Electron Energy Loss Microspectroscopy and the Characterization of Solids

The inelastic scattering of fast electrons provides a detailed means of characterizing the chemical composition and electronic properties of thin samples in an electron microscope. Collective and single-electron excitations occuring in the low energy region of the spectrum can be described in terms of the generalized dielectric formulation. Important information is contained in this part of the spectrum but some prior detailed knowledge of the sample is usually required for proper interpretation. The core excitations allow microanalytical information to be obtained and quantitative procedures are now quite well developed at least for K and L edges. Sample thickness is one factor that limits the quality of data in energy loss spectra and it is now possible to remove the effects of plural scattering from core edges as well as from the low loss spectrum. Several advances in instrumentation have been made recently both in electron optics and recording devices. It appears that the detection limits are very low, possibly 1 to 10 atoms in an optimized system. Measurements also show that the core edges offer a sensitive method for probing the chemical bonding and electronic structure, provided the energy resolution is sufficient (≤ 1 eV). Of particular interest is the momentum transfer and orientation dependence of the fine structure for crystalline materials. The transition elements exhibit very sharp features near the L23 threshold due to transitions to unoccupied d states and reasonable agreement is found with theory here. Another type of information can be obtained from the extended fine structure above the core edges (EXELFS). This is capable of yielding the local atomic environment around the different atomic species

Knowledge, documentation and a London location

Purpose – As documents, and the whole information and communication environment, become increasingly digital, it is natural to assume that physical location becomes of less importance. The aim of this paper is to highlight two newly published books, which remind us that this idea should be examined with a critical eye. Design/methodology/approach – This editorial takes the form of a literature review and a viewpoint. Findings – The paper finds books of this kind remind us that a physical place, a locality, has sometimes been a very powerful stimulus to the development of collections, of memory institutions, and of the advances in education and dissemination of knowledge which are associated with them. This is worth remembering as we move into a digital information world. Originality/value – The paper offers the author's viewpoint as well as highlighting these two books which join a small number which have analysed and celebrated the history of intellectual advances in London

Quantitative electron energy-loss spectroscopy (EELS) analyses of lead zirconate titanate

Electron energy-loss spectroscopy (EELS) analyses have been performed on a sol–gel deposited lead zirconate titanate film, showing that EELS can be used for heavy as well as light element analysis. The elemental distributions within the sol–gel layers are profiled using the Pb N<sub>6,7</sub>-edges, Zr M-edges, Ti L-edges and O K-edge. A multiple linear least squares fitting procedure was used to extract the Zr signal which overlaps with the Pb signal. Excellent qualitative information has been obtained on the distribution of the four elements. The non-uniform and complementary distributions of Ti and Zr within each sol–gel deposited layer are observed. The metal:oxygen elemental ratios are quantified using experimental standards of PbTiO<sub>3</sub>, PbZrO<sub>3</sub>, ZrO<sub>2</sub> and TiO<sub>2</sub> to provide relevant cross-section ratios. The quantitative results obtained for Ti/O and Pb/O are very good but the Zr/O results are less accurate. Methods of further improving the results are discussed

Digital Processing of Electron Energy Loss Spectra and Images

Processing in electron energy loss spectroscopy involves both data acquisition and analysis. The interface of an analytical electron microscope to a laboratory computer with a satellite microcomputer dedicated to data acquisition results in a system with a high degree of flexibility. In spectrum acquisition, channels may be selected around specific core edges, or dwell times may be varied continuously as a function of energy loss to reduce the dynamic range of the signal. Data transfer to the host computer allows further analysis such as the removal of plural scattering by spectral deconvolution. Elemental maps and line-scans can be recorded with real-time processing of energy loss data at each pixel. Images may be analyzed to provide quantitative information by means of pixel intensity histograms. If parameters for the background are stored at each pixel, the image data may sometimes be further processed to improve the signal-to-noise ratio

Quantitative Dark-Field Mass Analysis of Ultrathin Cryosections in the Field-Emission Scanning Transmission Electron Microscope

The availability of a cryotransfer stage, highly efficient electron energy loss spectrometers, and ultrathin-window energy-dispersive x-ray spectrometers for the VG Microscopes HB501 field-emission scanning transmission electron microscope (STEM) provides this instrument with the potential for high resolution biological microanalysis. Recent technical advances offer cryosections that are thin enough to take advantage of the analytical capabilities of this microscope. This paper first discusses the quantitative characterization of freeze-dried, ultrathin cryosections of directly frozen liver and brain by low-dose dark-field STEM imaging. Such images reveal high-quality sections with good structural detail, mainly due to reduced preparation artifacts and electron beam damage. These sections are thin enough for dark-field mass analysis, so that the mass of individual organelles can be measured in situ, and their water content deduced. This permits the measurement of mass loss-corrected subcellular elemental concentrations. The results suggest several new applications for cryosections as illustrated by data on synaptic activity-dependent calcium regulation in Purkinje cells of mouse cerebellum. Low-dose mass analysis of cryosections in combination with x-ray and electron spectroscopy is a promising approach to quantitating physiological changes in mass distribution and elemental composition

Photoluminescence of hexagonal boron nitride: effect of surface oxidation under UV-laser irradiation

We report on the UV laser induced fluorescence of hexagonal boron nitride (h-BN) following nanosecond laser irradiation of the surface under vacuum and in different environments of nitrogen gas and ambient air. The observed fluorescence bands are tentatively ascribed to impurity and mono (VN), or multiple (m-VN with m = 2 or 3) nitrogen vacancies. A structured fluorescence band between 300 nm and 350 nm is assigned to impurity-band transition and its complex lineshape is attributed to phonon replicas. An additional band at 340 nm, assigned to VN vacancies on surface, is observed under vacuum and quenched by adsorbed molecular oxygen. UV-irradiation of h-BN under vacuum results in a broad asymmetric fluorescence at ~400 nm assigned to m-VN vacancies; further irradiation breaks more B-N bonds enriching the surface with elemental boron. However, no boron deposit appears under irradiation of samples in ambient atmosphere. This effect is explained by oxygen healing of radiation-induced surface defects. Formation of the oxide layer prevents B-N dissociation and preserves the bulk sample stoichiometry

Data Processing For Atomic Resolution EELS

The high beam current and sub-angstrom resolution of aberration-corrected scanning transmission electron microscopes has enabled electron energy loss spectroscopic (EELS) mapping with atomic resolution. These spectral maps are often dose-limited and spatially oversampled, leading to low counts/channel and are thus highly sensitive to errors in background estimation. However, by taking advantage of redundancy in the dataset map one can improve background estimation and increase chemical sensitivity. We consider two such approaches- linear combination of power laws and local background averaging-that reduce background error and improve signal extraction. Principal components analysis (PCA) can also be used to analyze spectrum images, but the poor peak-to-background ratio in EELS can lead to serious artifacts if raw EELS data is PCA filtered. We identify common artifacts and discuss alternative approaches. These algorithms are implemented within the Cornell Spectrum Imager, an open source software package for spectroscopic analysis