Electron-specimen interactions in low-voltage scanning electron microscopy

Measurements of the electron range R, and the backscattering coefficient η and the secondary electron yield δ at normal and tilted incidence for different elements show characteristic differences for electron energies in the range of 0.5 to 5 keV, compared with energies larger than 5 keV. The backscattering coefficient does not increase monotonically with increasing atomic number; for example, the secondary electron yield shows a lesser increase with increasing tilt angle. This can be confirmed in back-scattered electron (BSE) and secondary electron (SE) micrographs of test specimens. The results are in rather good agreement with Monte Carlo simulations using elastic Mott cross-sections and a continuous-slowing-down model with a Rao Sahib-Wittry approach for the stopping power at low electron energies. Therefore, this method can be used to calculate quantities of BSE and SE emission, which need a larger experimental effort. Calculations of the angular distribution of BSEs show an increasing intensity with increasing atomic number at high takeoff angles than expected from a cosine law that describes the angular characteristics at high electron energies. When simulating the energy distribution of BSEs, the continuous-slowing-down model should be substituted by using an electron energy-loss spectrum (EELS) that considers plasmon losses and inner-shell ionizations individually (single-scattering-function model). The EELS can be approached via the theory for aluminium or from EELS spectra recorded in a transmission electron microscope for other elements. Measurements of electron range Rα Eⁿ of 1 to 10 keV electrons are obtained from transmission experiments with thin films of known mass thickness. In agreement with other authors the exponent n is lower than at higher electron energies.     

Spatially resolved electron energy-loss studies of metal–ceramic interfaces in transition metal/alumina cermets

Composites consisting of an alumina matrix and 20 vol.% transition metal (Ni or Fe) particles, prepared by hot pressing powder blends, have been studied using spatially resolved transmission electron energy-loss spectroscopy (EELS), and, to a lesser extent, by high-resolution electron microscopy (HREM). Particular attention was paid to the elucidation of the chemical bonding mechanisms at the metal-ceramic interface; EELS spectra from interfacial regions being obtained via a spatial difference technique. From both qualitative and quantitative interpretation of EELS near-edge structures, as well as observed HREM images, the data appear to be consistent with the presence of an Al-terminated alumina at the interface and the formation of direct transition metal – aluminium bonds in Al(O₃M) (M = Ni or Fe) tetrahedral units, possibly as a result of the dissolution and interfacial reprecipitation of Al during processing. These results correlate well with similar model studies on diffusion-bonded Nb/Al₂O₃ interfaces and may, in the light of recent theoretical electronic structure calculations, have implications for the resultant interfacial bond strength in such materials.     

A systematic approach to choosing parameters for modelling fine structure in electron energy-loss spectroscopy

A potential methodology is presented for the systematic prediction of EELS edges using DFT, suitable for codes that calculate ELNES for a specific atom in a unit cell. The method begins with the selection of a unit cell, chosen as the smallest cell that still provides a physically valid representation of the bulk material. Within this small cell, a single electron core–hole is included in the atom for which the EELS ionisation edge is to be calculated. The basis-set size and k-point mesh of the DFT calculation are converged specifically against the predicted EELS result. Subsequently, the cell size is increased until the theoretical core–holes no longer interfere. At this point one can then modify the exact core–hole approximation. This methodology was applied to the new EELS module of the CASTEP pseudopotential DFT code, as well as the all-electron code Wien2k. Aluminium K edges were investigated for various aluminium metal systems. It was observed that as the cell size was increased the predicted EELS result became less sensitive to the exact core–hole approximation used. It was noted however that due to high screening in metals a ground state single cell calculation is often acceptable. The semiconductor aluminium nitride (wurtzite form) was also investigated. It was observed that for both Wien2k and CASTEP, with careful convergence of the key DFT code parameters, single cell ground state calculations gave a reasonable agreement with experiment, contrary to what might be expected for a semiconductor with a large band gap. This was particularly true of the Wien2k result. Given the greater computational effort required for supercell calculations, these results are likely to form the beginnings of a detailed investigation into accepted methods of ELNES predictions.     

Characterization of nanophase Al-oxide/Al powders by electron energy-loss spectroscopy

Al nanoparticles were prepared by the inert gas condensation method. After passivation with oxygen and air exposure we obtained a powdered sample of an Al-oxide/Al nanocomposite material. In the present paper we describe the use of the electron energy-loss spectroscopy (EELS) technique in a transmission electron microscope to characterize such nanostructured powders compared with a microcrystalline commercial aluminium foil. Energy-filtered images showed the presence of an alumina overlayer of ≈ 4 nm covering the aluminium nanoparticles (23 nm in diameter). EELS analysis enabled us to determine the total amount of Al₂O₃ and metallic Al and the structure of the alumina passivation overlayer in the sample. In particular, the extended energy-loss fine structure analysis of the data showed a major presence of Al tetrahedrally coordinated with oxygen in the alumina passivation layer of Al nanoparticles instead of the octahedral coordination found for a conventional Al foil. This surprising effect has been attributed to the nanoscopic character of the grains. The analysis of the electron-loss near-edge structure also determines the presence of a certain degree of aggregation in this kind of powdered sample as result of the coalescence of the nanocrystalline grains. The procedure presented here may have the potential to solve other problems during characterization of nanostructured materials.     

Annular electron energy-loss spectroscopy in the scanning transmission electron microscope

We study atomic-resolution annular electron energy-loss spectroscopy (AEELS) in scanning transmission electron microscopy (STEM) imaging with experiments and numerical simulations. In this technique the central part of the bright field disk is blocked by a beam stop, forming an annular entry aperture to the spectrometer. The EELS signal thus arises only from electrons scattered inelastically to angles defined by the aperture. It will be shown that this method is more robust than conventional EELS imaging to variations in specimen thickness and can also provide higher spatial resolution. This raises the possibility of lattice resolution imaging of lighter elements or ionization edges previously considered unsuitable for EELS imaging.     

Image-EELS: Simultaneous recording of multiple electron energy-loss spectra from series of electron spectroscopic images

A new approach for element microanalysis with energy-filtering transmission electron microscopy (EFTEM) is presented which was accomplished with the CEM 902 electron microscope (Zeiss, Germany). This method is called Image-EELS, because it is a synthesis of electron energy-loss spectroscopy (EELS) and electron spectroscopic imaging (ESI). Series of energy-filtered images at increasing energy losses are recorded from one area with a TV camera. In a second step the intensity of selected regions in the image stack is measured with an image analysis system and plotted as a function of the energy loss. Thus many spectra from different objects can be calculated from one image series and compared with each other. The spatial resolution of EELS is considerably enhanced, the noise is decreased because many pixels from irregular objects are integrated, and the information from ESI can be analysed as a function of the energy loss.     

Some effects of electron channeling on electron energy loss spectroscopy

As an electron beam (of order 100 keV) travels through a crystalline solid it can be channeled down a zone axis of the crystal to form a channeling peak centered on the atomic columns. The channeling peak can be similar in size to the outer atomic orbitals. Electron energy loss spectroscopy (EELS) measures the losses that the electron experiences as it passes through the solid yielding information about the unoccupied density of states in the solid. The interaction matrix element for this process typically produces dipole selection rules for small angle scattering. In this paper, a theoretical calculation of the EELS cross section in the presence of strong channeling is performed for the silicon L23 edge. The presence of channeling is found to alter both the intensity and selection rules for this EELS signal as a function of depth in the solid. At some depths in the specimen small but significant non-dipole transition components can be produced, which may influence measurements of the density of states in solids.     

Thickness measurements with electron energy loss spectroscopy

Measurements of thickness using electron energy loss spectroscopy (EELS) are revised. Absolute thickness values can be quickly and accurately determined with the Kramers-Kronig sum method. The EELS data analysis is even much easier with the log-ratio method, however, absolute calibration of this method requires knowledge of the mean free path of inelastic electron scattering lambda. The latter has been measured here in a wide range of solids and a scaling law lambda approximately rho(-0.3) versus mass density rho has been revealed. EELS measurements critically depend on the excitation and collection angles. This dependence has been studied experimentally and theoretically and an efficient model has been formulated.     

Extracting physically interpretable data from electron energy-loss spectra

Principal component analysis is routinely applied to analyze data sets in electron energy-loss spectroscopy (EELS). We show how physically meaningful spectra can be obtained from the principal components using a knowledge of the scattering of the probe electron and the geometry of the experiment. This approach is illustrated by application to EELS data for the carbon K edge in graphite obtained using a conventional transmission electron microscope. The effect of scattering of the probe electron is accounted for, yielding spectra which are equivalent to experiments using linearly polarized X-rays. The approach is general and can also be applied to EELS in the context of scanning transmission electron microscopy.     

Investigation and use of plasmon losses in energy-filtering transmission electron microscopy

The electron spectroscopic imaging (ESI), diffraction (ESD) and different types of electron energy-loss spectroscopy (EELS) modes in an energy-filtering transmission electron microscope can all be used for the investigation and analytical use of plasmon losses. Shifts of plasmon losses caused by differences in composition can be detected with an accuracy of 0.1 eV by parallel-recorded EELS (PEELS). The dispersion of plasmon losses and the cut-off angle θ_c can be observed by angle-dispersive EELS and by recording spectra at different scattering angles θ. ESD patterns with a selected energy window width of 1 eV enable the dispersion and its anisotropy to be imaged by characteristic intensity distributions between the primary beam and the first Bragg diffracted beams. The ESI mode can be used for the selective imaging of precipitates and for the investigation of the excitation volume of plasmons in small particles.     

Ultrastructural and electron spectroscopic analyses of cyanobacteria and bacteria

The extracellular sheath material and some intracellular cell components of cyanobacteria and phosphate-accumulating sewage bacteria were analysed by electron spectroscopic imaging (ESI) and electron energy-loss spectroscopy (EELS). The specimens were embedded in water-soluble Nanoplast resin without any previous fixation and ultrathin sections were examined in a Zeiss CEM 902 microscope. A high sulphur content was detected in the inner sheath of the cyanobacterium Gloeothece. The elemental composition of some cell components and inclusion bodies, such as carboxysomes and cyanophycin, was determined by ESI and EELS. In addition, the phosphate content in specific granules of phosphate-accumulating sewage bacteria was estimated by EELS and nuclear magnetic resonance spectroscopy.     

A proposal for dichroic experiments in the electron microscope

Building upon the similarities between inelastic electron scattering and X-ray absorption we show that dichroism can be observed in electron energy loss spectrometry (EELS) in the transmission electron microscope (TEM). Natural or magnetic linear dichroism can be studied in electron scattering experiment with definite wave vector transfer in the interaction.The detection of circular dichroism in the TEM relies on interferometric EELS in a particular scattering geometry that allows extraction of the mixed dynamic form factor from energy loss spectra. Similarities between dichroic signals in energy loss near edge structures and X-ray absorption near edge structures are discussed, and a new experimental setup for dichroic measurements in the TEM is proposed.     

A system for acquiring simultaneous electron energy-loss and X-ray spectrum-images

A compositional imaging system based on simultaneous scanning electron energy‐loss spectroscopy (EELS) and energy‐dispersive X‐ray spectroscopy (EDS) was developed. This system utilizes the combined power of EELS and EDS for quantitative compositional imaging at nanometre resolution. The system is particularly suitable for, but not limited to, biological research, as it simultaneously provides sensitive maps of an element such as Ca or P from EELS and of many other elements from EDS. Degradation of resolution by specimen drift is prevented by correcting for drift during data acquisition, using image cross‐correlation. Several advanced features are implemented for real‐time and/or off‐line quantitative analysis, and the performance of the system is illustrated with practical applications to compositional imaging of cardiac muscle.     

Smart acquisition EELS

We have developed a novel acquisition methodology for the recording of electron energy loss spectra (EELS) using a scanning transmission electron microscope (STEM): “Smart Acquisition”. Smart Acquisition allows the independent control of probe scanning procedures and the simultaneous acquisition of analytical signals such as EELS. The original motivation for this work arose from the need to control the electron dose experienced by beam-sensitive specimens whilst maintaining a sufficiently high signal-to-noise ratio in the EEL signal for the extraction of useful analytical information (such as energy loss near edge spectral features) from relatively undamaged areas. We have developed a flexible acquisition framework which separates beam position data input, beam positioning, and EELS acquisition. In this paper we demonstrate the effectiveness of this technique on beam-sensitive thin films of amorphous aluminium trifluoride. Smart Acquisition has been used to expose lines to the electron beam, followed by analysis of the structures created by line-integrating EELS acquisitions, and the results are compared to those derived from a standard EELS linescan. High angle annular dark-field images show clear reductions in damage for the Smart Acquisition areas compared to the conventional linescan, and the Smart Acquisition low loss EEL spectra are more representative of the undamaged material than those derived using a conventional linescan. Atomically resolved EELS of all four elements of CaNdTiO show the high resolution capabilities of Smart Acquisition.     

Parallel recording of electron energy loss spectra

Two silicon photo diode array devices were tested as parallel recording detectors for electron energy loss spectrometry (EELS). The direct bombardment of a Reticon photodiode array detector with high energy electrons (80 keV) causes an irreversible increase in diode dark current. The dark current saturates the detector amplifier after a dose of 10^?6 C/diode making it unsuitable for EELS. A scintillator coupled SIT vidicon is sensitive enough to count two high energy electrons with a spatial resolution of 100 μm, corresponding to 5 eV energy resolution with the electron optical system described. The large pixel-to-pixel gain variation inherent in the scintillator and vidicon can be reduced by averaging the spectrum over a large area of the target perpendicular to the dispersion direction. The L-edge of calcium for a 4 × 10^?3 weight fraction concentration biological specimen is observable in a 40 s parallel recorded spectrum. The minimum detectable concentration of calcium is estimated tobe ten times better for EELS than EDS X-ray analysis.     

In situ analysis of gas composition by electron energy-loss spectroscopy for environmental transmission electron microscopy

We have developed methods for using in situ electron energy-loss spectroscopy (EELS) to perform quantitative analysis of gas in an environmental transmission electron microscope. Inner-shell EELS was able to successfully determine the composition of gas mixtures with an accuracy of about 15% or better provided that some precautions are taken during the acquisition to account for the extended gas path lengths associated with the reaction cell. The unique valence-loss spectrum associated with many gases allowed simple methodologies to be developed to determine gas composition from the low-loss region of the spectrum from a gas mixture. The advantage of the valence loss approach is that it allows hydrogen to be detected and quantified. EELS allows real-time analysis of the volume of gas inside the reaction cell and can be performed rapidly with typical acquisition times of a few seconds or less. This in situ gas analysis can also be useful for revealing mass transport issues associated with the differential gas diffusion through the system.     

Quantitative electron energy loss spectroscopy in biology

The potential for applying electron energy loss spectroscopy (EELS) in biology is assessed. Some recent developments in instrumentation, spectrometer design, parallel detection and elemental mapping are discussed. Quantitation is demonstrated by means of the spectrum from DNA which gives an elemental ratio for N:P close to the expected value. A range of biologically important elements that can be usefully analyzed by EELS is tabulated and some possible applications for each are indicated. Detection limits and the effects of radiation damage are illustrated by spectra from the protein, insulin, and from the fluorinated amino-acid, histidine. Calcium detectability under optimum conditions may be as low as 1 mmol/kg dry weight. The application of EELS to analysis of cryosectioned adrenomedullary (chromaffin) cells is described in order to help determine the composition of the secretory granule. Water content can be determined from the amount of inelastic scattering as measured by the low-loss spectrum. The nitrogen/phosphorus ratio can be measured to provide information about the relative concentrations of ATP, chromogranin, and catecholamines. Quantitative EELS elemental maps are obtained in the STEM mode from chromaffin cells in order to measure the distribution of light elements.     

Development of a high energy resolution electron energy-loss spectroscopy microscope

We have developed a high energy resolution electron energy-loss spectroscopy (EELS) microscope, which can take spectra from specified small specimen areas and specified small reciprocal space areas to investigate detailed electronic structures. The EELS microscope is equipped with retarding Wien filters as the monochromator and the analyser. The filters are designed to achieve a stigmatic focus. The energy resolutions are 12 meV and 25 meV for cases without and with a specimen, respectively. Spatial and momentum resolutions are 30–110 nm in diameter and 1.1 nm⁻¹ in angular diameter, respectively. EELS spectra are presented to show the performance of this instrument.     

Limits to the spatial, energy and momentum resolution of electron energy-loss spectroscopy

We discuss various factors that determine the performance of electron energy-loss spectroscopy (EELS) and energy-filtered (EFTEM) imaging in a transmission electron microscope. Some of these factors are instrumental and have undergone substantial improvement in recent years, including the development of electron monochromators and aberration correctors. Others, such as radiation damage, delocalization of inelastic scattering and beam broadening in the specimen, derive from basic physics and are likely to remain as limitations. To aid the experimentalist, analytical expressions are given for beam broadening, delocalization length, energy broadening due to core-hole and excited-electron lifetimes, and for the momentum resolution in angle-resolved EELS.     

A new analytical method for characterising the bonding environment at rough interfaces in high-k gate stacks using electron energy loss spectroscopy

Determining the bonding environment at a rough interface, using for example the near-edge fine structure in electron energy loss spectroscopy (EELS), is problematic since the measurement contains information from the interface and surrounding matrix phase. Here we present a novel analytical method for determining the interfacial EELS difference spectrum (with respect to the matrix phase) from a rough interface of unknown geometry, which, unlike multiple linear least squares (MLLS) fitting, does not require the use of reference spectra from suitable standards. The method is based on analysing a series of EELS spectra with variable interface to matrix volume fraction and, as an example, is applied to a TiN/poly-Si interface containing oxygen in a HfO₂-based, high-k dielectric gate stack. A silicon oxynitride layer was detected at the interface consistent with previous results based on MLLS fitting.