Stoichiometry and valence measurements of niobium oxides using electron energy-loss spectroscopy

Qualitative and quantitative electron energy‐loss spectroscopy analyses have been performed on niobium and stable niobium oxides (NbO, NbO₂ and Nb₂O₅). At integration windows (Δ) greater than 75 eV, k‐factor analysis can be used to distinguish between the stoichiometry of the three oxides within 5.7% error. As seen in other metal oxides, with increasing oxidation state the metal ionization edges shift to higher energies relative to the O‐K edge. Normalized M_2,3 white‐line intensities show a strong correlation with 4d occupancy for each compound. The data are in correspondence with that observed in the literature for 4d transition metals using normalized L_2,3 white lines. Lastly, a distinctive energy‐loss near‐edge, structure of the O‐K edge was observed for each oxide, which could be used as a fingerprint for analysis of unknowns.     

The influence of objective lens aberrations in energy-loss spectrometry

The conditions under which the energy resolution and collection efficiency in electron energy-loss spectrometry are limited by the spherical and chromatic aberrations of the objective lens have been studied. It is shown that, for the optimum settings of the pre-spectrometer optics, the energy resolution will be of the same order in diffraction mode as it is in magnification mode. The influence of the aberrations on the practice of energy-loss spectroscopy is discussed, and it is demonstrated that the chromatic aberration can act as a broadband filter for energy-loss electrons.     

Surface microanalysis by reflection electron energy-loss spectroscopy

Several basic physical concepts of applying eq. I_k = IσN^xt to surface microanalysis by reflection electron energy-loss spectroscopy (REELS) are clarified. Here I^k and I are the integrated intensities of the core ionization edge and the low loss part, σ is the scattering cross section of element x with atomic concentration N^x, and t is the specimen thickness. The reflected inelastic electrons are found to be distributed almost symmetrically around the Bragg sports and can be reasonably described by a Lorentzian function. EELS microanalysis can be performed by using the diffracted sports. The ω correction, arising from the angular contributions of the neighbouring spots into the spectrometer collecting aperture, is required to be considered.     

The impact of surface and retardation losses on valence electron energy-loss spectroscopy

The inelastic scattering of fast electrons transmitting thin foils of silicon (Si), silicon nitride (Si(3)N(4)), gallium arsenide (GaAs), gallium nitride (GaN) and cadmium selenide (CdSe) was analyzed using dielectric theory. In particular, the impact of surface and bulk retardation losses on valence electron energy-loss spectroscopy (VEELS) was studied as a function of the foil thickness. It is shown that for the materials analyzed, surface and retardation losses can cause a systematic, thickness-dependent modulation of the dielectric volume losses, which can hamper the determination of the bulk dielectric data as well as the identification of band-gap and interband transition energies by VEELS. For Si and GaAs, where the dielectric function is strongly peaked with high absolute values, retardation losses lead to additional intensity maxima in the spectrum. For thin films of these materials (below approximately 100 nm), the additional intensity maxima are related to retardation effects due to the finite size of the sample leading to the excitation of guided light modes. For thicker films, exceeding about 200 nm, the intensity maxima are caused by bulk retardation losses, i.e., Cerenkov losses. Although thickness-dependent modulations were observed for Si(3)N(4), GaN and CdSe, the form of the dielectric functions and their lower maxima, means that for TEM samples < 100 nm thick, the band-gap energies of these materials can be accurately identified by VEELS. Guidelines are given that allow for forecasting the impact of surface and retardation losses on VEELS.     

低色差GRIN棒透镜的设计原则

对梯度折射率(GRIN)棒透镜色差的影响因素进行了讨论,根据Fantone模型,在光学玻璃Nd-V图中直观地表示了离子交换法制备低色差GRIN棒透镜时交换离子对的选择原则和基础玻璃光学性能确定原则.分析表明,以具有常用光学性质的玻璃作为基础玻璃,可以通过Na⁺/Li⁺交换或K⁺/Cs⁺交换获得低色差GRIN棒透镜,而K⁺/Tl⁺交换和Na⁺/Ag⁺交换所制作的GRIN棒透镜具有很大的色差.上述原则对低色差GRIN棒透镜的制作具有指导意义.     

Measurement of radiation damage by electron energy-loss spectroscopy

Inner shell ionization edges in the energy-loss spectrum were used to measure the loss of gaseous elements from thin samples of nitrocellulose, polyvinyl formal, copper phthalocyanine, graphite bisulphate and sodium chloride during exposure to 80 keV electrons. The irradiation kinetics were measured for electron doses up to 10⁴ C m^?2 and for dose rates up to 10 mA m^?2. The energy-loss technique is discussed in relation to other methods for assessing radiation damage.     

Valence electron energy-loss spectroscopy in monochromated scanning transmission electron microscopy

With the development of monochromators for (scanning) transmission electron microscopes, valence electron energy-loss spectroscopy (VEELS) is developing into a unique technique to study the band structure and optical properties of nanoscale materials. This article discusses practical aspects of spatially resolved VEELS performed in scanning transmission mode and the alignments necessary to achieve the current optimum performance of approximately 0.15 eV energy resolution with an electron probe size of approximately 1 nm. In particular, a collection of basic concepts concerning the acquisition process, the optimization of the energy resolution, the spatial resolution and the data processing are provided. A brief study of planar defects in a Y(1)Ba(2)Cu(3)O(7-)(delta) high-temperature superconductor illustrates these concepts and shows what kind of information can be accessed by VEELS.     

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.     

Measurement of local thickness by electron energy-loss spectroscopy

We review various methods which can be used to derive the thickness of an electron-microscope specimen from its transmission energy-loss spectrum. We have applied a sum-rule technique to various kinds of specimen, using a variety of electron-optical conditions, and estimate its accuracy to be typically ±10% (or±2nm if larger) over the thickness range 10–150 nm. This method requires no knowledge of the physical or chemical properties of the specimen other than its refractive index (∞ for metal). It involves only a low radiation dose, allowing good lateral resolution (<10 nm) to be achieved even by selected-area techniques.     

Background subtraction for low-loss transmission electron energy-loss spectroscopy

We present a technique for removing the zero-loss background from electron energy-loss spectra at very low energies (down to approximately 2eV), generating results that are superior in a number of ways to the results of standard Fourier deconvolution techniques. Our technique is based on a separately measured background spectrum which is spline-interpolated and matched to the zero-loss peak in the low-loss spectrum using curve-fit techniques. The data points are weighted with the use of a semi-empirical model of the random error in the data produced by a spectrometer. We demonstrate in tests on real-world data that this model accounts for the random error within the energy range of interest. We discuss practical details of implementation and present detailed comparisons of the results of various algorithms on a piece of test data obtained from a carbon nanotube sample. Compared to the standard techniques, our algorithm tends to be more consistent, less dependent on arbitrary parameters, and better able to quantify spectral features with small signal-to-noise ratios, particularly those at very low energies.     

Parallel electron energy-loss spectroscopy free from gain variation

A new method is presented for removing the effect of the gain variation of parallel detectors used for the quantitation of trace elements with electron energy loss spectroscopy (EELS). Use of the ratio of two first-difference spectra eliminates the effect of gain variation of the detector, therefore eliminating the need for gain normalization and dark current subtraction. This method is particularly suitable for revealing small signals superimposed on a large background, a typical scenario for trace element quantitation of both biological and inorganic materials. This method has been tested on a system with a cooled CCD camera as the parallel detector and illustrated by the analysis of low concentration Ca in an organic matrix. The method is expected to be generally applicable to spectral analysis affected by gain variations of parallel detectors.     

The addition of chromatic aberration coefficients

The asymptotic chromatic aberration coefficients of electron lenses may be written as polynomials in reciprocal magnification. Expressions for the polynomial coefficients of a doublet are derived in terms of those of the individual members of the doublet.     

Reflection electron energy-loss spectroscopy and imaging for surface studies in transmission electron microscopes.

A review is given on the techniques and applications of high-energy reflection electron energy-loss spectroscopy (REELS) and reflection electron microscopy (REM) for surface studies in scanning transmission electron microscopes (STEM) and conventional transmission electron microscopes (TEM). A diffraction method is introduced to identify a surface orientation in the geometry of REM. The surface dielectric response theory is presented and applied for studying alpha-alumina surfaces. Domains of the alpha-alumina (012) surface initially terminated with oxygen can be reduced by an intense electron beam to produce Al metal; the resistance to beam damage of surface domains initially terminated with Al+3 ions is attributed to the screening effect of adsorbed oxygen. Surface energy-loss near-edge structure (ELNES), extended energy-loss fine structure (EXELFS), and microanalysis using REELS are illustrated based on the studies of TiO2 and MgO. Effects of surface resonances (or channeling) on the REELS signal-to-background ratio are described. The REELS detection of a monolayer of oxygen adsorption on diamond (111) surfaces is reported. It is shown that phase contrast REM image content can be significantly increased with the use of a field emission gun (FEG). Phase contrast effects close to the core of a screw dislocation are discussed and the associated Fresnel fringes around a surface step are observed. Finally, an in situ REM experiment is described for studying atomic desorption and diffusion processes on alpha-alumina surfaces at temperatures of 1,300-1,400 degrees C.     

Assessment of electron irradiation damage to biomolecules by electron diffraction and electron energy-loss spectroscopy

Electron radiation damage is one of the most severe problems in high resolution electron microscopy of biomolecules. The techniques of electron diffraction and electron energy-loss spectroscopy were applied to gain a better understanding of radiation damage in amino acids and nucleic acid bases. The results when compared with G-values for the release of ammonia and hydrogen sulphide from amino acids seem to indicate that bond scission is an important cause of radiation damage at moderate doses of irradiation. High resolution structural disorder in nucleic acid bases was found to involve loss of atoms peripheral to the main ring structure.     

Multivariate statistical analysis of electron energy-loss spectroscopy in anisotropic materials

Recently, an expression has been developed to take into account the complex dependence of the fine structure in core-level electron energy-loss spectroscopy (EELS) in anisotropic materials on specimen orientation and spectral collection conditions [Y. Sun, J. Yuan, Phys. Rev. B 71 (2005) 125109]. One application of this expression is the development of a phenomenological theory of magic-angle electron energy-loss spectroscopy (MAEELS), which can be used to extract the isotropically averaged spectral information for materials with arbitrary anisotropy. Here we use this expression to extract not only the isotropically averaged spectral information, but also the anisotropic spectral components, without the restriction of MAEELS. The application is based on a multivariate statistical analysis of core-level EELS for anisotropic materials. To demonstrate the applicability of this approach, we have conducted a study on a set of carbon K-edge spectra of multi-wall carbon nanotube (MWCNT) acquired with energy-loss spectroscopic profiling (ELSP) technique and successfully extracted both the averaged and dichroic spectral components of the wrapped graphite-like sheets. Our result shows that this can be a practical alternative to MAEELS for the study of electronic structure of anisotropic materials, in particular for those nanostructures made of layered materials.     

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.     

Breaking the spherical and chromatic aberration barrier in transmission electron microscopy

Since the invention of transmission electron microscopy (TEM) in 1932 (Z. Physik 78 (1932) 318) engineering improvements have advanced system resolutions to levels that are now limited only by the two fundamental aberrations of electron lenses; spherical and chromatic aberration (Z. Phys. 101 (1936) 593). Since both aberrations scale with the dimensions of the lens, research resolution requirements are pushing the designs to lenses with only a few mm space in the pole-piece gap for the specimen. This is in conflict with the demand for more and more space at the specimen, necessary in order to enable novel techniques in TEM, such as He-cooled cryo electron microscopy, 3D-reconstruction through tomography (Science 302 (2003) 1396) TEM in gaseous environments, or in situ experiments (Nature 427 (2004) 426). All these techniques will only be able to achieve Angstrom resolution when the aberration barriers have been overcome. The spherical aberration barrier has recently been broken by introducing spherical aberration correctors (Nature 392 (1998) 392, 418 (2002) 617), but the correction of the remaining chromatic aberrations have proved to be too difficult for the present state of technology (Optik 57 (1980) 73). Here we present an alternative and successful method to eliminate the chromatic blur, which consists of monochromating the TEM beam (Inst. Phys. Conf. Ser. 161 (1999) 191). We show directly interpretable resolutions well below 1A for the first time, which is significantly better than any TEM operating at 200 KV has reached before.     

Quantitative water mapping of cryosectioned cells by electron energy-loss spectroscopy

A direct technique based on electron energy-loss spectroscopy (EELS) in the scanning transmission electron microscope (STEM) has been developed to map subcellular distributions of water in frozen-hydrated biological cryosections. Previously, methods for water determination have been indirect in that they have required the cryosections to be dehydrated first. The new approach makes use of spectrum-imaging, where EELS data are collected in parallel at each pixel. Several operations are required to process the spectra including: subtraction of the detector dark current, deconvolution by the detector point-spread function, removal of plural inelastic scattering and correction for the support film. The resulting single scattering distributions are fitted to standard reference spectra at each pixel, and water content can be determined from the fitting coefficients. Although the darkfield or brightfield image from a hydrated cryosection shows minimal structure, the processed EELS image reveals strong contrast due to variations in water content. Reference spectra have been recorded from the major biomolecules (protein, lipid, carbohydrate, nucleic acid) as well as from vitrified water and crystalline ice. It has been found that quantitative results can be obtained for the majority of subcellular compartments by fitting only water and protein reference spectra, and the accuracy of the method for these compartments has been estimated as ± 3·5%. With the present instrumentation the maximum allowed dose of 2 × 10³ e/nm² limits the useful spatial resolution to around 80 nm for ± 5% precision at a single pixel. By averaging pixel intensities a value of 56·8% with a precision of ± 2·0% has been determined for the water content of liver mitochondria. The water mapping technique may prove useful for applications to cell physiology and pathophysiology.     

Fourier-ratio deconvolution techniques for electron energy-loss spectroscopy (EELS)

We discuss several ways of using Fourier-ratio deconvolution to process low-loss spectra. They include removal of the tail arising from the zero-loss peak, extraction of the spectrum of a particle from data recorded from the particle on a substrate, separation of the bulk and surface components in spectra recorded from samples of the same composition but different thickness, and investigation of interface energy-loss modes. We also demonstrate the use of a Bayesian-equivalent procedure based on the Richardson–Lucy algorithm.     

A method of dynamic chromatic aberration correction in low-voltage scanning electron microscopes

A time-of-flight concept that dynamically corrects for chromatic aberration effects in scanning electron microscopes (SEMs) is presented. The method is predicted to reduce the microscope's chromatic aberration by an order of magnitude. The scheme should significantly improve the spatial resolution of low-voltage scanning electron microscopes (LVSEMs). The dynamic means of correcting for chromatic aberration also allows for the possibility of obtaining high image resolution from electron guns that have relatively large energy spreads.