Calculation of the electronic structure of carbon films using electron energy loss spectroscopy.

The detailed understanding of the electronic properties of carbon-based materials requires the determination of their electronic structure and more precisely the calculation of their joint density of states (JDOS) and dielectric constant. Low electron energy loss spectroscopy (EELS) provides a continuous spectrum which represents all the excitations of the electrons within the material with energies ranging between zero and about 100 eV. Therefore, EELS is potentially more powerful than conventional optical spectroscopy which has an intrinsic upper information limit of about 6 eV due to absorption of light from the optical components of the system or the ambient. However, when analysing EELS data, the extraction of the single scattered data needed for Kramers Kronig calculations is subject to the deconvolution of the zero loss peak from the raw data. This procedure is particularly critical when attempting to study the near-bandgap region of materials with a bandgap below 1.5 eV. In this paper, we have calculated the electronic properties of three widely studied carbon materials; namely amorphous carbon (a-C), tetrahedral amorphous carbon (ta-C) and C60 fullerite crystal. The JDOS curve starts from zero for energy values below the bandgap and then starts to rise with a rate depending on whether the material has a direct or an indirect bandgap. Extrapolating a fit to the data immediately above the bandgap in the stronger energy loss region was used to get an accurate value for the bandgap energy and to determine whether the bandgap is direct or indirect in character. Particular problems relating to the extraction of the single scattered data for these materials are also addressed. The ta-C and C60 fullerite materials are found to be direct bandgap-like semiconductors having a bandgaps of 2.63 and 1.59eV, respectively. On the other hand, the electronic structure of a-C was unobtainable because it had such a small bandgap that most of the information is contained in the first 1.2 eV of the spectrum, which is a region removed during the zero loss deconvolution.     

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.     

基于超声波技术的高性能牛乳成分快速测定仪

介绍了一种基于超声波技术的高性能牛乳成分快速测定仪的设计方案,阐述了超声波声速测定原理、仪器的硬件组成、主要电路和软件设计及其实现方法.     

Performance and applications of electron energy loss spectroscopy in stem

When coupled in the image mode to a VG-HB501 microscope, the spectrometer designed by O. Krivanek and manufactured by Gatan Inc. is well suited for resolving analytical problems with a high spatial resolution. It actually records energy loss spectra from areas as small as 0.5 nm with a typical energy resolution of 1 eV over the energy loss range and with a good efficiency in collecting inelastic electrons. During the last few months, this high performance combination of microscope and spectrometer has been used to investigate (a) detection limits in EELS which are presently estimated of the order of ten atoms in a test situation such as metallic clusters deposited on a very thin carbon layer; (b) quantitative chemical analysis of representative nanovolumes of complex oxide specimens, emphasizing several aspects of elemental segregation in the neighborhood of grain boundaries and within vitreous areas; (c) changes of fine structures close to the K-oxygen threshold, due to different bonding states; and (d) efficient Z-contrast imaging modes on sections of embedded biological material without metallic staining.     

Experimental and theoretical evidence for the magic angle in transmission electron energy loss spectroscopy

We present experimental measurements of the C K-ELNES of high temperature pyrolysed graphite and related crystalline materials as a function of collection angle and sample tilt. These results together with a corresponding theoretical analysis indicate that the so-called "magic angle" for EELS measurements of an anisotropic crystal such as graphite, where spectra are independent of sample orientation, is approximately two times the characteristic scattering angle. We briefly discuss the implications of this result for the experimental measurement of anisotropic structures, including interfaces, as well as for the detailed modelling of ELNES structures using advanced electronic structure calculations.     

A fast beam switch for controlling the intensity in electron energy loss spectrometry

The fast deflection system described in this paper is suitable for controlling the intensity reaching the detector of a magnetic sector electron spectrometer mounted below an analytical transmission electron microscope. Amongst other things, this allows the low loss region of the spectrum to be recorded with the same electron probe conditions used to record core losses, something that is essential for high spatial resolution studies. The plate assembly restricts the width of the electron distribution reaching the viewing screen to a strip approximately 17 mm wide in the direction approximately normal to the dispersion direction of the spectrometer. The resulting deflection has no detectable effect on the FWHM of the zero-loss peak for exposure times as short as 1 micros. At incident energies up to 300 keV, positioning the deflection plates in the 35 mm camera port above the viewing chamber allows voltages of < +/- 3 kV to deflect the electrons out of the spectrometer and beyond the edge of the annular detector. When the deflection is switched on, the electrons are deflected out of the spectrometer in < 40 ns and when the deflection is switched off, the electrons return to within 10 microm of the undeflected position within 100 ns. Thus, even at an exposure time of 30 micros, the smallest time likely to be used in practice with a GATAN 666 spectrometer, < 1% of the signal in the spectrum is from electrons whose scattering conditions differ from those in the undeflected position. The performance of the deflection system is such that it will also be suitable for use with the new and much faster GATAN ENFINA spectrometer system. At incident energies up to 200 keV and possibly up to 300 keV, deflection voltages of +/- 3 kV are sufficient to deflect the electrons off a 1 k x 1 k charge coupled device (CCD) camera placed below the photographic camera. Thus the deflection system can be used as a very fast, non-mechanical shutter for such a CCD camera.     

Comparison between off-resonance and electron Bernstein waves heating regime in a microwave discharge ion source

A microwave discharge ion source (MDIS) operating at the Laboratori Nazionali del Sud of INFN, Catania has been used to compare the traditional electron cyclotron resonance (ECR) heating with an innovative mechanisms of plasma ignition based on the electrostatic Bernstein waves (EBW). EBW are obtained via the inner plasma electromagnetic-to-electrostatic wave conversion and they are absorbed by the plasma at cyclotron resonance harmonics. The heating of plasma by means of EBW at particular frequencies enabled us to reach densities much larger than the cutoff ones. Evidences of EBW generation and absorption together with X-ray emissions due to high energy electrons will be shown. A characterization of the discharge heating process in MDISs as a generalization of the ECR heating mechanism by means of ray tracing will be shown in order to highlight the fundamental physical differences between ECR and EBW heating.     

Valence electron energy loss study of Fe-doped SrTiO3 and a sigma13 boundary: electronic structure and dispersion forces

Valence electron energy loss spectroscopy in a dedicated scanning transmission electron microscope has been used to obtain the interband transition strength of a sigma13 tilt grain boundary in SrTiO3. In a first step the electronic structure of bulk SrTiO3 has been analysed quantitatively by comparing VEELS spectra with vacuum ultraviolet spectra and with ab initio density of states calculations. The electronic structure of a near sigma13 grain boundary and the corresponding dispersion forces were then determined by spatially resolved VEELS. Also the effects of delocalization of the inelastic scattering processes were estimated and compared with results from the literature.     

Deadtime corrections for a pulse counting system in electron energy loss spectroscopy

We have measured the relationship between the input and output pulse rates for an EELS pulse counting system. Two simple formulae for predicting the behaviour of such a system are compared with the data. One is for a system which has extendible deadtime. The other is for the counting system which has non-extendible deadtime. The latter provides agreement with our experimental results over the range 0–20 MHz.     

Contribution of electron energy loss spectroscopy to the development of analytical electron microscopy.

The combined use of an electron energy loss spectrometer and an electron microscope provides some chemical information at the nanometer scale. The physics of the interaction processes between the incident electron beam and the thin sample foil is reviewed in terms of energy and momentum transfer. This analysis of the content of an electron energy loss spectrum allows us to establish rules for a satisfactory use of the information and to discuss the detection limits of this newly developed microanalytical technique.     

Optimization of quantitative electron energy loss spectroscopy in the low loss region: phosphorus L-edge.

The purpose of this study was to optimize quantitative electron energy loss spectroscopy (EELS) of elements that have characteristic edges in the low energy loss region and are components of organic matrices. The optimum parameters for phosphorus L2,3-edge (at 135 eV) detection were determined by numerical analysis of computer-generated, Poisson-noisy spectra and by experimental measurements (at 80 keV) of films of the phosphoprotein, phosvitin. When the first, second and third valence electron/plasmon scatterings are included in the multiple least-squares (MLS) fit, the background subtraction of (first-difference) spectra is significantly more accurate than that obtained with the "inverse power law" method, even for a specimen thickness of only 0.25 lambda. Taking into account the effects of plural scattering, the optimal thickness for P quantitation is approximately 0.3 lambda. Signal-to-noise (S/N) ratio decreases rapidly with thickness, and at 1.0 lambda, it is only about 60% of the optimum S/N. The combined effects of the statistical uncertainty of measurements and of the systematic error due to gain variations of the parallel detector were evaluated, and the relative sensitivities of the no-difference (raw spectrum), first-difference and second-difference methods were compared. For channel-to-channel gain variations greater than 0.1% and up to 0.8%, the first-difference method results in the lowest uncertainty of P measurements. In the absence of gain variations, direct fitting provides the greatest sensitivity (least uncertainty), whereas at larger gain variations it may be necessary to use the second-difference method. The optimum energy shift for collecting a first-difference spectrum, approximately 15 eV, did not show any great variation between 5 and 25 eV, and is, in general, specimen dependent. Quantitation with EELS showed excellent correlation with simultaneous electron probe X-ray microanalysis, but, for the detection of P in a 0.25 lambda thick specimen, EELS was approximately five to six times more sensitive than X-ray. The minimal detectable P concentration, with 0.5 nA beam current for 100 s in a 0.25 lambda thick specimen, was 8.4 mmol/kg (0.01 at%) at the 99% confidence level, equivalent to 34 phosphorus atoms for a 15 nm probe. This value is close to the theoretical prediction of 7.5 mmol/kg, and can be improved only by further reducing the gain variation and directly fitting the non-difference spectrum. Appropriate reduction of the gain variations to less than 0.1% would result in a further, approximately two-fold, improvement in the parallel EELS detection system.(ABSTRACT TRUNCATED AT 400 WORDS)     

The potential of energy loss spectroscopy for electronic characterization of structures on the nanometer scale

The last few years have seen a dramatic increase in the use of electron spectroscopy coupled with microscopy. Though dominant consideration has been aimed at elemental analysis and the use of ELS as a complementary tool with EDX for elemental determination, much less consideration has been given to one of the more powerful aspects of this spectroscopy, namely, electronic structure determination on the nanometer scale. It is the purpose here to consider certain aspects of such determination on the nanometer scale (with reference to elucidation and evaluation of man-made nanostructures) and to discuss some aspects of spectrometer design relevant to such determinations.     

Optimizing the window size for multiple least squares fitting of electron energy loss spectra

The purpose of this study was to determine the effect of the fitting window size used with the linear least squares fit method when quantitating trace elements with electron energy loss spectroscopy. Theory and computer simulation with a simple model of two 'signals' show that, when the background underlying the signal is slowly varying and the signal is localized, there exists a minimum window optimal for fitting raw spectra. The width of the minimum fitting window can be determined directly from the reference standard spectrum of the signal alone and the estimates of signal and background are related. Use of narrower than the minimum window will increase the fitting uncertainty of the signal and yield less reliable results. More complicated experimental spectra must be fitted to more than two standards and a simple analytical expression of the minimum fitting window cannot be derived, but can be determined empirically. Our study shows that the empirical value obtained from experimental spectra is only slightly larger than the theoretical value derived from the simple model, indicating that this conclusion is still valid. When fitting difference spectra with a slowly varying background, the estimates of signal and background are independent and windows wider than the size of the signal will yield the same fitting uncertainty. In the presence of a non-slowly varying background, common in difference spectra, the minimum window size depends on the fine structure of the signal and the background.     

Mass thickness determination by electron energy loss for quantitative X-ray microanalysis in biology

As is well known, electron energy loss spectroscopy can be used to determine the relative sample thickness in the electron microscope. This paper considers how such measurements can be applied to biological samples in order to obtain the mass thickness for quantitative X-ray microanalysis. The important quantity in estimating the mass thickness from an unknown sample is the total inelastic cross section per unit mass. Models for the cross section suggest that this quantity is constant to within ±20% for most biological compounds. This is comparable with the approximation made in the continuum method for measuring mass thickness. The linearity of the energy loss technique is established by some measurements on evaporated films and quantitation is demonstrated by measurements on thin calcium standards. A significant advantage of the method is that the energy loss spectrum can be recorded at very low dose, so that mass thickness determination can be made before even the most sensitive samples suffer damage resulting in mass loss. The energy loss measurements avoid the necessity to correct the continuum measurement for stray radiation produced in the vicinity of the sample holder. Unlike the continuum method the energy loss technique requires uniform mass thickness across the probe area, but this is not usually a problem when small probes (<100 nm diameter) are used.     

Extended fine structure in electron energy loss spectra of MgO crystallites

EXAFS-like features in energy loss spectra (known as EXELFS) were observed by using an imaging energy filter built into an electron microscope. Single crystal micro-platelets of MgO were used as test samples. Extended fine structures were obtained reproducibly in the energy range up to 150 eV beyond the OK, MgK and MgL edges. Comparison with single scattering calculations for the K edges showed a fair agreement, indicating the feasibility of this type of analysis.     

Visualization of bloch waves of high energy electrons in high resolution electron microscopy

By applying the Bloch wave theory of electron diffraction to the problem of lattice images in high resolution electron microscopy, it is shown that those characteristic type of images as found for Ge <110> can be interpreted as images of individual Bloch waves formed by the incident electron inside the lattice.