Soft X-ray spectro-ptychography of boron nitride nanobamboos, carbon nanotubes and permalloy nanorods.

Spectro-ptychography offers improved spatial resolution and additional phase spectral information relative to that provided by scanning transmission X-ray microscopes. However, carrying out ptychography at the lower range of soft X-ray energies (e.g. below 200 eV to 600 eV) on samples with weakly scattering signals can be challenging. Here, results of soft X-ray spectro-ptychography at energies as low as 180 eV are presented, and its capabilities are illustrated with results from permalloy nanorods (Fe 2p), carbon nanotubes (C 1s) and boron nitride bamboo nanostructures (B 1s, N 1s). The optimization of low-energy X-ray spectro-ptychography is described and important challenges associated with measurement approaches, reconstruction algorithms and their effects on the reconstructed images are discussed. A method for evaluating the increase in radiation dose when using overlapping sampling is presented.

Soft X-ray nanospectroscopy for quantification of X-ray linear dichroism on powders.

X-ray linear dichroism (XLD) is a fundamental property of many ordered materials that can for instance provide information on the origin of magnetic properties and the existence of differently ordered domains. Conventionally, measurements of XLD are performed on single crystals, crystalline thin films, or highly ordered nanostructure arrays. Here, it is demonstrated how quantitative measurements of XLD can be performed on powders, relying on the random orientation of many particles instead of the controlled orientation of a single ordered structure. The technique is based on a scanning X-ray transmission microscope operated in the soft X-ray regime. The use of a Fresnel zone plate allows X-ray absorption features to be probed at ∼40 nm lateral resolution - a scale small enough to probe the individual crystallites in most powders. Quantitative XLD parameters were then retrieved by determining the intensity distributions of certain diagnostic dichroic absorption features, estimating the angle between their transition dipole moments, and fitting the distributions with four-parameter dichroic models. Analysis of several differently produced ZnO powders shows that the experimentally obtained distributions indeed follow the theoretical model for XLD. Making use of Monte Carlo simulations to estimate uncertainties in the calculated dichroic model parameters, it was established that longer X-ray exposure times lead to a decrease in the amplitude of the XLD effect of ZnO.

Combining X-ray excited optical luminescence and X-ray absorption spectroscopy for correlative imaging on the nanoscale.

X-ray absorption and optical luminescence can both provide valuable but very different information on the chemical and physical properties of materials. Although it is known that the spectral characteristics of many materials are highly heterogeneous on the micro- and/or nanoscale, no methodology has so far been shown to be capable of spatially resolving both full X-ray absorption and X-ray excited optical luminescence (XEOL) spectra on the nanoscale in a correlative manner. For this purpose, the scanning transmission X-ray microscope at the HERMES beamline of the SOLEIL synchrotron was equipped with an optical detection system capable of recording high-resolution XEOL spectra using a 40 nm soft X-ray probe. The functionality of the system was demonstrated by analyzing ZnO powder dispersions - showing simultaneously the X-ray linear dichroism and XEOL behavior of individual submicrometric ZnO crystallites.

Backside-illuminated scientific CMOS detector for soft X-ray resonant scattering and ptychography.

The impressive progress in the performance of synchrotron radiation sources is nowadays driven by the so-called `ultimate storage ring' projects which promise an unprecedented improvement in brightness. Progress on the detector side has not always been at the same pace, especially as far as soft X-ray 2D detectors are concerned. While the most commonly used detectors are still based on microchannel plates or CCD technology, recent developments of CMOS (complementary metal oxide semiconductor)-type detectors will play an ever more important role as 2D detectors in the soft X-ray range. This paper describes the capabilities and performance of a camera equipped with a newly commercialized backside-illuminated scientific CMOS (sCMOS-BSI) sensor, integrated in a vacuum environment, for soft X-ray experiments at synchrotron sources. The 4 Mpixel sensor reaches a frame rate of up to 48 frames s-1 while matching the requirements for X-ray experiments in terms of high-intensity linearity (>98%), good spatial homogeneity (<1%), high charge capacity (up to 80 ke-), and low readout noise (down to 2 e- r.m.s.) and dark current (3 e- per second per pixel). Performance evaluations in the soft X-ray range have been carried out at the METROLOGIE beamline of the SOLEIL synchrotron. The quantum efficiency, spatial resolution (24 line-pairs mm-1), energy resolution (<100 eV) and radiation damage versus the X-ray dose (<600 Gy) have been measured in the energy range from 40 to 2000 eV. In order to illustrate the capabilities of this new sCMOS-BSI sensor, several experiments have been performed at the SEXTANTS and HERMES soft X-ray beamlines of the SOLEIL synchrotron: acquisition of a coherent diffraction pattern from a pinhole at 186 eV, a scattering experiment from a nanostructured Co/Cu multilayer at 767 eV and ptychographic imaging in transmission at 706 eV.

Fast X-ray reflectivity measurements using an X-ray pixel area detector at the DiffAbs beamline, Synchrotron SOLEIL.

This paper describes a method for rapid measurements of the specular X-ray reflectivity signal using an area detector and a monochromatic, well collimated X-ray beam (divergence below 0.01°), combined with a continuous data acquisition mode during the angular movements of the sample and detector. In addition to the total integrated (and background-corrected) reflectivity signal, this approach yields a three-dimensional mapping of the reciprocal space in the vicinity of its origin. Grazing-incidence small-angle scattering signals are recorded simultaneously. Measurements up to high momentum transfer values (close to 0.1 nm-1, also depending on the X-ray beam energy) can be performed in total time ranges as short as 10 s. The measurement time can be reduced by up to 100 times as compared with the classical method using monochromatic X-ray beams, a point detector and rocking scans (integrated reflectivity signal).

HERMES: a soft X-ray beamline dedicated to X-ray microscopy.

The HERMES beamline (High Efficiency and Resolution beamline dedicated to X-ray Microscopy and Electron Spectroscopy), built at Synchrotron SOLEIL (Saint-Auban, France), is dedicated to soft X-ray microscopy. The beamline combines two complementary microscopy methods: XPEEM (X-ray Photo Emitted Electron Microscopy) and STXM (Scanning Transmission X-ray Microscopy) with an aim to reach spatial resolution below 20 nm and to fully exploit the local spectroscopic capabilities of the two microscopes. The availability of the two methods within the same beamline enables the users to select the appropriate approach to study their specific case in terms of sample environment, spectroscopy methods, probing depth etc. In this paper a general description of the beamline and its design are presented. The performance and specifications of the beamline will be reviewed in detail. Moreover, the article is aiming to demonstrate how the beamline performances have been specifically optimized to fulfill the specific requirements of a soft X-ray microscopy beamline in terms of flux, resolution, beam size etc. Special attention has been dedicated to overcome some limiting and hindering problems that are usually encountered on soft X-ray beamlines such as carbon contamination, thermal stability and spectral purity.

Two-dimensional resonant magnetic soft X-ray scattering set-up for extreme sample environment.

The newly built MagSAXS (magnetic small-angle X-ray scattering) set-up dedicated to the direct two-dimensional measurement of magnetic scattering using polarized synchrotron radiation in extreme sample environments is presented. Pure optical transport of the image is used to record the magnetic scattering with a two-dimensional CCD visible-light camera. The set-up is able to probe magnetic correlation lengths from the micrometer down to the nanometer scale. A detailed layout is presented along with preliminary results obtained at several beamlines at Synchrotron SOLEIL. The presented examples underline the wide range of possible applications spanning from correlation lengths determination to Fourier transform holography.

X-ray diffraction imaging of metal-oxide epitaxial tunnel junctions made by optical lithography: use of focused and unfocused X-ray beams.

X-ray diffraction techniques are used in imaging mode in order to characterize micrometre-sized objects. The samples used as models are metal-oxide tunnel junctions made by optical lithography, with lateral sizes ranging from 150 µm down to 10 µm and various shapes: discs, squares and rectangles. Two approaches are described and compared, both using diffraction contrast: full-field imaging (topography) and raster imaging (scanning probe) using a micrometre-sized focused X-ray beam. It is shown that the full-field image gives access to macroscopic distortions (e.g. sample bending), while the local distortions, at the micrometre scale (e.g. tilts of the crystalline planes in the vicinity of the junction edges), can be accurately characterized only using focused X-ray beams. These local defects are dependent on the junction shape and larger by one order of magnitude than the macroscopic curvature of the sample.

Enhancement of the Solar Water Splitting Efficiency Mediated by Surface Segregation in Ti-Doped Hematite Nanorods.

Band engineering is employed thoroughly and targets technologically scalable photoanodes for solar water splitting applications. Complex and costly recipes are necessary, often for average performances. Here, we report simple photoanode growth and thermal annealing with effective band engineering results. By comparing Ti-doped hematite photoanodes annealed under nitrogen to photoanodes annealed in air, we found a strongly enhanced photocurrent of more than 200% in the first case. Using electrochemical impedance spectroscopy and synchrotron X-ray spectromicroscopy, we demonstrate that oxidized surface states and increased density of charge carriers are responsible for the enhanced photoelectrochemical (PEC) activity. Surface states are found to be related to the formation of pseudo-brookite clusters by surface Ti segregation. Spectro-ptychography is used for the first time at the Ti L3 absorption edge to isolate Ti chemical coordination arising from pseudo-brookite cluster contribution. Correlated with electron microscopy investigation and density functional theory calculations, the synchrotron spectromicroscopy data unambiguously prove the origin of enhanced PEC activity of N2-annealed Ti-doped hematite nanorods. Finally, we present here a handy and cheap surface engineering method beyond the known oxygen vacancy doping, allowing a net gain in the PEC activity for the hematite-based photoanodes.

Skyrmions in synthetic antiferromagnets and their nucleation via electrical current and ultra-fast laser illumination.

Magnetic skyrmions are topological spin textures that hold great promise as nanoscale information carriers in non-volatile memory and logic devices. While room-temperature magnetic skyrmions and their current-induced motion were recently demonstrated, the stray field resulting from their finite magnetisation and their topological charge limit their minimum size and reliable motion. Antiferromagnetic skyrmions allow to lift these limitations owing to their vanishing magnetisation and net zero topological charge, promising ultra-small and ultra-fast skyrmions. Here, we report on the observation of isolated skyrmions in compensated synthetic antiferromagnets at zero field and room temperature using X-ray magnetic microscopy. Micromagnetic simulations and an analytical model confirm the chiral antiferromagnetic nature of these skyrmions and allow the identification of the physical mechanisms controlling their size and stability. Finally, we demonstrate the nucleation of synthetic antiferromagnetic skyrmions via local current injection and ultra-fast laser excitation.

Supramolecular control of the magnetic anisotropy in two-dimensional high-spin Fe arrays at a metal interface.

Magnetic atoms at surfaces are a rich model system for solid-state magnetic bits exhibiting either classical or quantum behaviour. Individual atoms, however, are difficult to arrange in regular patterns. Moreover, their magnetic properties are dominated by interaction with the substrate, which, as in the case of Kondo systems, often leads to a decrease or quench of their local magnetic moment. Here, we show that the supramolecular assembly of Fe and 1,4-benzenedicarboxylic acid molecules on a Cu surface results in ordered arrays of high-spin mononuclear Fe centres on a 1.5 nm square grid. Lateral coordination with the molecular ligands yields unsaturated yet stable coordination bonds, which enable chemical modification of the electronic and magnetic properties of the Fe atoms independently from the substrate. The easy magnetization direction of the Fe centres can be switched by oxygen adsorption, thus opening a way to control the magnetic anisotropy in supramolecular layers akin to that used in metallic thin films.

Correlative Microscopy Insight on Electrodeposited Ultrathin Graphite Oxide Films.

Here, we present a correlative microscopic analysis of electrodeposited films from catechol solutions in aqueous electrolytes. The films were prepared in a miniaturized electrochemical cell and were analyzed by identical location transmission electron microscopy, scanning transmission X-ray microscopy, and atomic force microscopy. Thanks to this combined approach, we have shown that the electrodeposited films are constituted of ultrathin graphite oxide nanosheets. Detailed information about the electronic structure of the films was obtained by X-ray absorption near edge structure spectroscopy. These results show the large potential of soft electrochemical conditions for the bottom-up production of ultrathin graphite oxide nanosheet films via a one-pot green chemistry approach from simple organic building blocks.

A pressure-actuated flow cell for soft X-ray spectromicroscopy in liquid media.

We present and fully characterize a flow cell dedicated to imaging in liquid at the nanoscale. Its use as a routine sample environment for soft X-ray spectromicroscopy is demonstrated, in particular through the spectral analysis of inorganic particles in water. The care taken in delineating the fluidic pathways and the precision associated with pressure actuation ensure the efficiency of fluid renewal under the beam, which in turn guarantees a successful utilization of this microfluidic tool for in situ kinetic studies. The assembly of the described flow cell necessitates no sophisticated microfabrication and can be easily implemented in any laboratory. Furthermore, the design principles we relied on are transposable to all microscopies involving strongly absorbed radiation (e.g. X-ray, electron), as well as to all kinds of X-ray diffraction/scattering techniques.

Soft X-ray coherent scattering: instrument and methods at ESRF ID08.

An experimental setup has been developed to perform soft x-ray coherent scattering at beamline ID08 of the European Synchrotron Radiation Facility. An intense coherent beam was obtained by filtering the primary beam with the monochromator and a circular pinhole. A pinhole holder with motorized translations was installed inside the UHV chamber of the diffractometer. The scattered intensity was recorded in reflection geometry with a back-illuminated charge coupled device camera. As a demonstration we report experimental results of resonant magnetic scattering using coherent beam. The degree of coherence is evaluated, and it is shown that, while the vertical coherence is much higher than the horizontal one at the source, the situation is reversed at the diffractometer. The intensity of the coherent beam is also discussed.

Finite size effect on the structural and magnetic properties of MnAs/GaAs(001) patterned microstructures thin films.

MnAs epitaxial thin films on GaAs(001) single crystalline substrates crystallize at room temperature (RT) in a mixture of two crystalline phases with distinct magnetic properties, organized as stripes along the MnAs [0001] direction. This particular morphology is driven by anisotropic epitaxial strain. We elucidate here the physical mechanisms at the origin of size reduction effect on the MnAs crystalline phase transition. We investigated the structural and magnetic changes in MnAs patterned microstructures (confined geometry) when the lateral dimension is reduced to values close to the periodicity and width of the stripes observed in continuous films. The effects of the microstructure's lateral size, shape and orientation (with respect to the MnAs [Formula: see text] direction) were characterized by local probe synchrotron X-ray diffraction (µ-XRD) using a focused X-ray beam, X-ray Magnetic Circular Dichroïsm - Photo Emission Electron Microscopy (XMCD-PEEM) and Low Energy Electron Microscopy (LEEM). Changes in the transition temperature and the crystalline phase distribution inside the microstructures are evidenced and quantitatively measured. The effect of finite size and strain relaxation on the magnetic domain structure is also discussed. Counter-intuitively, we demonstrate here that below a critical microstructure size, bulk MnAs structural and magnetic properties are restored. To support our observations we developed, tested and validated a model based on the size-dependence of the elastic energy and strain relaxation to explain this phase re-distribution in laterally confined geometry.