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 using differentially pumped analyzers, we survey in this short review several alternative APPES approaches, developed recently in the scanning photoelectron microscope (SPEM) at the Elettra laboratory. The reported set-ups allow for performing dynamic near-ambient pressure experiments without introducing additional differential pumping stages. They include implementation of pulsed-gas injection in the vicinity of samples or placing the sample inside reaction cells with very small apertures. The major part of the review is dedicated to construction and performance of novel environmental cells, where ultrathin electron-transparent but molecularly impermeable membranes are used to isolate the gas or liquid ambient from the electron detector operated 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 liquid or gaseous media. Representative results illustrate the performance of reported APPES approaches using tunable synchrotron X-rays, combined with the sub-micrometer lateral resolution of SPEM. They demonstrate the unique opportunities for addressing the chemical composition and electronic structure of surfaces and interfaces under realistic operation conditions with unprecedented lateral and spectral resolution.
The performance of new materials and devices often depends on processes taking place at the interface between an active solid element and the environment (such as air, water or other fluids). ...Understanding and controlling such interfacial processes require surface-specific spectroscopic information acquired under real-world operating conditions, which can be challenging because standard approaches such as X-ray photoelectron spectroscopy generally require high-vacuum conditions. The state-of-the-art approach to this problem relies on unique and expensive apparatus including electron analysers coupled with sophisticated differentially pumped lenses. Here, we develop a simple environmental cell with graphene oxide windows that are transparent to low-energy electrons (down to 400 eV), and demonstrate the feasibility of X-ray photoelectron spectroscopy measurements on model samples such as gold nanoparticles and aqueous salt solution placed on the back side of a window. These proof-of-principle results show the potential of using graphene oxide, graphene and other emerging ultrathin membrane windows for the fabrication of low-cost, single-use environmental cells compatible with commercial X-ray and Auger microprobes as well as scanning or transmission electron microscopes.
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.
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.
Batteries with inorganic solid-state electrolytes (ISSE) are attracting notable interest for next-generation systems implementing Lithium (Li) metal anodes, in view of achieving higher energy ...densities combined with superior safety. Notwithstanding extensive research and development work, this technology is not yet ready for industrial implementation, one of the key challenges being the stability of ISSEs, chiefly at the anodic interface. This work attacks this issue for the specific case of the LAGP/Li (Lithium Aluminium Germanium Phosphate/Lithium) interface with a micro-spectroscopic approach centred on post mortem Scanning Transmission X-ray Microscopy (STXM) of intact LMO/LAGP/Li thin-film batteries, microfabricated in discharged state. Pristine and cycled cells were mapped to pinpoint morphochemical changes, induced by electrochemical ageing. The evidenced shape changes, corresponding to mechanical damaging of the solid/solid electrodic interfaces correlate with LAGP decomposition at the anode, leading to reduction of Ge, whereas the chemical state at the cathodic interface is preserved. Thanks to its submicron spacial resolution, the STXM at the Ge L-edge and O K-edge spectra allowed to assess the highly localized nature of the chemical transformation of LAGP and its correlation with the formation of Li outgrowth features.
•Scanning X-ray Microscopy of local degradation at the Lithium-LAGP interface in a thin-film battery.•STXM maps revealed morphochemical changes induced by electrochemical ageing.•Germanium chemical state changes occur only at the anode-electrolyte interface.
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.
Solid-state batteries (SSB), characterized by solid-state electrolytes—in particular inorganic ones (ISSE)—are an ideal option for the safe implementation of metallic Li anodes. Even though SSBs with ...ISSEs have been extensively investigated over the last two decades, they still exhibit a series of technological drawbacks. In fact, mechano-chemical issues, mainly the stability of the electrolyte/anode interface, hinder their widespread application. The present investigation focusses on a thin-film LMO (Lithium-Manganese-Oxide)/LAGP (LiAlGe Phosphate)/Copper, anodeless Lithium-metal battery and explores the morphochemical evolution of the electrode/electrolyte interfaces with synchrotron-based Scanning Photoelectron Microscopy (SPEM) of intact pristine and cycled cells. Chemical images were acquired with submicrometer resolution, to highlight the coupled geometrical and chemical-state changes caused by electrochemical ageing. Geometrical changes of the electrolyte/cathode interface were induced by periodic volume changes, causing de-cohesion of the solid-solid contact, but no chemical-state changes accompany the cathodic damaging mode. Instead, shape changes of the electrolyte/anode region pinpoint the correlation between mechanical damaging with the decomposition of the LAGP ISSE, due to the reduction of Ge, triggered by the contact with elemental Li. The micro-spectroscopic approach adopted in this study enabled the assessment of the highly localized nature of the cathodic and anodic degradation modes in SSB devices and to single out the chemical and mechanical contributions.
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.
The gasification process, which increases the number of broken CC bonds and the abundance of particular oxygenated functional groups, is shown to destroy carbon nanotubes (CNTs). The expansion of ...the defect density and dimensions leads to nonlinear consumption of the CNTs with increasing O dose. Some nanotubes are consumed faster than others, most probably due to higher defect densities.
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