X-ray Beam Induced Current Measurements for Multi-Modal X-ray Microscopy of Solar Cells

X-ray beam induced current (XBIC) measurements allow mapping of&#160;the nanoscale performance of electronic devices such as solar cells. Ideally, XBIC is ...

Deutsches Elektronen-Synchrotron

The magnetic field sensors enabling birds to extract orientational information from the Earth's magnetic field have remained enigmatic. Our previously published results from homing pigeons have made us suggest that the iron containing sensory dendrites in the inner dermal lining of the upper beak are a candidate structure for such an avian magnetometer system. Here we show that similar structures occur in two species of migratory birds (garden warbler, Sylvia borin and European robin, Erithacus rubecula) and a non-migratory bird, the domestic chicken (Gallus gallus). In all these bird species, histological data have revealed dendrites of similar shape and size, all containing iron minerals within distinct subcellular compartments of nervous terminals of the median branch of the Nervus ophthalmicus. We also used microscopic X-ray absorption spectroscopy analyses to identify the involved iron minerals to be almost completely Fe III-oxides. Magnetite (Fe II/III) may also occur in these structures, but not as a major Fe constituent. Our data suggest that this complex dendritic system in the beak is a common feature of birds, and that it may form an essential sensory basis for the evolution of at least certain types of magnetic field guided behavior.

Avian magnetoreception: elaborate iron mineral containing dendrites in the upper beak seem to be a common feature of birds.

X-ray scanning microscopy relies on intensive nanobeams generated by imaging a highly brilliant synchrotron radiation source onto the sample with a nanofocusing X-ray optic. Here, using a Gaussian model for the central cone of an undulator source, the nanobeam generated by refractive X-ray lenses is modeled in terms of size, flux and coherence. The beam properties are expressed in terms of the emittances of the storage ring and the lateral sizes of the electron beam. Optimal source parameters are calculated to obtain efficient and diffraction-limited nanofocusing. With decreasing emittance, the usable fraction of the beam for diffraction-limited nanofocusing experiments can be increased by more than two orders of magnitude compared with modern storage ring sources. For a diffraction-limited storage ring, nearly the whole beam can be focused, making these sources highly attractive for X-ray scanning microscopy. 

Hard X-ray nanofocusing at low-emittance synchrotron radiation sources.

Microprobe X-ray fluorescence tomography was used to investigate metal poison deposition in individual, intact and industrially deactivated fluid catalytic cracking (FCC) particles at two differing catalytic life-stages. 3 D multi-element imaging, at submicron resolution was achieved by using a large-array Maia fluorescence detector. Our results show that Fe, Ni and Ca have significant concentration at the exterior of the FCC catalyst particle and are highly co-localized. As concentrations increase as a function of catalytic life-stage, the deposition profiles of Fe, Ni, and Ca do not change significantly. V has been shown to penetrate deeper into the particle with increasing catalytic age. Although it has been previously suggested that V is responsible for damaging the zeolite components of FCC particles, no spatial correlation was found for V and La, which was used as a marker for the embedded zeolite domains. This suggests that although V is known to be detrimental to zeolites in FCC particles, a preferential interaction does not exist between the two.

X-ray Fluorescence Tomography of Aged Fluid-Catalytic-Cracking Catalyst Particles Reveals Insight into Metal Deposition Processes.

Elemental distribution images acquired by imaging X-ray fluorescence analysis can contain high degrees of redundancy and weakly discernible correlations. In this article near real-time non-negative matrix factorization (NMF) is described for the analysis of a number of data sets acquired from samples of a bi-modal α+β Ti-6Al-6V-2Sn alloy. NMF was used for the first time to reveal absorption artefacts in the elemental distribution images of the samples, where two phases of the alloy, namely α and β, were in superposition. The findings and interpretation of the NMF results were confirmed by Monte Carlo simulation of the layered alloy system. Furthermore, it is shown how the simultaneous factorization of several stacks of elemental distribution images provides uniform basis vectors and consequently simplifies the interpretation of the representation. 

Non-negative matrix factorization for the near real-time interpretation of absorption effects in elemental distribution images acquired by X-ray fluorescence imaging.

Arsenic (As) pollution is a serious concern worldwide. Recent studies under environmentally relevant conditions revealed that, in the aquatic plant Ceratophyllum demersum, pigments are the first observable target of toxicity, prior to any effect on photosynthetic parameters or to oxidative stress. Lethal toxicity was initiated by a change of As species and their distribution pattern in various tissues. Here, the localization of As was investigated at the subcellular level through X-ray fluorescence using a submicron beam and a Maia detector. Further, it was possible to obtain useful tissue structural information from the ratio of the tomogram of photon flux behind the sample to the tomogram of Compton scattering. The micro-X-ray fluorescence tomograms showed that As predominantly accumulated in the nucleus of the epidermal cells in young mature leaves exposed to sublethal 1 µM As. This suggests that As may exert toxic effects in the nucleus, for example, by interfering with nucleic acid synthesis by replacing phosphorous with As. At higher cellular concentrations, As was mainly stored in the vacuole, particularly in mature leaves. An analysis of precursors of chlorophyll and degradation metabolites revealed that the observed decrease in chlorophyll concentration was associated with hindered biosynthesis, and was not due to degradation. Coproporphyrinogen III could not be detected after exposure to only 0.5 µM As. Levels of subsequent precursors, for example, protoporphyrin IX, Mg-protoporphyrin, Mg-protoporphyrin methyl ester, and divinyl protochlorophyllide, were significantly decreased at this concentration as well, indicating that the pathway was blocked upstream of tetrapyrrole synthesis.

Analysis of sublethal arsenic toxicity to Ceratophyllum demersum: subcellular distribution of arsenic and inhibition of chlorophyll biosynthesis.

The high brilliance of third-generation synchrotron sources increases the demand for faster detectors to utilize the available flux. The Maia detector is an advanced imaging scheme for energy-dispersive detection realising dwell times per image-pixel as low as 50 µs and count rates higher than 10 × 10 s. In this article the integration of such a Maia detector in the Microprobe setup of beamline P06 at the storage ring PETRA III at the Deutsches Elektronen-Synchrotron (DESY) in Hamburg, Germany, is described. The analytical performance of the complete system in terms of rate-dependent energy resolution, scanning-speed-dependent spatial resolution and lower limits of detection is characterized. The potential of the Maia-based setup is demonstrated by key applications from materials science and chemistry, as well as environmental science with geological applications and biological questions that have been investigated at the P06 beamline.

Fast X-ray microfluorescence imaging with submicrometer-resolution integrating a Maia detector at beamline P06 at PETRA III.

In recent years, X-ray ptychography has been established as a valuable tool for high-resolution imaging. Nevertheless, the spatial resolution and sensitivity in coherent diffraction imaging are limited by the signal that is detected over noise and over background scattering. Especially, coherent imaging of weakly scattering specimens suffers from incoherent background that is generated by the interaction of the central beam with matter along its propagation path in particular close to and inside of the detector. Common countermeasures entail evacuated flight tubes or detector-side beamstops, which improve the experimental setup in terms of background reduction or better coverage of high dynamic range in the diffraction patterns. Here, we discuss an alternative approach: we combine two ptychographic scans with and without beamstop and reconstruct them simultaneously taking advantage of the complementary information contained in the two scans. We experimentally demonstrate the potential of this scheme for hard X-ray ptychography by imaging a weakly scattering object composed of catalytic nanoparticles and provide the analysis of the signal-to-background ratio in the diffraction patterns.

Beamstop-based low-background ptychography to image weakly scattering objects.

Due to their short wavelength, X-rays can in principle be focused down to a few nanometres and below. At the same time, it is this short wavelength that puts stringent requirements on X-ray optics and their metrology. Both are limited by today's technology. In this work, we present accurate at wavelength measurements of residual aberrations of a refractive X-ray lens using ptychography to manufacture a corrective phase plate. Together with the fitted phase plate the optics shows diffraction-limited performance, generating a nearly Gaussian beam profile with a Strehl ratio above 0.8. This scheme can be applied to any other focusing optics, thus solving the X-ray optical problem at synchrotron radiation sources and X-ray free-electron lasers.

Perfect X-ray focusing via fitting corrective glasses to aberrated optics.

The future of solid-state lighting can be potentially driven by applications of InGaN/GaN core-shell nanowires. These heterostructures provide the possibility for fine-tuning of functional properties by controlling a strain state between mismatched layers. We present a nondestructive study of a single 400 nm-thick InGaN/GaN core-shell nanowire using two-dimensional (2D) X-ray Bragg ptychography (XBP) with a nanofocused X-ray beam. The XBP reconstruction enabled the determination of a detailed three-dimensional (3D) distribution of the strain in the particular nanowire using a model based on finite element method. We observed the strain induced by the lattice mismatch between the GaN core and InGaN shell to be in the range from -0.1% to 0.15% for an In concentration of 30%. The maximum value of the strain component normal to the facets was concentrated at the transition region between the main part of the nanowire and the GaN tip. In addition, a variation in misfit strain relaxation between the axial growth and in-plane directions was revealed.

X-ray Bragg Ptychography on a Single InGaN/GaN Core-Shell Nanowire.

Synchrotron radiation phase-contrast computed nanotomography (nano-CT) and two- and three-dimensional (2D and 3D) nanoscopic X-ray fluorescence (nano-XRF) were used to investigate the internal distribution of engineered cobalt nanoparticles (Co NPs) in exposed individuals of the nematode Caenorhabditis elegans. Whole nematodes and selected tissues and organs were 3D-rendered: anatomical 3D renderings with 50 nm voxel size enabled the visualization of spherical nanoparticle aggregates with size up to 200 nm within intact C. elegans. A 20 × 37 nm high-brilliance beam was employed to obtain XRF elemental distribution maps of entire nematodes or anatomical details such as embryos, which could be compared with the CT data. These maps showed Co NPs to be predominantly present within the intestine and the epithelium, and they were not colocalized with Zn granules found in the lysosome-containing vesicles or Fe agglomerates in the intestine. Iterated XRF scanning of a specimen at 0° and 90° angles suggested that NP aggregates were translocated into tissues outside of the intestinal lumen. Virtual slicing by means of 2D XRF tomography, combined with holotomography, indicated presumable presence of individual NP aggregates inside the uterus and within embryos.

Combined Computed Nanotomography and Nanoscopic X-ray Fluorescence Imaging of Cobalt Nanoparticles in Caenorhabditis elegans.

Wavefront errors of rotationally parabolic refractive X-ray lenses made of beryllium (Be CRLs) have been recovered for various lens sets and X-ray beam configurations. Due to manufacturing via an embossing process, aberrations of individual lenses within the investigated ensemble are very similar. By deriving a mean single-lens deformation for the ensemble, aberrations of any arbitrary lens stack can be predicted from the ensemble with \bar{\sigma} = 0.034λ. Using these findings the expected focusing performance of current Be CRLs are modeled for relevant X-ray energies and bandwidths and it is shown that a correction of aberrations can be realised without prior lens characterization but simply based on the derived lens deformation. The performance of aberration-corrected Be CRLs is discussed and the applicability of aberration-correction demonstrated over wide X-ray energy ranges.

Nanofocusing with aberration-corrected rotationally parabolic refractive X-ray lenses.

A new fast X-ray absorption spectroscopy scanning method was recently implemented at the Hard X-ray Microprobe endstation P06, PETRA III, DESY, utilizing a Maia detector. Spectromicroscopy maps were acquired with spectra for X-ray absorption near-edge structure (XANES) acquisition in the sub-second regime. The method combines XANES measurements with raster-scanning of the sample through the focused beam. The order of the scanning sequence of the axes, one beam energy axis and two (or more) spatial axes, is a variable experimental parameter and, depending on it, the dwell at each location can be either single and continuous (if the energy axis is the inner loop) or in shorter discontinuous intervals (if a spatial axis is innermost). The combination of improved spatial and temporal resolution may be necessary for rapidly changing samples, e.g. for following in operando chemical reactions or samples highly susceptible to beam damage where the rapid collection of single XANES spectra avoids issues with the emergence of chemical changes developing from latent damage. This paper compares data sets collected on a specially designed test pattern and a geological thin-section scanning the energy as inner, middle and outer axis in the sequence. The XANES data of all three scanning schemes is found to show excellent agreement down to the single-pixel level.

Fast XANES fluorescence imaging using a Maia detector.

Chelation of iron and zinc in wheat as phytates lowers their bio-accessibility. Steeping and germination (15 °C, 120 h) lowered phytate content from 0.96% to only 0.81% of initial dry matter. A multifactorial experiment in which (steeped/germinated) wheat was subjected to different time (2-24 h), temperature (20-80 °C) and pH (2.0-8.0) conditions showed that hydrothermal processing of germinated (15 °C, 120 h) wheat at 50 °C and pH 3.8 for 24 h reduced phytate content by 95%. X-ray absorption near-edge structure imaging showed that it indeed abolished chelation of iron to phytate. It also proved that iron was oxidized during steeping, germination and hydrothermal processing. It was further shown that zinc and iron bio-accessibility were respectively 3 and 5% in wheat and 27 and 37% in hydrothermally processed wheat. Thus, hydrothermal processing of (germinated) wheat paves the way for increasing elemental bio-accessibility in whole grain-based products.

The impact of steeping, germination and hydrothermal processing of wheat (Triticum aestivum L.) grains on phytate hydrolysis and the distribution, speciation and bio-accessibility of iron and zinc elements.

Gerald Falkenberg

Deutsches Elektronen-Synchrotron

X-ray Beam Induced Current Measurements for Multi-Modal X-ray Microscopy of Solar Cells