Mapping topological magnetization and magnetic skyrmions

A 2014 study by the US Department of Energy conducted at Lawrence Berkeley National Laboratory estimated that U.S. data centers consumed 70 billion kWh of electricity[1]. This represents about 1.8% of the total U.S. electricity consumption. Putting this in perspective 70 billion kWh of electricity is the equivalent of roughly 8 big nuclear reactors, or around double the nation's solar panel output[2]. Developing new memory technologies capable of reducing this power consumption would be greatly beneficial as our demand for connectivity increases in the future. One newly emerging candidate for an information carrier in low power memory devices is the magnetic skyrmion. This magnetic texture is characterized by its specific non-trivial topology, giving it particle-like characteristics. Recent experimental work has shown that these skyrmions can be stabilized at room temperature and moved with extremely low electrical current densities. This rapidly developing field requires new measurement techniques capable of determining the topology of these textures at greater speed than previous approaches. In this dissertation, I give a brief introduction to the magnetic structures found in Fe/Gd multilayered systems. I then present newly developed techniques that streamline the analysis of Lorentz Transmission Electron Microscopy (LTEM) data. These techniques are then applied to further the understanding of the magnetic properties of these Fe/Gd based multilayered systems. This dissertation includes previously published and unpublished co-authored material

Probing Light Atoms at Sub-nanometer Resolution: Realization of Scanning Transmission Electron Microscope Holography

Atomic resolution imaging in transmission electron microscopy (TEM) and scanning TEM (STEM) of light elements in electron-transparent materials has long been a challenge. Biomolecular materials, for example, are rapidly altered when illuminated with electrons. These issues have driven the development of TEM and STEM techniques that enable the structural analysis of electron beam-sensitive and weakly scattering nano-materials. Here, we demonstrate such a technique, STEM holography, capable of absolute phase and amplitude object wave measurement with respect to a vacuum reference wave. We use an amplitude-dividing nanofabricated grating to prepare multiple spatially separated electron diffraction probe beams focused at the sample plane, such that one beam transmits through the specimen while the others pass through vacuum. We raster-scan the diffracted probes over the region of interest. We configure the post specimen imaging system of the microscope to diffraction mode, overlapping the probes to form an interference pattern at the detector. Using a fast-readout, direct electron detector, we record and analyze the interference fringes at each position in a 2D raster scan to reconstruct the complex transfer function of the specimen, t(x). We apply this technique to image a standard target specimen consisting of gold nanoparticles on a thin amorphous carbon substrate, and demonstrate 2.4 angstrom resolution phase images. We find that STEM holography offers higher phase-contrast of the amorphous material while maintaining Au atomic lattice resolution when compared with high angle annular dark field STEM.Comment: 9 pages, 5 figures in main text, 1 supplemental figure in the appendi

Serum Proteins Enhance Dispersion Stability and Influence the Cytotoxicity and Dosimetry of ZnO Nanoparticles in Suspension and Adherent Cancer Cell Models

Agglomeration and sedimentation of nanoparticles (NPs) within biological solutions is a major limitation in their use in many downstream applications. It has been proposed that serum proteins associate with the NP surface to form a protein corona that limits agglomeration and sedimentation. Here, we investigate the effect of fetal bovine serum (FBS) proteins on the dispersion stability, dosimetry, and NP-induced cytotoxicity of cationic zinc oxide nanoparticles (nZnO) synthesized via forced hydrolysis with a core size of 10 nm. Two different in vitro cell culture models, suspension and adherent, were evaluated by comparing a phosphate buffered saline (PBS) nZnO dispersion (nZnO/PBS) and an FBS-stabilized PBS nZnO dispersion (nZnO – FBS/PBS). Surface interactions of FBS on nZnO were analyzed via spectroscopic and optical techniques. Fourier transformed infrared spectroscopy (FTIR) confirmed the adsorption of negatively charged protein components on the cationic nZnO surface through the disappearance of surfaced-adsorbed carboxyl functional groups and the subsequent detection of vibrational modes associated with the protein backbone of FBS-associated proteins. Further confirmation of these interactions was noted in the isoelectric point shift of the nZnO from the characteristic pH of 9.5 to a pH of 6.1.In nZnO – FBS/PBS dispersions, the FBS reduced agglomeration and sedimentation behaviors to impart long-term improvements (\u3e24 h) to the nZnO dispersion stability. Furthermore, mathematical dosimetry models indicate that nZnO – FBS/PBS dispersions had consistent NP deposition patterns over time unlike unstable nZnO/PBS dispersions. In suspension cell models, the stable nZnO – FBS/PBS dispersion resulted in a ~33 % increase in the NP-induced cytotoxicity for both Jurkat leukemic and Hut-78 lymphoma cancer cells. In contrast, the nZnO – FBS/PBS dispersion resulted in 49 and 71 % reductions in the cytotoxicity observed towards the adherent breast (T-47D) and prostate (LNCaP) cancer cell lines, respectively. Presence of FBS in the NP dispersions also increased the reactive oxygen species generation. These observations indicate that the improved dispersion stability leads to increased NP bioavailability for suspension cell models and reduced NP sedimentation onto adherent cell layers resulting in more accurate in vitro toxicity assessments

Role of Oxygen Defects on the Magnetic Properties of Ultra-Small Sn\u3csub\u3e1−x\u3c/sub\u3eFe\u3csub\u3ex\u3c/sub\u3eO\u3csub\u3e2\u3c/sub\u3e Nanoparticles

Although the role of oxygen defects in the magnetism of metal oxide semiconductors has been widely discussed, it is been difficult to directly measure the oxygen defect concentration of samples to verify this. This work demonstrates a direct correlation between the photocatalytic activity of Sn1−xFexO2 nanoparticles and their magnetic properties. For this, a series of ~2.6 nm sized, well characterized, single-phase Sn1−xFexO2 crystallites with x = 0−0.20 were synthesized using tin acetate, urea, and appropriate amounts of iron acetate. X-ray photoelectron spectroscopy confirmed the concentration and 3+ oxidation state of the doped Fe ions. The maximum magnetic moment/Fe ion, μ, of 1.6 × 10−4 μB observed for the 0.1% Fe doped sample is smaller than the expected spin-only contribution from either high or low spin Fe3+ ions, and μ decreases with increasing Fe concentration. This behavior cannot be explained by the existing models of magnetic exchange. Photocatalytic studies of pure and Fe-doped SnO2 were used to understand the roles of doped Fe3+ ions and of the oxygen vacancies and defects. The photocatalytic rate constant k also showed an increase when SnO2 nanoparticles were doped with low concentrations of Fe3+, reaching a maximum at 0.1% Fe, followed by a rapid decrease of k for further increase in Fe%. Fe doping presumably increases the concentration of oxygen vacancies, and both Fe3+ ions and oxygen vacancies act as electron acceptors to reduce e−-h+ recombination and promote transfer of electrons (and/or holes) to the nanoparticle surface, where they participate in redox reactions. This electron transfer from the Fe3+ ions to local defect density of states at the nanoparticle surface could develop a magnetic moment at the surface states and leads to spontaneous ferromagnetic ordering of the surface shell under favorable conditions. However, at higher doping levels, the same Fe3+ ions might act as recombination centers causing a decrease of both k and magnetic moment μ

Dopant Spin States and Magnetism of Sn\u3csub\u3e1−x\u3c/sub\u3eFe\u3csub\u3ex\u3c/sub\u3eO\u3csub\u3e2\u3c/sub\u3e Nanoparticles

This work reports detailed investigations of a series of ∼2.6 nm sized, Sn1−xFexO2 crystallites with x = 0–0.10 using Mossbauer spectroscopy, x-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance spectroscopy (EPR), and magnetometry to determine the oxidation state of Fe dopants and their role in the observed magnetic properties. The magnetic moment per Fe ion μ was the largest ∼6.48 × 10−3 μB for the sample with the lowest (0.001%) Fe doping, and it showed a rapid downward trend with increasing Fe doping. Majority of the Fe ions are in 3+ oxidation state occupying octahedral sites. Another significant fraction of Fe dopant ions is in 4+ oxidation state and a still smaller fraction might be existing as Fe2+ ions, both occupying distorted sites, presumably in the surface regions of the nanocrystals, near oxygen vacancies. These studies also suggest that the observed magnetism is not due to exchange coupling between Fe3+ spins. A more probable role for the multi-valent Fe ions may be to act as charge reservoirs, leading to charge transfer ferromagnetism

Comparative metal oxide nanoparticle toxicity using embryonic zebrafish

AbstractEngineered metal oxide nanoparticles (MO NPs) are finding increasing utility in the medical field as anticancer agents. Before validation of in vivo anticancer efficacy can occur, a better understanding of whole-animal toxicity is required. We compared the toxicity of seven widely used semiconductor MO NPs made from zinc oxide (ZnO), titanium dioxide, cerium dioxide and tin dioxide prepared in pure water and in synthetic seawater using a five-day embryonic zebrafish assay. We hypothesized that the toxicity of these engineered MO NPs would depend on physicochemical properties. Significant agglomeration of MO NPs in aqueous solutions is common making it challenging to associate NP characteristics such as size and charge with toxicity. However, data from our agglomerated MO NPs suggests that the elemental composition and dissolution potential are major drivers of toxicity. Only ZnO caused significant adverse effects of all MO particles tested, and only when prepared in pure water (point estimate median lethal concentration=3.5–9.1mg/L). This toxicity was life stage dependent. The 24h toxicity increased greatly (∼22.7 fold) when zebrafish exposures started at the larval life stage compared to the 24h toxicity following embryonic exposure. Investigation into whether dissolution could account for ZnO toxicity revealed high levels of zinc ion (40–89% of total sample) were generated. Exposure to zinc ion equivalents revealed dissolved Zn2+ may be a major contributor to ZnO toxicity