes. This work explores the effect that these rigid ligands have on the reactivity of the resulting metal complexes and the thermal stability of the solid state structures. Both neutral and cationic mono alkyl complexes have been isolated, and several are highly active catalysts for intra- and intermolecular hydroamination or ethylene polymerization.