Investigations of thin hydrogenated amorphous carbon films using electron energy loss spectroscopy (EELS)

Transmission EELS measurements have been carried out on a-C:H films deposited by ion plating from acetone or n-hexane plasma using various substrate potentials. The calculated dielectric functions show low optical absorption in the range of 4 eV to 8 eV. The amount of sp³ hybridizised C atoms has been estimated by integration over the * and * band ranges in the core loss spectra.     

Coincidence electron spectrometer for studying electron–atom collisions

The details of our recently developed coincidence electron spectrometer system with the block diagram and characteristics of the coincidence circuit are presented. As a first application we measured the continuous energy spectra of the scattered electron projectiles producing an L_2,3 inner-shell ionization/excitation of argon. The studied energy region was the neighbourhood of the ionization edge, where nearly the total excess energy is taken away by the scattered projectile. Above the edge we identify the peaks of the scattered electrons that produced 2p_3/2→4s or 2p_3/2→3d excitation.     

Auger and electron energy loss spectroscopies of small palladium particles supported on (111) oriented MgO films

The most common tool used to characterize supported metal clusters is the transmission electron microscope. The main advantage of TEM is the combination of high (lateral) resolution imaging with electron diffraction. However the TEM observations are usually made ex-situ i.e. UHV deposited clusters have to be exposed to the atmosphere during transfer to the TEM. This could be a severe limitation for very small reactive clusters. This paper demonstrates that electron spectroscopies can provide in-situ information on the cluster growth (AES), on the electronic structure (ELS) and on the local atomic order (SEELFS) of the clusters. These techniques were applied to Pd clusters of varying size (～10–200 Å) vapor-deposited on thin (111) MgO support films under UHV conditions. An expansion of the lattice and a shift of the loss peaks towards higher energies are observed with decreasing particle size.     

Momentum transfer effects in near surface electron energy loss

We examine two formulations for the differential surface excitation parameter (DSEP): one provided by Tung et al. and the other given by the Chen–Kwei position‐dependent differential inverse inelastic mean free path integrated over the electron trajectory. We demonstrate that the latter converges to the former provided that the dielectric function of the solid does not depend on the momentum transfer or it depends on just the momentum transfer component parallel to the surface. Tung's DSEP represents therefore an approximation to the Chen–Kwei DSEP calculated for a dielectric function with no restrictions on the momentum dependence. The approximation is shown to work in the limit of small momentum transfer and to imply an error of 4%–5% for electrons traveling through the solid with energy E = 1 keV. Copyright © 2015 John Wiley & Sons, Ltd.     

A study of the sodium tungsten bronzes by high-resolution electron energy loss spectroscopy

Effective masses of conduction electrons in the sodium tungsten bronzes have been determined from the frequency of surface plasmon features in high-resolution electron energy loss spectra. Good agreement is found with effective masses from optical experiments. The results support the view that there is no major depletion in the carrier concentration at the surface of the bronzes.     

Synthesis of electron energy loss spectra for the quantification of detection limits.

We describe a method for predicting detection limits of minority elements in electron energy loss spectroscopy (EELS), and its implementation as a software package that gives quantitative predictions for user-specified materials and experimental conditions. The method is based on modeling entire energy loss spectra, including shot noise as well as instrumental noise, and taking into account all the relevant experimental parameters. We describe the steps involved in modeling the entire spectrum, from the zero loss up to inner shell edges, and pay particular attention to the contributions to the pre-edge background. The predicted spectra are used to evaluate the signal-to-noise ratios (SNRs) for inner shell edges from user-specified minority elements. The software also predicts the minimum detectable mass (MDM) and minimum mass fraction (MMF). It can be used to ascertain whether an element present at a particular concentration should be detectable for given experimental conditions, and also to quickly and quantitatively explore ways of optimizing the experimental conditions for a particular EELS analytical task. We demonstrate the usefulness of the software by confirming the recent empirical observation of single atom detection using EELS of phosphorus in thin carbon films, and show the effect on the SNR of varying the acquisition parameters. The case of delta-doped semiconductors is also considered as an important example from materials science where low detection limits and high spatial resolution are essential, and the feasibility of such characterization using EELS is assessed.     

A rapid-scanning electron paramagnetic resonance spectrometer with stopped-flow mixing

Modifications to a commercial electron paramagnetic resonance (e.p.r.) spectrometer are described which allow data to be obtained from 64 e.p.r, spectra (0.1–100 gauss per scan) with scan times of 0.010–0.900 s and with 0.020–900 s delay times between scans. Reagents are delivered into an e.p.r, cell from a stopped-flow mixer that triggers the generation of a microprocessor-controlled waveform to drive a rapid-scan unit. This digitally synthesized waveform is designed to correct inherent imperfections in the Helmholtz-type sweep coil circuit in the rapid-scan unit. The spectra are digitized (250 points per scan) and can be processed to determine rates of reaction. Performance of the system is demonstrated by the determination of the kinetics of rearrangement of a bis(di- peptide)nickelate(III) complex.     

Determination of the parameters of atomic pair correlations in nickel oxide films by the electron energy loss fine structure method

The electron energy loss extended fine structure (EELFS) spectra were obtained from the pure nickel surface (M _2,3 EELFS) of a stoichiometric NiO film (NiM _2,3 and OK EELFS spectra) and the “nonhomogeneous” oxide film on the surface of nickel Ni-O (NiM _2,3 and OK EELFS spectra). The amplitudes and intensities of electron transitions for the core levels of atoms were calculated with regard for the multiplicity of electron impact excitation of the corresponding core levels of atoms. The corresponding normalized oscillating terms were isolated using the results of calculations based on the experimental EELFS spectra. Agreement between the experimental and calculated (on Ni and NiO test objects) data showed that the theoretical approaches used and the calculated data for describing the EELFS spectra are good approximations. Using the results of calculations and the parameters of secondary electron elastic scattering (FEEF-8 data) we obtained the atomic pair correlation functions from the experimental normalized oscillating parts of the EELFS spectra by Tikhonov’s regularization method.     

High-resolution electron energy loss spectroscopy study of O-Cu(410)

We have investigated oxygen adsorption on Cu(410) by high-resolution electron energy loss spectroscopy, dosing O2 with a supersonic molecular beam at different surface temperatures and for different angles of incidence and beam energies or by backfilling. In the investigated crystal temperature range (127 < T < 570 K), adsorption is always dissociative. Depending on T, impact energy, and angle of incidence, the oxygen atoms end up in different adsorption configurations, characterized by different vibrational signatures. In particular, at grazing incidence when only the step edge is exposed to O2, the adatoms end up initially preferentially at the step edge. An ordered overlayer forms at half monolayer coverage when the adsorbate is mobile. Oxide patches develop eventually for large exposures performed by backfilling and at high crystal temperature.     

On the defect center electron energy loss structures from MgO surfaces

Electron energy loss spectroscopy (EELS) was applied to surfaces of (1) clean MgO(100), (2) ultrathin (0.5 Å average thickness) Cu layers deposited on MgO(100) by an electron beam evaporation technique, and (3) a carbon-contaminated MgO(100). The surface-defect-related energy loss peak was ascribed to the presence of surface states arising from the V_s⁻ centers rather than from the F_s⁺ centers. The copper deposit is supposed to be trapped by the magnesium ion vacancies and bonded to the oxygen ligands as ions. The new electronic structures caused by the Cu deposit aie explained in terms of Cu impurity levels.     

Electronic structure of lithium nickel oxides by electron energy loss spectroscopy

The electronic structures of NiO, LiNiO2, and NiO2 are studied by the electron energy loss spectroscopy at Ni L(2,3), Ni M(2,3), and O K edges. The Ni L(2,3) edge spectra suggest that the formal charge of nickel is +2 in NiO, +3 with a low-spin state in LiNiO2, and +4 with a low-spin state in NiO2. This is well confirmed by first-principles calculations. The Ni M(2,3) edge spectra show similar chemical shifts to those of the Ni L(2,3) edge. Superposition of the Li K edge spectrum, however, hinders further analysis. Although the formal charge of oxygen is -2 in all the three phases, the O K edge spectra indicate a more remarkable difference in the electronic structure of the oxygen in NiO2 than that in either NiO or LiNiO2. The spectra suggest that lithium extraction from LiNiO2 reinforces the covalent bonding between the oxygen and nickel atoms and causes a notable reduction in electron density at the oxygen atoms.     

Richardson–Lucy deconvolution of reflection electron energy loss spectra

A procedure for deconvolving the energy spread introduced by the primary beam and the analyzer in a reflection electron energy loss spectrum (REELS) has been developed. The procedure is based on the Richardson–Lucy (RL) algorithm. The approach has been successfully tested on experimental spectra by comparison with spectra with an inherent high‐energy resolution. As a typical result, it was found that the effective energy resolution of spectra with a full width half maximum (FWHM) of the elastic peak of ～1.5 eV in the raw experimental data can be reduced to ～0.7 eV in the deconvoluted spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Low energy electron stimulated desorption from DNA films dosed with oxygen

Desorption of anions stimulated by 1-18 eV electron impact on self-assembled monolayer (SAM) films of single DNA strands is measured as a function of film temperature (50-250 K). The SAMs, composed of 10 nucleotides, are dosed with O(2). The OH(-) desorption yields increase markedly with exposure to O(2) at 50 K and are further enhanced upon heating. In contrast, the desorption yields of O(-), attributable to dissociative electron attachment to trapped O(2) molecules decrease with heating. Irradiation of the DNA films prior to the deposition of O(2) shows that this surprising increase in OH(-) desorption, at elevated temperatures, arises from the reaction of O(2) with damaged DNA sites. These results thus appear to be a manifestation of the so-called "oxygen fixation" effect, well known in radiobiology.     

Simultaneous multichannel mass-specific detection for high-performance liquid chromatography using an array detector sector-field mass spectrometer

The use of a separation step, such as liquid chromatography, prior to inductively coupled plasma mass spectrometry (ICP–MS) has become a common tool for highly selective and sensitive analyses. This type of coupling has several benefits including the ability to perform speciation analysis or to remove isobaric interferences. Several limitations of conventional instruments result from the necessity to scan or pulse the mass spectrometer to obtain a complete mass spectrum. When the instrument is operated in such a non-continuous manner, duty cycle is reduced, resulting in poorer absolute limits of detection. Additionally, with scanning instruments, spectral skew can be introduced into the measurement, limiting quantitation accuracy. To address these shortcomings, a high-performance liquid chromatograph has been coupled to an ICP–MS capable of continuous sample introduction and simultaneous multimass detection. These features have been realized with a novel detector array, the focal plane camera. Instrument performance has been tested for both speciation analysis and for the elimination of isobaric interferences. Absolute limits of detection in the sub picogram to tens of picograms regime are obtainable, while the added mass dimension introduced by simultaneous detection dramatically increases chromatographic peak capacity.     

Spatially resolved energy electron loss spectroscopy studies of iron oxide nanoparticles.

The oxidation state of iron oxide nanoparticles co-generated with soot during a combustion process was studied using electron energy-loss spectroscopy (EELS). Spatially resolved EELS spectra in the scanning transmission electron microscopy mode were collected to detect changes in the oxidation state between the cores and surfaces of the particles. Quantification of the intensity ratio of the white lines of the iron L-ionization edge was used to measure the iron oxidation state. Quantitative results obtained from Pearson's method, which can be directly compared with the literature data, indicated that the L3 /L2-intensity ratio for these particles changes from 5.5 +/- 0.3 in the particles' cores to 4.4 +/- 0.3 at their surfaces. This change can be directly related to the reduction of the iron oxidation state at the surface of the particles. Experimental results indicate that the cores of the particles are composed of gamma-Fe2O3, which seems to be reduced to FeO at their surfaces. These results were also supported by the fine structure of the oxygen K-edge and by the significant chemical shift of the iron L-edge.     

Structural analysis of SiO2 gel films by high energy electron diffraction

The structure of SiO₂ gel-films prepared from acid and basic TEOS solutions is analyzed by high energy transmission electron diffraction method. The Si-O bond length of gel-films is 1.58 to 1.60 Å, which is shorter than that of vitreous silica (1.61 Å) but similar to that of 80 Å thick evaporated a-SiO₂ film. An atomic pair peak with 0.81 Å distance exists on the reduced radial distribution functions of the gel-films, which is believed to be O-H, but being smaller than that of H₂O (0.969 Å).     

Improved background removal method using principal components analysis for spatially resolved electron energy loss spectroscopy.

Principal components analysis (PCA) factor filtering is implemented for the improvement of background removal in noisy spectra. When PCA is used as a method for filtering before background removal in electron energy loss spectroscopy elemental maps, an improvement in the accuracy of the background fit with very short fitting intervals is achieved, leading to improved quality of elemental maps from noisy spectra. This opens the possibility to use shorter exposure times for elemental mapping, leading to fewer problems with, for example, drift and beam damage.     

Interaction of thin metal films with the polyimide surface: electron energy loss spectroscopy of surface vibrations and uv photoemission of electronic states

We have applied electron energy loss spectroscopy to the study of metal—polymer bonding. Changes in polymer surface vibrational structure after deposition of Pd or Cr onto a thin polyimide film at room temperature are analyzed. Pd does not react with polyimide, but Cr reacts readily near carbonyl sites as evidenced by the rapid shift and attenuation of the CO vibrational band. The condensation of the metal overlayer is also determined by the onset of broadening of the elastic peak providing insight into the structural homogeneity of these metal films.     

Design of electron energy analyzers for electron impact studies

The design and construction of an electron energy analyzer for the study of electron impact processes in atoms, molecules and solids is described. The analyzer incorporates a 180° hemispherical deflector and five-element entrance optics. Focusing characteristics and angular behavior of the analyzer have been investigated by using the electron-ray tracing simulation program, SIMION. The entrance lens system to the hemispherical deflector has been designed to have high collection efficiency for low-energy electrons. The fringing field correction has been done by tilting the input beam angle outward for real aperture configuration.