We report a new simple but effective method to extract the weak surface signals from a “thickness series” of recorded electron energy-loss spectra. Using precise thickness measurements and energy-loss near-edge structures measured at increasing thicknesses, we are able to extract the surface and bulk components in the series. The electronic structure and bonding information from SrTiO3 (001) reconstructed surfaces have been successfully obtained by applying this approach. This approach can be applied to study many other cases including absorbed monolayers and beam-sensitive interfaces.

Taking advantage of previous measurements by Geiger and co-workers, we discuss the possibilities and problems of measuring vibrational modes of energy loss in a transmission electron microscope fitted with a monochromator and a high-resolution energy-loss spectrometer. The tail of the zero-loss peak is seen to be a major limitation, rather than its full-width at half-maximum. Because of the low oscillator strengths and small cross-sections involved, radiation damage will limit the spatial resolution if this technique is applied to organic specimens. Delocalization of the inelastic scattering may also be a limitation, if a dipole description of the scattering process is valid.

The recently discovered compound BeP2N4 that crystallizes in the phenakite-type structure has potential application as a high strength optoelectronic material. Therefore, it is important to analyze experimentally the electronic structure, which was done in the present work by monochromated electron energy-loss spectroscopy. The detection of Be is challenging due to its low atomic number and easy removal under electron bombardment. We were able to determine the bonding behavior and coordination of the individual atomic species including Be. This is evident from a good agreement between experimental electron energy-loss near-edge structures of the Be-K-, P-L2,3-, and N-K-edges and density functional theory calculations.

The recently developed in-column monochromators make it possible to record energy-c spectra with resolutions better than 30 meV from nanometer-sized regions. It should therefore in principle be possible to detect localized vibrational excitations. The scattering geometry in the electron microscope means that bond stretching in the specimen plane or longitudinal optic phonons dominate the scattering. Most promising for initial studies are vibrations with energies between 300 and 400 meV from hydrogen bonded to other atoms. Estimates of the scattering cross-sections on the basis of a simple model show that they are about the same as inner shell scattering cross-sections. Cross-sections also increase with charge transfer between the atoms, and theory incorporating realistic charge distributions shows that signal/noise is the only limitation to high-resolution imaging. Given the magnitude of the scattering cross-sections, minimizing the tail of the zero-loss peak is just as important as achieving a small-width at half-maximum. Improvements in both resolution and controlling the zero-loss tail will be necessary before it is practical to detect optic phonons in solids between 40 and 60 meV.

The classical implementation for putting quantitative figures on maps to reveal elemental compositions in transmission electron microscopy is by analytical methods like X-ray and energy-loss spectroscopy. Typically, the technique in use often depends on whether lighter or heavier elements are present and—more practically—which calibrations are available or sample-related properties are known. A framework linking electron energy-loss spectroscopy (EELS) and energy-dispersive X-ray (EDX) signals such that absolute volumetric concentrations can be derived without assumptions made a priori about the unknown sample, is largely missing. In order to combine both techniques and harness their respective potentials for a light and heavy element analysis, we have set up a powerful hardware configuration and implemented an experimental approach, which reduces the need for estimates on many parameters needed for quantitative work such as densities, absolute thicknesses, theoretical ionization cross-sections, etc. Calibrations on specimens with known geometry allow the measurement of inelastic mean free paths. As a consequence, mass-thicknesses obtained from the EDX ζ-factor approach can be broken up and quantities like concentrations and partial energy-differential ionization cross-sections become accessible. ζ-factors can then be used for conversion into EELS cross-sections that are hard to determine otherwise, or conversely, connecting EDXS and EELS in a quantitative manner quite effectively.

Electron-beam-induced soft-X-ray emission spectroscopy (SXES) that uses a grating spectrometer has been introduced to a conventional scanning electron microscope (SEM) for characterizing desired specimen areas of bulk materials. The spectrometer was designed as a grazing incidence flat-field optics by using aberration corrected (varied line spacing) gratings and a multichannel plate detector combined with a charge-coupled device camera, which has already been applied to a transmission electron microscope. The best resolution was confirmed as 0.13 eV at Mg L-emission (50 eV), which is comparable with that of recent dedicated electron energy-loss spectroscopy instruments. This SXES-SEM instrument presents density of states of simple metals of bulk Mg and Li. Apparent band-structure effects have been observed in Si L-emission of Si wafer, P L-emission of GaP wafer, and Al L-emissions of intermetallic compounds of AlCo, AlPd, Al2Pt, and Al2Au.

A solid solution of Nd1−xSrxCoO3−δ (with x=0, 1/3, 2/3, and 1) has been prepared and characterized by a combination of X-ray diffraction, electron microscopy, and electron energy-loss spectroscopy (EELS). The structural characterization indicates that Nd-doped materials present an orthorhombic symmetry with a=√2xap, b=√2xap, and c=2xap (ap refers to lattice parameter of simple cubic perovskite), while SrCoO2.5 has an orthorhombic symmetry with a=√2xap, b=4xap, and c=√2xap. EELS analysis revealed that Co are in 3+ oxidation states but in different spin configurations.

Physicochemical properties of transition metal oxides are directly determined by the oxidation state of the metallic cations. To address the increasing need to accurately evaluate the oxidation states of transition metal oxide systems at the nanoscale, here we present “Oxide Wizard.” This script for Digital Micrograph characterizes the energy-loss near-edge structure and the position of the transition metal edges in the electron energy-loss spectrum. These characteristics of the edges can be linked to the oxidation states of transition metals with high spatial resolution. The power of the script is demonstrated by mapping manganese oxidation states in Fe3O4/Mn3O4 core/shell nanoparticles with sub-nanometer resolution in real space.

Energy filtered transmission electron microscopy techniques are regularly used to build elemental maps of spatially distributed nanoparticles in materials and biological specimens. When working with thick biological sections, electron energy loss spectroscopy techniques involving core-loss electrons often require exposures exceeding several minutes to provide sufficient signal to noise. Image quality with these long exposures is often compromised by specimen drift, which results in blurring and reduced resolution. To mitigate drift artifacts, a series of short exposure images can be acquired, aligned, and merged to form a single image. For samples where the target elements have extremely low signal yields, the use of charge coupled device (CCD)-based detectors for this purpose can be problematic. At short acquisition times, the images produced by CCDs can be noisy and may contain fixed pattern artifacts that impact subsequent correlative alignment. Here we report on the use of direct electron detection devices (DDD’s) to increase the signal to noise as compared with CCD’s. A 3× improvement in signal is reported with a DDD versus a comparably formatted CCD, with equivalent dose on each detector. With the fast rolling-readout design of the DDD, the duty cycle provides a major benefit, as there is no dead time between successive frames.

It is demonstrated that energy-filtered transmission electron microscope enables following of in situ changes of the Ca-L2,3 edge which can originate from variations in both local symmetry and bond lengths. Low accelerating voltages of 20 and 40 kV slow down radiation damage effects and enable study of the start and finish of phase transformations. We observed electron beam-induced phase transformation of single crystalline calcite (CaCO3) to polycrystalline calcium oxide (CaO) which occurs in different stages. The coordination of Ca in calcite is close to an octahedral one streched along the <111> direction. Changes during phase transformation to an octahedral coordination of Ca in CaO go along with a bond length increase by 5 pm, where oxygen is preserved as a binding partner. Electron loss near-edge structure of the Ca-L2,3 edge show four separated peaks, which all shift toward lower energies during phase transformation at the same time the energy level splitting increases. We suggest that these changes can be mainly addressed to the change of the bond length on the order of picometers. An important pre-condition for such studies is stability of the energy drift in the range of meV over at least 1 h, which is achieved with the sub-Ångström low-voltage transmission electron microscope I prototype microscope.

Characteristic energies of photonic modes are a sensitive function of a nanostructures’ geometrical parameters. In the case of translationally invariant planar waveguides, the eigen-energies reside in the infrared to ultraviolet parts of the optical spectrum and they sensitively depend on the thickness of the waveguide. Using swift electrons and the inherent Cherenkov radiation in dielectrics, the energies of such photonic states can be effectively probed via monochromated electron energy-loss spectroscopy (EELS). Here, by exploiting the strong photonic signals in EELS with 200 keV electrons, we correlate the energies of waveguide peaks in the 0.5–3.5 eV range with planar thicknesses of the samples. This procedure enables us to measure the thicknesses of cross-sectional transmission electron microscopy samples over a 1–500 nm range and with best-case accuracies below ±2%. The measurements are absolute with the only requirement being the optical dielectric function of the material. Furthermore, we provide empirical formulation for rapid and direct thickness estimations for a 50–500 nm range. We demonstrate the methodology for two semiconducting materials, silicon and gallium arsenide, and discuss how it can be applied to other dielectrics that produce strong optical fingerprints in EELS. The asymptotic form of the loss function for two-dimensional materials is also discussed.

In this work we report a study of the chemical and structural order of the double perovskite compound Sr2-xGdxMnTiO6 for compositions x=0, 0.25, 0.5, 0.75, and 1. A noticeable disorder at the B-site in the Mn and Ti sublattice is detected at the atomic scale by electron energy-loss spectroscopy for all x values, resulting in Mn-rich and Ti-rich regions. For x≥0.75, the cubic unit cell doubles and lowers its symmetry because of structural rearrangements associated with a giant ferroelectric displacement of the perovskite B-site cation. We discuss this finding in the light of the large electroresistance observed in Sr2-xGdxMnTiO6, x≥0.75.

Ultrathin ferroelectric heterostructures (SrTiO3/BaTiO3/BaRuO3/SrRuO3) were studied by scanning transmission electron microscopy (STEM) in terms of structural distortions and atomic displacements. The TiO2-termination at the top interface of the BaTiO3 layer was changed into a BaO-termination by adding an additional BaRuO3 layer. High-angle annular dark-field (HAADF) imaging by aberration-corrected STEM revealed that an artificially introduced BaO-termination can be achieved by this interface engineering. By using fast sequential imaging and frame-by-frame drift correction, the effect of the specimen drift was significantly reduced and the signal-to-noise ratio of the HAADF images was improved. Thus, a quantitative analysis of the HAADF images was feasible, and an in-plane and out-of-plane lattice spacing of the BaTiO3 layer of 3.90 and 4.22 Å were determined. A 25 pm shift of the Ti columns from the center of the unit cell of BaTiO3 along the c-axis was observed. By spatially resolved electron energy-loss spectroscopy studies, a reduction of the crystal field splitting (CFS, ΔL3=1.93 eV) and an asymmetric broadening of the eg peak were observed in the BaTiO3 film. These results verify the presence of a ferroelectric polarization in the ultrathin BaTiO3 film.

In this study we combine scanning transmission electron microscopy, electron energy loss spectroscopy and electron magnetic circular dichroism to get new insights into the electronic and magnetic structure of LaSr-2×4 manganese oxide molecular sieve nanowires integrated on a silicon substrate. These nanowires exhibit ferromagnetism with strongly enhanced Curie temperature (Tc>500 K), and we show that the new crystallographic structure of these LaSr-2×4 nanowires involves spin orbital coupling and a mixed-valence Mn3+/Mn4+, which is a must for ferromagnetic ordering to appear, in line with the standard double exchange explanation.

Monochromated electron energy-loss spectroscopy (EELS) is employed to determine the optical properties of carbonaceous aerosols from the infrared to the ultraviolet region of the spectrum. It is essential to determine their optical properties to understand their accurate contribution to radiative forcing for climate change. The influence of surface and interface plasmon effects on the accuracy of dielectric data determined from EELS is discussed. Our measurements show that the standard thin film formulation of Kramers−Kronig analysis can be employed to make accurate determination of the dielectric function for carbonaceous particles down to about 40 nm in size. The complex refractive indices of graphitic and amorphous carbon spherules found in the atmosphere were determined over the wavelength range 200–1,200 nm. The graphitic carbon was strongly absorbing black carbon, whereas the amorphous carbon shows a more weakly absorbing brown carbon profile. The EELS approach provides an important tool for exploring the variation in optical properties of atmospheric carbon.

Energy resolution is one of the most important parameters in electron energy-loss spectroscopy. This is especially true for measurement of surface plasmon resonances, where high-energy resolution is crucial for resolving individual resonance peaks, in particular close to the zero-loss peak. In this work, we improve the energy resolution of electron energy-loss spectra of surface plasmon resonances, acquired with a monochromated beam in a scanning transmission electron microscope, by the use of the Richardson–Lucy deconvolution algorithm. We test the performance of the algorithm in a simulated spectrum and then apply it to experimental energy-loss spectra of a lithographically patterned silver nanorod. By reduction of the point spread function of the spectrum, we are able to identify low-energy surface plasmon peaks in spectra, more localized features, and higher contrast in surface plasmon energy-filtered maps. Thanks to the combination of a monochromated beam and the Richardson–Lucy algorithm, we improve the effective resolution down to 30 meV, and evidence of success up to 10 meV resolution for losses below 1 eV. We also propose, implement, and test two methods to limit the number of iterations in the algorithm. The first method is based on noise measurement and analysis, while in the second we monitor the change of slope in the deconvolved spectrum.

We report the analysis of the changes in local carbon structure and chemistry caused by the self-implantation of carbon into diamond via electron energy-loss spectroscopy (EELS) plasmon energy shifts and core-edge fine structure fingerprinting. These two very different EELS energy and intensity ranges of the spectrum can be acquired under identical experimental conditions and nearly simultaneously using specially designed deflectors and energy offset devices known as “DualEELS.” In this way, it is possible to take full advantage of the unique and complementary information that is present in the low- and core-loss regions of the EELS spectrum. We find that self-implanted carbon under the implantation conditions used for the material investigated in this paper creates an amorphous region with significant sp2 content that varies across the interface.

We present a theoretical framework for calculating probe-position-dependent electron energy-loss near-edge structure for the scanning transmission electron microscope by combining density functional theory with dynamical scattering theory. We show how simpler approaches to calculating near-edge structure fail to include the fundamental physics needed to understand the evolution of near-edge structure as a function of probe position and investigate the dependence of near-edge structure on probe size. It is within this framework that density functional theory should be presented, in order to ensure that variations of near-edge structure are truly due to local electronic structure and how much from the diffraction and focusing of the electron beam.

A model-based fitting algorithm for electron energy-loss spectroscopy spectra is introduced, along with an intuitive user-interface. As with Verbeeck & Van Aert, the measured spectrum, rather than the single scattering distribution, is fit over a wide range. An approximation is developed that allows for accurate modeling while maintaining linearity in the parameters that represent elemental composition. Also, a method is given for generating a model for the low-loss background that incorporates plural scattering. Operation of the user-interface is described to demonstrate the ease of use that allows even nonexpert users to quickly obtain elemental analysis results.