Elettra-Sincrotrone Trieste: present and future.

We present an overview of the Elettra-Sincrotrone Trieste research center, which hosts synchrotron and free-electron laser light sources. We review the current status, provide examples of recent achievements in basic and applied research and discuss the upgrade programs of the facility.

Publisher Correction: Seeded X-ray free-electron laser generating radiation with laser statistical properties.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Kirkpatrick-Baez active optics system at FERMI: system performance analysis.

FERMI is the first and only seeded EUV-SXR free-electron laser (FEL) facility available to users; it operates at Elettra - Sincrotrone Trieste (Italy) and it presents five operating endstations. Three of them, namely LDM (Low Density Matter), DiProI (Diffraction and Projection Imaging) and MagneDyn (Magneto-Dynamical studies), use a Kirkpatrick-Baez (KB) active X-ray optics system to focus the FEL pulses into the experimental chambers. The present work reports on the final results of the upgraded KB Active Optics Systems (KAOS), which have been mechanically modified in order to improve stability and repeatability with respect to the original design. The results have been obtained on both the FERMI FEL lines, FEL1 and FEL2, and are particularly relevant for the latter as it is the low-wavelength line recently opened to users. After a thorough description of the new mechanical layout of the system and the aspects that have been improved after the refurbishment, a set of simulations of the optical performances are presented. The code used to simulate the behavior of KAOS is WISEr, a physical-optics-based tool, which is freely accessible, and integrated into the Oasys platform, that takes into account the specific surface metrology characterization of the beamline mirrors, including figure errors and microroughness power spectral density. The results of WISEr are then used as a reference for the actual optimization of the optical system. This procedure relies heavily on a wavefront sensor (WFS) mounted out of focus to optimize the refocusing mirrors alignment as well as their curvature bending (by minimization of the coefficients of the Zernike wavefront expansion). Moreover, the WFS data are used to reconstruct the focal spot parameters by means of a back-propagation of the electric field. Finally, these results are compared with those obtained after the FEL ablation of a PMMA layer positioned on the focal plane, and analyzed ex situ in a post-mortem fashion. The mechanically refurbished optical system and the multi-technique alignment approach, aimed at optimizing the mirrors' curvature, pitch and roll angles, allowed a focal spot of 1.8 µm × 2.4 µm at 4.14 nm wavelength (FEL2) to be inferred, confirmed by the PMMA ablation imprints.

Seeded X-ray free-electron laser generating radiation with laser statistical properties.

The invention of optical lasers led to a revolution in the field of optics and to the creation of such fields of research as quantum optics. The reason was their unique statistical and coherence properties. The emerging, short-wavelength free-electron lasers (FELs) are sources of very bright coherent extreme-ultraviolet and X-ray radiation with pulse durations on the order of femtoseconds, and are presently considered to be laser sources at these energies. FELs are highly spatially coherent to the first-order but in spite of their name, behave statistically as chaotic sources. Here, we demonstrate experimentally, by combining Hanbury Brown and Twiss interferometry with spectral measurements that the seeded XUV FERMI FEL-2 source does indeed behave statistically as a laser. The results may be useful for quantum optics experiments and for the design and operation of next generation FEL sources.

Recent approaches for bridging the pressure gap in photoelectron microspectroscopy.

Ambient-pressure photoelectron spectroscopy (APPES) and microscopy are at the frontier of modern chemical analysis at liquid-gas, solid-liquid and solid-gas interfaces, bridging science and engineering of functional materials. Complementing the current state-of-the art of the instruments, we survey in this short review several alternative APPES approaches, developed recently in the scanning photoelectron microscope (SPEM) at the Elettra laboratory. In particular, we report on experimental setups for dynamic near-ambient pressure environment, using pulsed-gas injection in the vicinity of samples or reaction cells with very small apertures, allowing for experiments without introducing additional differential pumping stages. The major part of the review is dedicated to the construction and performance of novel environmental cells using ultrathin electron-transparent but molecularly impermeable membranes to isolate the gas or liquid ambient from the electron detector operating in ultra-high vacuum (UHV). We demonstrate that two dimensional materials, such as graphene and derivatives, are mechanically robust to withstand atmospheric - UHV pressure differences and are sufficiently transparent for the photoelectrons emitted from samples immersed in the liquid or gaseous media. There are many unique opportunities for APPES using X-rays over a wide energy range. We show representative results that illustrate the potential of these 'ambient-pressure' approaches. Combined with the ca 100 nm lateral resolution of SPEM, they can overcome the pressure gap challenges and address the evolution of chemical composition and electronic structure at surface and interfaces under realistic operation conditions with unprecedented lateral and spectral resolution.

Experimental setups for FEL-based four-wave mixing experiments at FERMI.

The recent advent of free-electron laser (FEL) sources is driving the scientific community to extend table-top laser research to shorter wavelengths adding elemental selectivity and chemical state specificity. Both a compact setup (mini-TIMER) and a separate instrument (EIS-TIMER) dedicated to four-wave-mixing (FWM) experiments has been designed and constructed, to be operated as a branch of the Elastic and Inelastic Scattering beamline: EIS. The FWM experiments that are planned at EIS-TIMER are based on the transient grating approach, where two crossed FEL pulses create a controlled modulation of the sample excitations while a third time-delayed pulse is used to monitor the dynamics of the excited state. This manuscript describes such experimental facilities, showing the preliminary results of the commissioning of the EIS-TIMER beamline, and discusses original experimental strategies being developed to study the dynamics of matter at the fs-nm time-length scales. In the near future such experimental tools will allow more sophisticated FEL-based FWM applications, that also include the use of multiple and multi-color FEL pulses.

Multipurpose end-station for coherent diffraction imaging and scattering at FERMI@Elettra free-electron laser facility.

The Diffraction and Projection Imaging (DiProI) beamline at FERMI, the Elettra free-electron laser (FEL), hosts a multi-purpose station that has been opened to users since the end of 2012. This paper describes the core capabilities of the station, designed to make use of the unique features of the FERMI-FEL for performing a wide range of static and dynamic scattering experiments. The various schemes for time-resolved experiments, employing both soft X-ray FEL and seed laser IR radiation are presented by using selected recent results. The ongoing upgrade is adding a reflection geometry setup for scattering experiments, expanding the application fields by providing both high lateral and depth resolution.

Quasi-in-situ single-grain photoelectron microspectroscopy of Co/PPy nanocomposites under oxygen reduction reaction.

This paper reports an investigation into the aging of pyrolyzed cobalt/polypyrrole (Co/PPy) oxygen reduction reaction (ORR) electrocatalysts, based on quasi-in-situ photoelectron microspectroscopy. The catalyst precursor was prepared by potentiostatic reverse-pulse coelectrodeposition from an acetonitrile solution on graphite. Accelerated aging was obtained by quasi-in-situ voltammetric cycling in an acidic electrolyte. Using photoelectron imaging and microspectroscopy of single Co/PPy grains at a resolution of 100 nm, we tracked the ORR-induced changes in the morphology and chemical state of the pristine material, consisting of uniformly distributed ∼20 nm nanoparticles, initially consisting of a mixture of Co(II) and Co(III) oxidation states in almost equal amounts. The evolution of the Co 2p, O 1s, and N 1s spectra revealed that the main effects of aging are a gradual loss of the Co present at the surface and the reduction of Co(III) to Co(II), accompanied by the emergence and growth of a N 1s signal, corresponding to electrocatalytically active C-N sites.

Multi-colour pulses from seeded free-electron-lasers: towards the development of non-linear core-level coherent spectroscopies.

We report on new opportunities for ultrafast science thanks to the use of two-colour extreme ultraviolet (XUV) pulses at the FERMI free electron laser (FEL) facility. The two pulses have been employed to carry out a pioneering FEL-pump/FEL-probe diffraction experiment using a Ti target and tuning the FEL pulses to the M(2/3)-edge in order to explore the dependence of the dielectric constant on the excitation fluence. The future impact that the use of such a two-colour FEL emission will have on the development of ultrafast wave-mixing methods in the XUV/soft X-ray range is addressed and discussed.

Photoelectron spectroscopy of wet and gaseous samples through graphene membranes.

Photoelectron spectroscopy (PES) and microscopy are highly important for exploring morphologically and chemically complex liquid-gas, solid-liquid and solid-gas interfaces under realistic conditions, but the very small electron mean free path inside dense media imposes serious experimental challenges. Currently, near ambient pressure PES is conducted using dexterously designed electron energy analyzers coupled with differentially pumped electron lenses which make it possible to conduct PES measurements at a few hPa. This report proposes an alternative ambient pressure approach that can be applied to a broad class of samples and be implemented in conventional PES instruments. It uses ultrathin electron transparent but molecular impermeable membranes to isolate the high pressure sample environment from the high vacuum PES detection system. We demonstrate that the separating graphene membrane windows are both mechanically robust and sufficiently transparent for electrons in a wide energy range to allow soft X-ray PES of liquid and gaseous water. The performed proof-of-principle experiments confirm the possibility to probe vacuum-incompatible toxic or reactive samples placed inside such hermetic, gas flow or fluidic environmental cells.

Electrodeposition of Co/CoO nanoparticles onto graphene for ORR electrocatalysis: a study based on micro-X-ray absorption spectroscopy and X-ray fluorescence mapping.

Electrodeposition of graphene-supported Co for ORR electrocatalysts from an acetonitrile solution has been studied by a multi-technique approach, combining a suite of spectroscopic methods with electrochemical measurements, allowing a molecular-level understanding of potentiostatic and pulsed-potential plating processes from the organic solvent onto a freestanding graphene film. The formation of the graphene film by the light-scribe approach has been monitored by Raman spectroscopy; the electrodeposition process has been clarified by cyclic voltammetry and the compositional and chemical-state distribution of Co have been investigated ex situ by soft X-ray absorption spectroscopy and fluorescence mapping, showing that both spatial distribution and valence state are homogeneous and independent of the local current density. The deposit consists in micrometric aggregates of Co/CoO nanoparticles with diameter ca. 30 nm (pulsed) and 200 nm (potentiostatic deposition). Potentiostatic deposition allows to obtain better ORR electrocatalytic perfomance in terms of nnumber of transferred electrons, onset/ half-wave potential and current density.

Towards jitter-free pump-probe measurements at seeded free electron laser facilities.

X-ray free electron lasers (FEL) coupled with optical lasers have opened unprecedented opportunities for studying ultrafast dynamics in matter. The major challenge in pump-probe experiments using FEL and optical lasers is synchronizing the arrival time of the two pulses. Here we report a technique that benefits from the seeded-FEL scheme and uses the optical seed laser for nearly jitter-free pump-probe experiments. Timing jitter as small as 6 fs has been achieved and confirmed by measurements of FEL-induced transient reflectivity changes of Si3N4 using both collinear and non-collinear geometries. Planned improvements of the experimental set-up are expected to further reduce the timing jitter between the two pulses down to fs level.

Conformation sequence recovery of a non-periodic object from a diffraction-before-destruction experiment.

Knowledge of the sequence of different conformational states of a protein molecule is key to better understanding its biological function. A diffraction pattern from a single conformational state can be captured with an ultrafast X-ray Free-Electron Laser (XFEL) before the target is completely annihilated by the radiation. In this paper, we report the first experimental demonstration of conformation sequence recovery using diffraction patterns from randomly ordered conformations of a non-periodic object using the dimensional reduction technique Isomap and coherent diffraction imaging.

In-situ photoelectron microspectroscopy and imaging of electrochemical processes at the electrodes of a self-driven cell.

The challenges in development of solid oxide fuel cells (SOFCs) are reducing their dimensions and increasing their efficiency and durability, which requires physicochemical characterization at micro-scales of the device components during operation conditions. Recently, the unique potential of scanning photoelectron microscopy (SPEM) has been demonstrated by in-situ studies of externally-driven SOFCs, which mimic real devices. Here we overcome the gap between model and real systems using a single-chamber Ni|YSZ|Mn SOFC, supporting a range of self-driven electrochemical reactions in variable gas environments and temperatures. The reported SPEM results, obtained during spontaneous electrochemical processes occurring in reactive gas ambient, demonstrate the chemical evolution of electrodic material, in particular the lateral distribution of the oxidation state and the induced local potential, clearly marking out the electrochemically most active micro-regions of the Ni anode.

Effect of ingested tungsten oxide (WOx) nanofibers on digestive gland tissue of Porcellio scaber (Isopoda, Crustacea): fourier transform infrared (FTIR) imaging.

Tungsten nanofibers are recognized as biologically potent. We study deviations in molecular composition between normal and digestive gland tissue of WOx nanofibers (nano-WOx) fed invertebrate Porcellio scaber (Iosopda, Crustacea) and revealed mechanisms of nano-WOx effect in vivo. Fourier Transform Infrared (FTIR) imaging performed on digestive gland epithelium was supplemented by toxicity and cytotoxicity analyses as well as scanning electron microscopy (SEM) of the surface of the epithelium. The difference in the spectra of the Nano-WOx treated and control cells showed up in the central region of the cells and were related to lipid peroxidation, and structural changes of nucleic acids. The conventional toxicity parameters failed to show toxic effects of nano-WOx, whereas the cytotoxicity biomarkers and SEM investigation of digestive gland epithelium indicated sporadic effects of nanofibers. Since toxicological and cytological measurements did not highlight severe effects, the biochemical alterations evidenced by FTIR imaging have been explained as the result of cell protection (acclimation) mechanisms to unfavorable conditions and indication of a nonhomeostatic state, which can lead to toxic effects.

Cellular internalization of dissolved cobalt ions from ingested CoFe2O4 nanoparticles: in vivo experimental evidence.

With a model invertebrate animal, we have assessed the fate of magnetic nanoparticles in biologically relevant media, i.e., digestive juices. The toxic potential and the internalization of such nanoparticles by nontarget cells were also examined. The aim of this study was to provide experimental evidence on the formation of Co(2+), Fe(2+), and Fe(3+) ions from CoFe2O4 nanoparticles in the digestive juices of a model organism. Standard toxicological parameters were assessed. Cell membrane stability was tested with a modified method for measurement of its quality. Proton-induced X-ray emission and low energy synchrotron radiation X-ray fluorescence were used to study internalization and distribution of Co and Fe. Co(2+) ions were found to be more toxic than nanoparticles. We confirmed that Co(2+) ions accumulate in the hepatopancreas, but Fe(n+) ions or CoFe2O4 nanoparticles are not retained in vivo. A model biological system with a terrestrial isopod is suited to studies of the potential dissolution of ions and other products from metal-containing nanoparticles in biologically complex media.

The interaction of asbestos and iron in lung tissue revealed by synchrotron-based scanning X-ray microscopy.

Asbestos is a potent carcinogen associated with malignant mesothelioma and lung cancer but its carcinogenic mechanisms are still poorly understood. Asbestos toxicity is ascribed to its particular physico-chemical characteristics, and one of them is the presence of and ability to adsorb iron, which may cause an alteration of iron homeostasis in the tissue. This observational study reports a combination of advanced synchrotron-based X-ray imaging and micro-spectroscopic methods that provide correlative morphological and chemical information for shedding light on iron mobilization features during asbestos permanence in lung tissue. The results show that the processes responsible for the unusual distribution of iron at different stages of interaction with the fibres also involve calcium, phosphorus and magnesium. It has been confirmed that the dominant iron form present in asbestos bodies is ferritin, while the concurrent presence of haematite suggests alteration of iron chemistry during asbestos body permanence.

Soft X-ray imaging and spectromicroscopy: new insights in chemical state and morphology of the key components in operating fuel-cells.

Fuel cells are one of the most appealing environmentally friendly devices for the effective conversion of chemical energy into electricity and heat, but still there are key barriers to their broad commercialization. In addition to efficiency, a major challenge of fuel-cell technology is the durability of the key components (interconnects, electrodes, and electrolytes) that can be subject to corrosion or undesired morphology and chemical changes occurring under operating conditions. The complementary capabilities of synchrotron-based soft X-ray microscopes in terms of imaging, spectroscopy, spatial and time resolution, and variable probing depths are opening unique opportunities to shed light on the multiple processes occurring in these complex systems at microscopic length scales. This type of information is prerequisite for understanding and controlling the performance and durability of such devices. This paper reviews the most recent efforts in the implementation of these methods for exploring the evolving structure and chemical composition of some key fuel cell components. Recent achievements are illustrated by selected results obtained with simplified versions of proton-exchange fuel-cells (PEFC) and solid-oxide fuel-cells (SOFC), which allow in situ monitoring of the redox reactions resulting in: 1) undesired deposits at interconnects and electrodes (PEFC); 2) material interactions at the electrode-electrolyte interface (PEFC); 3) release of corrosion products to the electrolyte phase (PEFC, and 4) mass-transport processes and structural changes occurring at the high operation temperatures of SOFC and promoted by the polarization.

Unsupervised classification of single-particle X-ray diffraction snapshots by spectral clustering.

Single-particle experiments using X-ray Free Electron Lasers produce more than 10(5) snapshots per hour, consisting of an admixture of blank shots (no particle intercepted), and exposures of one or more particles. Experimental data sets also often contain unintentional contamination with different species. We present an unsupervised method able to sort experimental snapshots without recourse to templates, specific noise models, or user-directed learning. The results show 90% agreement with manual classification.

Cellular distribution and degradation of cobalt ferrite nanoparticles in Balb/3T3 mouse fibroblasts.

The effect of the concentration of cobalt ferrite (CoFe(2)O(4)) nanoparticles (NPs) on their intracellular location and distribution has been explored by synchrotron radiation X-ray and fluorescence microscopy (SR-XRF) monitoring the evolution of NPs elemental composition as well. In cells exposed to low concentrations of CoFe(2)O(4) NPs, the NPs preferentially segregate in the perinuclear region preserving their initial chemical content. At concentrations exceeding 500 µM the XRF spectra indicate the presence of Co and Fe also in the nuclear region, accompanied by sensible changes in the cellular morphology. The increase of the Co/Fe ratio measured in the nuclear compartment indicates that above certain concentrations the CoFe(2)O(4) NPs intracellular distribution could be accompanied by biodegradation resulting in Co accumulation in the nucleus.