Development of small particle speciation for nuclear forensics by soft X-ray scanning transmission spectromicroscopy.

Synchrotron radiation spectromicroscopy provides a combination of submicron spatial resolution and chemical sensitivity that is well-suited to analysis of heterogeneous nuclear materials. The chemical and physical characteristics determined by scanning transmission X-ray microscopy (STXM) are complementary to information obtained from standard radiochemical analysis methods. In addition, microscopic quantities of radioactive material can be characterized rapidly by STXM with minimal sample handling and intrusion, especially in the case of particulate materials. The STXM can accommodate a diverse range of samples including wet materials, complex mixtures, and small quantities of material contained in a larger matrix. In these cases, the inventory of species present in a sample is likely to carry information on its process history; STXM has the demonstrated capability to identify contaminants and sample matrices. Operating in the soft X-ray regime provides particular sensitivity to the chemical state of specimens containing low-Z materials, via the K-edges of light elements. Here, recent developments in forensics-themed spectromicroscopy, sample preparation, and data acquisition methods at the Molecular Environmental Science Beamline 11.0.2 of the Advanced Light Source are described. Results from several initial studies are presented, demonstrating the capability to identify the distribution of the species present in heterogeneous uranium-bearing materials. Future opportunities for STXM forensic studies and potential methodology development are discussed.

The non-random walk of chiral magnetic charge carriers in artificial spin ice.

The flow of magnetic charge carriers (dubbed magnetic monopoles) through frustrated spin ice lattices, governed simply by Coulombic forces, represents a new direction in electromagnetism. Artificial spin ice nanoarrays realise this effect at room temperature, where the magnetic charge is carried by domain walls. Control of domain wall path is one important element of utilizing this new medium. By imaging the transit of domain walls across different connected 2D honeycomb structures we contribute an important aspect which will enable that control to be realized. Although apparently equivalent paths are presented to a domain wall as it approaches a Y-shaped vertex from a bar parallel to the field, we observe a stark non-random path distribution, which we attribute to the chirality of the magnetic charges. These observations are supported by detailed statistical modelling and micromagnetic simulations. The identification of chiral control to magnetic charge path selectivity invites analogy with spintronics.

Chemically and geographically distinct solid-phase iron pools in the Southern Ocean.

Iron is a limiting nutrient in many parts of the oceans, including the unproductive regions of the Southern Ocean. Although the dominant fraction of the marine iron pool occurs in the form of solid-phase particles, its chemical speciation and mineralogy are challenging to characterize on a regional scale. We describe a diverse array of iron particles, ranging from 20 to 700 nanometers in diameter, in the waters of the Southern Ocean euphotic zone. Distinct variations in the oxidation state and composition of these iron particles exist between the coasts of South Africa and Antarctica, with different iron pools occurring in different frontal zones. These speciation variations can result in solubility differences that may affect the production of bioavailable dissolved iron.

Real space soft x-ray imaging at 10 nm spatial resolution.

Using Fresnel zone plates made with our robust nanofabrication processes, we have successfully achieved 10 nm spatial resolution with soft x-ray microscopy. The result, obtained with both a conventional full-field and scanning soft x-ray microscope, marks a significant step forward in extending the microscopy to truly nanoscale studies.

Correlation between the magnetic imaging of cobalt nanoconstrictions and their magnetoresistance response.

Scanning transmission x-ray microscopy (STXM) and magnetoresistance (MR) measurements are used to investigate the magnetic behavior of a nanoconstriction joining two micrometric electrodes (a pad and a wire). The reversal of the magnetization under variable external static magnetic fields is imaged. By means of a detailed analysis of the STXM images at the nanocontact area, the MR is calculated, based on diffusive anisotropic-MR. This MR agrees well with that obtained from electrical transport measurements, allowing a direct correlation between the MR signal and the magnetic reversal of the system. The magnetization behavior depends on the sample thickness and constriction dimensions. In 40 nm-thick samples, with 20 × 175 nm(2) contact areas, the magnetization at the two sides of the constriction forms a net angle of 90°, with a progressive evolution of the magnetization structure between the electrodes during switching. The MR in those cases has a more peaked shape than with 20 nm-thick electrodes and 10 × 80 nm(2) contact areas, where the magnetization forms 180° between them, with a wide domain wall pinned at the constriction. As a consequence of this configuration, a plateau in the MR is observed for about 20 Oe.

Advances in the detection of as in environmental samples using low energy X-ray fluorescence in a scanning transmission X-ray microscope: arsenic immobilization by an Fe(II)-oxidizing freshwater bacteria.

Speciation and quantitative mapping of elements, organic and inorganic compounds, and mineral phases in environmental samples at high spatial resolution is needed in many areas of geobiochemistry and environmental science. Scanning transmission X-ray microscopes (STXMs) provide a focused beam which can interrogate samples at a fine spatial scale. Quantitative chemical information can be extracted using the transmitted and energy-resolved X-ray fluorescence channels simultaneously. Here we compare the relative merits of transmission and low-energy X-ray fluorescence detection of X-ray absorption for speciation and quantitative analysis of the spatial distribution of arsenic(V) within cell-mineral aggregates formed by Acidovorax sp. strain BoFeN1, an anaerobic nitrate-reducing Fe(II)-oxidizing ß-proteobacteria isolated from the sediments of Lake Constance. This species is noted to be highly tolerant to high levels of As(V). Related, As-tolerant Acidovorax-strains have been found in As-contaminated groundwater wells in Bangladesh and Cambodia wherein they might influence the mobility of As by providing sorption sites which might have different properties as compared to chemically formed Fe-minerals. In addition to demonstrating the lower detection limits that are achieved with X-ray fluorescence relative to transmission detection in STXM, this study helps to gain insights into the mechanisms of As immobilization by biogenic Fe-mineral formation and to further the understanding of As-resistance of anaerobic Fe(II)-oxidizing bacteria.

Images of a spin-torque-driven magnetic nano-oscillator.

We present the first space- and time-resolved images of the spin-torque-induced steady-state oscillation of a magnetic vortex in a spin-valve nanostructure. We find that the vortex structure in a nanopillar is considerably more complicated than the 2D idealized structure often-assumed, which has important implications for the driving efficiency. The sense of the vortex gyration is uniquely determined by the vortex core polarity, confirming that the spin-torque acts as a source of negative damping even in such a strongly nonuniform magnetic system. The orbit radius is ∼10 nm, in agreement with micromagnetic simulations.

PolLux: a new facility for soft x-ray spectromicroscopy at the Swiss Light Source.

We report on the successful installation and operation of a scanning transmission x-ray microspectroscope (STXM) at the PolLux facility at the Swiss Light Source. This integration of an advanced STXM with improved sample handling capabilities and a novel beamline provides unique capabilities. PolLux uses linearly or circularly polarized x-rays from a bending magnet with an extended photon energy range (200-1400 eV). It is therefore well suited to determine a sample's quantitative chemical composition, molecular orientation, or thickness of organic as well as condensed matter materials. The local magnetic state of magnetic thin films is accessible through fast helicity switching by steering the electron beam off axis through the bending magnet. Ex vacuo girder movers allow fast and highly reproducible (<1 microm) alignment of the instrument with respect to the photon beam. The present spatial resolution is approximately 20 nm, limited by the zone plates utilized. The instrument has the stability and positional resolution to operate with much higher resolution optics as it becomes available. In addition to characterization experiments, we present several typical examples from materials research and environmental science to exemplify the capabilities.

A high-resolution chemical and structural study of framboidal pyrite formed within a low-temperature bacterial biofilm.

A novel, anaerobically grown microbial biofilm, scraped from the inner surface of a borehole, 1474 m below land surface within a South African, Witwatersrand gold mine, contains framboidal pyrite. Water flowing from the borehole had a temperature of 30.9 degrees C, a pH of 7.4, and an Eh of -50 mV. Examination of the biofilm using X-ray diffraction, field emission gun scanning electron microscope equipped for energy dispersive X-ray microanalysis demonstrated that the framboids formed within a matrix of bacteria and biopolymers. Focused ion beam sectioning of framboids followed by NEXAFS measurements using both scanning transmission X-ray microscopy and X-ray photoelectron emission microscopy revealed that the pyrite crystals grew within an organic carbon matrix consisting of exopolysaccharides and possibly extracellular DNA, which is intuitively important in sulfide mineral diagenesis. Growth of individual pyrite crystals within the framboid occurred inside organic templates confirms the association between framboidal pyrite and organic materials in low-temperature diagenetic environments and the important role of microenvironments in biofilms in regulating geochemical cycles.

Direct observation of spin-torque driven magnetization reversal through nonuniform modes.

We present time-resolved x-ray images with 30 nm spatial and 70 ps temporal resolution, which reveal details of the spatially resolved magnetization evolution in nanoscale samples of various dimensions during reversible spin-torque switching processes. Our data in conjunction with micromagnetic simulations suggest a simple unified picture of magnetic switching based on the motion of a magnetic vortex. With decreasing size of the magnetic element the path of the vortex core moves from inside to outside of the nanoelement, and the switching process evolves from a curled nonuniform to an increasingly uniform mode.

Synchronized and configurable source of electrical pulses for x-ray pump-probe experiments.

A method is described for the generation of software tunable patterns of nanosecond electrical pulses. The bipolar, high repetition rate (up to 250 MHz), fast rise time (<30 ps), square pulses are suitable for applications such as the excitation sequence in dynamic pump-probe experiments. Synchronization with the time structure of a synchrotron facility is possible as well as fine control of the relative delay in steps of 10 ps. The pulse generator described here is used to excite magnetic nanostructures with current pulses. Having an excitation system which can match the high repetition rate of a synchrotron allows for utilization of the full x-ray flux and is needed in experiments which require a large photon flux. The fast rise times allow for picosecond time resolution in pump-probe experiments. All pulse pattern parameters are configurable by software.

Software defined photon counting system for time resolved x-ray experiments.

The time structure of synchrotron radiation allows time resolved experiments with sub-100 ps temporal resolution using a pump-probe approach. However, the relaxation time of the samples may require a lower repetition rate of the pump pulse compared to the full repetition rate of the x-ray pulses from the synchrotron. The use of only the x-ray pulse immediately following the pump pulse is not efficient and often requires special operation modes where only a few buckets of the storage ring are filled. We designed a novel software defined photon counting system that allows to implement a variety of pump-probe schemes at the full repetition rate. The high number of photon counters allows to detect the response of the sample at multiple time delays simultaneously, thus improving the efficiency of the experiment. The system has been successfully applied to time resolved scanning transmission x-ray microscopy. However, this technique is applicable more generally.

pi-electron ferromagnetism in metal-free carbon probed by soft x-ray dichroism.

Elemental carbon represents a fundamental building block of matter and the possibility of ferromagnetic order in carbon has attracted widespread attention. However, the origin of magnetic order in such a light element is only poorly understood and has puzzled researchers. We present a spectromicroscopy study at room temperature of proton irradiated metal-free carbon using the elemental and chemical specificity of x-ray magnetic circular dichroism. We demonstrate that the magnetic order in the investigated system originates only from the carbon pi-electron system.

In situ azimuthal rotation device for linear dichroism measurements in scanning transmission x-ray microscopy.

A novel miniature rotation device used in conjunction with a scanning transmission x-ray microscope is described. It provides convenient in situ sample rotation to enable measurements of linear dichroism at high spatial resolution. The design, fabrication, and mechanical characterization are presented. This device has been used to generate quantitative maps of the spatial distribution of the orientation of proteins in several different spider and silkworm silks. Specifically, quantitative maps of the dichroic signal at the C 1s-->pi* (amide) transition in longitudinal sections of the silk fibers give information about the spatial orientation, degree of alignment, and spatial distribution of protein peptide bonds. A new approach for analyzing the dichroic signal to extract orientation distributions, in addition to magnitudes of aligned components, is presented and illustrated with results from Nephila clavipes dragline spider silk measured using the in situ rotation device.

Magnetic vortex core reversal by excitation with short bursts of an alternating field.

The vortex state, characterized by a curling magnetization, is one of the equilibrium configurations of soft magnetic materials and occurs in thin ferromagnetic square and disk-shaped elements of micrometre size and below. The interplay between the magnetostatic and the exchange energy favours an in-plane, closed flux domain structure. This curling magnetization turns out of the plane at the centre of the vortex structure, in an area with a radius of about 10 nanometres--the vortex core. The vortex state has a specific excitation mode: the in-plane gyration of the vortex structure about its equilibrium position. The sense of gyration is determined by the vortex core polarization. Here we report on the controlled manipulation of the vortex core polarization by excitation with small bursts of an alternating magnetic field. The vortex motion was imaged by time-resolved scanning transmission X-ray microscopy. We demonstrate that the sense of gyration of the vortex structure can be reversed by applying short bursts of the sinusoidal excitation field with amplitude of about 1.5 mT. This reversal unambiguously indicates a switching of the out-of-plane core polarization. The observed switching mechanism, which can be understood in the framework of micromagnetic theory, gives insights into basic magnetization dynamics and their possible application in data storage.

Time-resolved imaging of spin transfer switching: beyond the macrospin concept.

Time-resolved images of the magnetization switching process in a spin transfer structure, obtained by ultrafast x-ray microscopy, reveal the limitations of the macrospin model. Instead of a coherent magnetization reversal, we observe switching by lateral motion of a magnetic vortex across a nanoscale element. Our measurements reveal the fundamental roles played independently by the torques due to charge and spin currents in breaking the magnetic symmetry on picosecond time scales.

Interferometer-controlled scanning transmission X-ray microscopes at the Advanced Light Source.

Two new soft X-ray scanning transmission microscopes located at the Advanced Light Source (ALS) have been designed, built and commissioned. Interferometer control implemented in both microscopes allows the precise measurement of the transverse position of the zone plate relative to the sample. Long-term positional stability and compensation for transverse displacement during translations of the zone plate have been achieved. The interferometer also provides low-distortion orthogonal x, y imaging. Two different control systems have been developed: a digital control system using standard VXI components at beamline 7.0, and a custom feedback system based on PC AT boards at beamline 5.3.2. Both microscopes are diffraction limited with the resolution set by the quality of the zone plates. Periodic features with 30 nm half period can be resolved with a zone plate that has a 40 nm outermost zone width. One microscope is operating at an undulator beamline (7.0), while the other is operating at a novel dedicated bending-magnet beamline (5.3.2), which is designed specifically to illuminate the microscope. The undulator beamline provides count rates of the order of tens of MHz at high-energy resolution with photon energies of up to about 1000 eV. Although the brightness of a bending-magnet source is about four orders of magnitude smaller than that of an undulator source, photon statistics limited operation with intensities in excess of 3 MHz has been achieved at high energy resolution and high spatial resolution. The design and performance of these microscopes are described.

Optimization of scanning transmission X-ray microscopy for the identification and quantitation of reinforcing particles in polyurethanes.

The morphology, size distributions, spatial distributions, and quantitative chemical compositions of co-polymer polyol-reinforcing particles in a polyurethane have been investigated with scanning transmission X-ray microscopy (STXM). A detailed discussion of microscope operating procedures is presented and ways to avoid potential artifacts are discussed. Images at selected photon energies in the C 1s, N 1s and O 1s regions allow unambiguous identification of styrene-acrylonitrile-based (SAN) copolymer and polyisocyanate polyaddition product-based (PIPA) reinforcing particles down to particle sizes at the limit of the spatial resolution (50 nm). Quantitative analysis of the chemical composition of individual reinforcing particles is achieved by fitting C 1s spectra to linear combinations of reference spectra. Regression analyses of sequences of images recorded through the chemically sensitive ranges of the C 1s, N 1s and O 1s spectra are used to generate quantitative compositional maps, which provide a fast and effective means of investigating compositional distributions over a large number of reinforcing particles. The size distribution of all particles determined by STXM is shown to be similar to that determined by TEM. The size distributions of each type of reinforcing particle, which differ considerably, were obtained by analysis of STXM images at chemically selective energies.