X-ray Nanoprobe Research Articles

Local lattice distortions in single Co-implanted ZnO nanowires

This work reports on the local structure of as-implanted and thermally-treated single Co:ZnO nanowires studied using a hard X-ray nanoprobe. Although the Co ions are incorporated into the wurtzite ZnO lattice, X-ray absorption near edge structure data show high structural disorder in the as-implanted nanowires compared with the annealed ones. In particular, extended X-ray absorption fine structure from single wires reveals a lattice distortion around Zn sites of the as-implanted nanowires, which involves an expansion of the stable wurtzite lattice. The observed local lattice response confirms good recovery of the implantation-induced damage within the ZnO lattice through a thermal treatment.

Ex- and In-situ Metrology Based on the Shack-Hartmann Technique for Sub-nanometric Metrology

In recent years, there has been growing interest in the design of electron accelerators in order to reduce beam emittance and to increase photon brilliance (from third-generation synchrotron sources to free electron lasers). This has increased the coherent properties of the beam and has opened up new branches of microscopy and spectroscopy at nanometer-length scales. The X-ray nano probe is going to be an important tool for future research, hence there has been substantial research carried out in order to develop nano focusing optics of diffraction-limited performance.

Hard X-ray nanoprobe investigations of the subtissue metal distributions within Daphnia magna

The unique potential of nanoscale elemental imaging of major/minor and trace-level elemental distributions within thin biological tissue sections of the ecotoxicological model organism Daphnia magna is demonstrated by synchrotron radiation nano-X-ray fluorescence (nano-XRF). The applied highly specialized sample preparation method, coupled with the high spatial resolution (∼180nm) and high X-ray photon flux (6 × 10(11) photons/s) available at the European Synchrotron Radiation Facility (ESRF) ID22NI beamline proved to be critical for the high-quality visualization of (trace-)metal distributions on the submicron level within the target structures of interest. These include the branchial sacs on the thoracic appendages (epipodites) of D. magna, which are osmoregulatory regions where ion exchange occurs. For the main element of interest (Zn), detection limits of 0.7ppm (3ag) was reached in fast-scanning mode using an acquisition time of 0.3s/pixel. As demonstrated, synchrotron radiation nano-XRF revealed the elemental distributions of Ca, Fe, and Zn within this osmoregulatory region on the submicron scale, aiding the exploration of possible detoxification mechanisms of Zn within D. magna at the subtissue level.

A hard X-ray nanospectroscopy station at SPring-8 BL39XU

We upgraded the hard X-ray spectroscopy beamline BL39XU at SPring-8 by installing Kirkpatrick-Baez mirrors to equip it with submicron-focusing capability. At the new experimental end-station located 74 m from the undulator source, an X-ray nanoprobe with a size of 120 × 100 nm2 has become available at 5–16 keV. This upgrade is fully compatible with the X-ray polarization tunability and helicity-switching between right- and left-circular polarizations; these are unique features of the beamline, which is equipped with a diamond X-ray phase retarder. A spatial resolution of ≈100 nm for X-ray absorption fine structure and X-ray magnetic circular dichroism (XMCD) spectroscopy has been achieved. We show a magnetization reversal process of an individual magnetic dot in bit-patterned perpendicular recording media using element-specific XMCD magnetization measurements to demonstrate the performance of the new station.

Design of the X-ray Nanoprobe Beamline at the Taiwan Photon Source

The X-ray Nanoprobe (XNP) Beamline Project has been granted as one of the first seven beamlines at the Taiwan Photon Source (TPS). The XNP beamline and the associated instruments are designed to utilize the highly brilliant TPS light source for resolving the atomic, chemical and electronic structures of semiconductor-based devices with tens nm spatial resolution in tomographic and nondestructive manners. The beamline optics is deliberated to deliver focal spot around 40 nm with photon flux in the level of 1010 photons/sec. The stability of the focal position will be highly improved by operating the double crystal monochromator (DCM) in horizontally diffracting geometry, with minor sacrifice in energy resolution. The relative movement between sample and focusing optics is controlled by ultra-precise linear translational/flexure stages and monitored by laser interferometers. The end stations will provide conventional X-ray probes including, X-ray fluorescence (XRF), X-ray absorption fine structures (XAFS), X-ray excited optical luminescence (XEOL), and the emerging techniques, such as the Bragg-ptychography (BP) to overcome the spatial resolution set by the focusing optics. A novel scanning mechanism incorporating surface diffraction and BP for mapping the 3D interfacial strains is under development. The XNP beamline and associated instruments are expected to take the first synchrotron light by the end of 2015.

High-resolution fluorescence mapping of impurities in historical zinc oxide pigments: hard X-ray nanoprobe applications to the paints of Pablo Picasso

Here for the first time we describe the use of high resolution nanoprobe X-ray fluorescence (XRF) mapping for the analysis of artists’ paints, hierarchically complex materials typically composed of binder, pigments, fillers, and other additives. The work undertaken at the nanoprobe sought to obtain highly spatially resolved, highly sensitive mapping of metal impurities (Pb, Cd, Fe, and other metals) in submicron particles of zinc oxide pigments used in early 20th century artists’ tube paints and enamel paints, with particular emphasis on Ripolin, a popular brand of French house paint used extensively by Pablo Picasso and some of his contemporaries. Analysis revealed that the Zn oxide particles only contain a little Fe, proving that the highest quality Zn oxide pigment, free of Pb and Cd, was used for Ripolin house paints as well as artists’ paints. Nanoprobe XRF mapping also demonstrated that artists’ tube paints generally have more abundant fillers and additional whites (based on Pb, Ti, Ca) than Ripolin paints, which contain mostly pure zinc oxide. The chemical characterization of paints at the nanoscale opens the path to a better understanding of their fabrication and chemical reactivity.

Optimization of multilayer Laue lenses for a scanning X-ray microscope

Multilayer Laue lenses (MLLs) have demonstrated great capabilities for efficiently focusing hard X-rays down to the nanometer scale. Optimized use of MLLs in a scanning X-ray microscope requires careful consideration of a number of practical parameters other than resolution and efficiency in order to optimize the microscope's performance and scientific throughput. Here, relationships among the apodization effect owing to the presence of a beamstop, the monochromaticity requirement and the allowable working distance are discussed, as well as their impacts on the performance of the optics. Based on these discussions, optimal MLL schemes aiming at 10 nm resolution for a scanning X-ray microscope for the Hard X-ray Nanoprobe (HXN) beamline at National Synchrotron Light Source II are presented.

A hard X-ray nanoprobe beamline for nanoscale microscopy.

The Hard X-ray Nanoprobe Beamline (or Nanoprobe Beamline) is an X-ray microscopy facility incorporating diffraction, fluorescence and full-field imaging capabilities designed and operated by the Center for Nanoscale Materials and the Advanced Photon Source at Sector 26 of the Advanced Photon Source at Argonne National Laboratory. This facility was constructed to probe the nanoscale structure of biological, environmental and material sciences samples. The beamline provides intense focused X-rays to the Hard X-ray Nanoprobe (or Nanoprobe) which incorporates Fresnel zone plate optics and a precision laser sensing and control system. The beamline operates over X-ray energies from 3 to 30 keV, enabling studies of most elements in the periodic table, with a particular emphasis on imaging transition metals.

Aligned hemozoin crystals in curved clusters in malarial red blood cells revealed by nanoprobe X-ray Fe fluorescence and diffraction

The human malaria parasite Plasmodium falciparum detoxifies the heme byproduct of hemoglobin digestion in infected red blood cells by sequestration into submicron-sized hemozoin crystals. The crystal is composed of heme units interlinked to form cyclic dimers via reciprocal Fe─O (propionate) bonds. Templated hemozoin nucleation was envisaged to explain a classic observation by electron microscopy of a cluster of aligned hemozoin crystals within the parasite digestive vacuole. This dovetails with evidence that acylglycerol lipids are involved in hemozoin nucleation in vivo, and nucleation of β-hematin, the synthetic analogue of hemozoin, was consistently induced at an acylglycerol-water interface via their {100} crystal faces. In order to ascertain the nature of hemozoin nucleation in vivo, we probed the mutual orientations of hemozoin crystals in situ within RBCs using synchrotron-based X-ray nanoprobe Fe fluorescence and diffraction. The X-ray patterns indicated the presence of hemozoin clusters, each comprising several crystals aligned along their needle c axes and exposing {100} side faces to an approximately cylindrical surface, suggestive of nucleation via a common lipid layer. This experimental finding, and the associated nucleation model, are difficult to reconcile with recent reports of hemozoin formation within lipid droplets in the digestive vacuole. The diffraction results are verified by a study of the nucleation process using emerging tools of three-dimensional cellular microscopy, described in the companion paper.

Deciphering the Resistance-Counteracting Functions of Ferroquine in Plasmodium falciparum-Infected Erythrocytes.

The aminoquinoline chloroquine (CQ) has been widely used for treating malaria since World War II. Resistance to CQ began to spread around 1957 and is now found in all malarious areas of the world. CQ resistance is caused by multiple mutations in the Plasmodium falciparum chloroquine resistance transporter (PfCRT). These mutations result in an increased efflux of CQ from the acidic digestive vacuole (DV) to the cytosol of the parasite. This year, we proposed a strategy to locate and quantify the aminoquinolines in situ within infected red blood cells (iRBCs) using synchrotron based X-ray nanoprobe fluorescence. Direct measurements of unlabeled CQ and ferroquine (FQ) (a ferrocene-CQ conjugate, extremely active against CQ-resistant strains) enabled us to evidence fundamentally different transport mechanisms from the cytosol to the DV between CQ and FQ in the CQ-susceptible strain HB3. These results inspired the present study of the localization of CQ and FQ in the CQ-resistant strain W2. The introduction of the ferrocene core in the lateral side chain of CQ has an important consequence: the transporter is unable to efflux FQ from the DV. We also found that resistant parasites treated by FQ accumulate a sulfur-containing compound, credibly glutathion, in their DV.

Chemical Heterogeneities on La0.6Sr0.4CoO3−δ Thin Films—Correlations to Cathode Surface Activity and Stability

La0.6Sr0.4CoO3−δ(LSC) thin film cathodes synthesized by pulsed laser deposition at 450°C (LSC_450°C) and 650°C (LSC_650°C) exhibit different electrochemical performance. The origin of the differences in the oxygen reduction activity and stability of these cathodes is investigated on the basis of their surface chemistry and their surface atomic and electronic structures. Angle resolved X-ray photoelectron spectroscopy and nanoprobe Auger electron spectroscopy are used to identify the surface cation content, chemical bonding environment, and the spatial heterogeneities with nanoscale resolution. The higher electrochemical activity of LSC_450°C is attributed to the more stoichiometric cation content on the surface and the more uniform lateral and depth distribution of constituent cations. The poorly crystalline atomic structure of the LSC_450°C was found to prohibit the extensive segregation and phase separation on the surface because of the more favorable elastic and electrostatic interactions of Sr in the bulk. Upon annealing in air at 600 °C, the surface of the LSC_650°C undergoes a structural change from a Sr-rich LSC state to a SrO/Sr(OH)2-rich phase-separated state. The partial blockage of the surface with the heterogeneously distributed SrO/Sr(OH)2-rich phases, the decrease in oxygen vacancy content, and the deterioration of the electron transfer properties as evidenced from the Co oxidation state near the surface are found responsible for the severe electrochemical deactivation of the LSC_650°C. These results are important for advancing our ability to tailor the electrochemical performance of solid oxide fuel cell cathodes by understanding the relation of surface chemistry and structure to the oxygen reduction activity and stability, and the dependence of cation segregation on its driving forces including material microstructure.

Nano-X-ray Absorption Spectroscopy of Single Co-Implanted ZnO Nanowires

We report on the local structure of single Co-implanted ZnO nanowires studied using a hard X-ray nanoprobe. X-ray fluorescence maps show uniform Zn and Co distributions along the wire within the length scale of the beam size. The X-ray fluorescence data allow the estimation of the Co content within the nanowire. Polarization dependent X-ray absorption near edge structure shows no structural disorder induced neither in the radial nor axial directions of the implanted nanowires after subsequent annealing. Co2+ ions occupy Zn sites into the wurtzite ZnO lattice. Extended X-ray absorption fine structure data reveal high structural order in the host lattice without distortion in their interatomic distances, confirming the recovery of the radiation damaged ZnO structure through thermal annealing.

Studying single nanocrystals under high pressure using an x-ray nanoprobe

In this report, we demonstrate the feasibility of applying a 250-nm focused x-ray beam to study a single crystalline NbSe(3) nanobelt under high-pressure conditions in a diamond anvil cell. With such a small probe, we not only resolved the distribution and morphology of each individual nanobelt in the x-ray fluorescence maps but also obtained the diffraction patterns from individual crystalline nanobelts with thicknesses of less than 50 nm. Single crystalline diffraction measurements on NbSe(3) nanobelts were performed at pressures up to 20 GPa.

Nanometre multi-axis manipulator with interferometer control

As one of the latest beamlines at the Synchrotron Radiation SOLEIL facility, ANTARES beamline will offer an X-ray nanoprobe able to combine four powerful non-destructive techniques: (i) angle-resolved photoemission spectroscopy, (ii) core-level photoemission (X-ray photo electron spectroscopy), (iii) X-ray absorption spectroscopy and (iv) X-ray fluorescence. ANTARES microscope has implemented a powerful and innovative nano-scanning photoemission microscope technique using three independent detectors in combination with a 14 integrated-axes manipulator. Microscope motion requirements involve linear and rotary positioning based on non-magnetic ceramic servo motors, compatible with ultra-high-vacuum conditions. A complete four-head interferometer system monitors continuously, with nano-metric precision, the alignment of the sample and focalization optics during the scanning operation. An accurate electronic feedback avoids image distortion due to mechanical vibrations or thermal effects.

Contactless monitoring of the diameter-dependent conductivity of GaAs nanowires

Contactless monitoring with photoelectron microspectroscopy of the surface potential along individual nanostructures, created by the X-ray nanoprobe, opens exciting possibilities to examine quantitatively size- and surface-chemistry-effects on the electrical transport of semiconductor nanowires (NWs). Implementing this novel approach-which combines surface chemical microanalysis with conductivity measurements-we explored the dependence of the electrical properties of undoped GaAs NWs on the NW width, temperature and surface chemistry. By following the evolution of the Ga 3d and As 3d core level spectra, we measured the position-dependent surface potential along the GaAs NWs as a function of NW diameter, decreasing from 120 to ?20 nm, and correlated the observed decrease of the conductivity with the monotonic reduction in the NW diameter from 120 to ~20 nm. Exposure of the GaAs NWs to oxygen ambient leads to a decrease in their conductivity by up to a factor of 10, attributed to the significant decrease in the carrier density associated with the formation of an oxide shell.

Hard X-ray Nanoprobe Characterization of Advanced Materials

Extended abstract of a paper presented at Microscopy and Microanalysis 2010 in Portland, Oregon, USA, August 1 – August 5, 2010.

D-30 Invited—Nanoscale Scanning Probe Diffraction Microscopy at the Hard X-ray Nanoprobe Beamline

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Hard X-ray nanoprobe at beamline P06 at PETRA III

We describe the hard X-ray scanning microscope planned for the new synchrotron radiation source PETRA III at DESY in Hamburg, Germany. It is based on nanofocusing refractive X-ray lenses and is designed for two-dimensional mapping and scanning tomography. It supports X-ray fluorescence and (coherent) diffraction contrast, yielding elemental and structural information from inside the sample. Spatial resolutions down to well below 50 nm are aimed for in direct space. A further increase in spatial resolution is expected by applying ptychographic scanning schemes. The optical scheme with a two-stage focusing optic is described.

X-ray linear dichroism of defects in GaN:Mg using hard x-ray nanoprobe

In this study, we report the application of synchrotron radiation nanoprobe techniques to the structural analysis of pyramidal defects in Mg doped GaN. A combination of fluorescence mapping with spectroscopic techniques enabled us to examine not only the elemental nature but also their crystallographic orientation on the submicron scale. Our observations provide strong evidence for the diffusion and subsequent segregation of background impurities of Fe and Cr on the sample surface, with the absence of pronounced sequential stacking compared with Ga atoms. The strong polarization-dependent x-ray absorption near-edge structure features showed the preservation of the hexagonal crystalline structure in both defect-free and hexagonal pyramids. From the spatially resolved x-ray linear dichroism, no preferential disorder was observed in the direction parallel or perpendicular to the crystal growth.

Mechanical design of ultraprecision weak-link stages for nanometer-scale x-ray imaging

A nanopositioning diagnostic setup has been built to support the Argonne Center for Nanoscale Materials (CNM) nanoprobe instrument commissioning process at the APS. Its laser Doppler interferometer system provides subnanometer positioning diagnostic resolution with large dynamic range. A set of original APS designed ultraprecision PZT-driven weak-link stages with high-stiffness motor-driven stages has been tested with this diagnostic setup.In this paper we present a preliminary test result of the ultraprecision weak-link stage system developed for the CNM hard x-ray nanoprobe instrument at APS sector 26. A test result for a novel laminar weak-link mechanism with sub-centimeter travel range and sub-nanometer positioning resolution is also introduced in this paper as a future work.