No Arabic abstract
Experimental valence electron energy loss spectra (VEELS), up to the Li K edge, obtained on different phases of LixFePO4 are compared to first principles calculations using the density functional code WIEN2k. In the 4-7 eV range, a large peak is identified in the FePO4 spectrum, but is absent in LiFePO4, which could allow the easy formation of energy filtered images. The intensity of this peak, non sensitive to the precise orientation of the crystal, is large enough to rapidly determine existing phases in the sample and permit future dynamical studies. Solid solution and two-phases regions are also differentiated using Fe M2,3 / Li K edges.
Exploiting the information provided by electron energy-loss spectroscopy (EELS) requires reliable access to the low-loss region where the zero-loss peak (ZLP) often overwhelms the contributions associated to inelastic scatterings off the specimen. Here we deploy machine learning techniques developed in particle physics to realise a model-independent, multidimensional determination of the ZLP with a faithful uncertainty estimate. This novel method is then applied to subtract the ZLP for EEL spectra acquired in flower-like WS$_2$ nanostructures characterised by a 2H/3R mixed polytypism. From the resulting subtracted spectra we determine the nature and value of the bandgap of polytypic WS$_2$, finding $E_{rm BG} = 1.6_{-0.2}^{+0.3},{rm eV}$ with a clear preference for an indirect bandgap. Further, we demonstrate how this method enables us to robustly identify excitonic transitions down to very small energy losses. Our approach has been implemented and made available in an open source Python package dubbed EELSfitter.
The spatial distributions of anti-bonding $pi^ast$ and $sigma^ast$ states in epitaxial graphene multilayers are mapped using electron energy-loss spectroscopy in a scanning transmission electron microscope. Inelastic channeling simulations validate the interpretation of the spatially-resolved signals in terms of electronic orbitals, and demonstrate the crucial effect of the material thickness on the experimental capability to resolve the distribution of unoccupied states. This work illustrates the current potential of core-level electron energy-loss spectroscopy towards the direct visualization of electronic orbitals in a wide range of materials, of huge interest to better understand chemical bonding among many other properties at interfaces and defects in solids.
The electronic excitation spectra of undoped, and potassium as well as calcium doped phenantrene-type hydrocarbons have been investigated using electron energy-loss spectroscopy (EELS) in transmission. In the undoped materials, the lowest energy excitations are excitons with a relatively high binding energy. These excitons also are rather localized as revealed by their vanishing dispersion. Upon doping, new low energy excitation features appear in the former gaps of the materials under investigation. In K$_3$picene and K$_3$chrysene they are characterized by a negative dispersion while in Ca$_3$picene they are dispersionless.
Transmission electron microscopy, scanning transmission electron tomography, and electron energy loss spectroscopy were used to characterize three-dimensional artificial Si nanostructures called metalattices, focusing on Si metalattices synthesized by high-pressure confined chemical vapor deposition in 30-nm colloidal silica templates with ~7 and ~12 nm meta-atoms and ~2 nm meta-bonds. The meta-atoms closely replicate the shape of the tetrahedral and octahedral interstitial sites of the face-entered cubic colloidal silica template. Composed of either amorphous or nanocrystalline silicon, the metalattice exhibits long-range order and interconnectivity in two-dimensional micrographs and three-dimensional reconstructions. Electron energy loss spectroscopy provides information on local electronic structure. The Si L2,3 core-loss edge is blue-shifted compared to the onset for bulk Si, with the meta-bonds displaying a larger shift (0.55 eV) than the two types of meta-atoms (0.30 and 0.17 eV). Local density of state calculations using an empirical tight binding method are in reasonable agreement.
A quantum mechanical scattering theory for relativistic, highly focused electron beams near nanoscopic platelets is presented, revealing a new excitation mechanism due to the electron wave scattering from the platelet edges. Radiative electromagnetic excitations within the light cone are shown to arise, allowed by the breakdown of momentum conservation along the beam axis in the inelastic scattering process. Calculated for metallic (silver and gold) and insulating (SiO2 and MgO) nanoplatelets, new radiative features are revealed above the main surface plasmon-polariton peak, and dramatic enhancements in the electron energy loss probability at gaps of the classical spectra, are found. The corresponding radiation should be detectable in the vacuum far-field zone, with e-beams exploited as sensitive tip-detectors of electronically excited nanostructures.