Mistakes encountered during automatic peak identification of minor and trace constituents in electron‐excited energy dispersive X‐ray microanalysis

Automated peak identification in electron beam‐excited X‐ray microanalysis with energy dispersive X‐ray spectrometry has been shown to be subject to occasional mistakes even on well‐separated, high‐intensity peaks arising from major constituents (arbitrarily defined as a concentration, C, which exceeds a mass fraction of 0.1). The peak identification problem becomes even more problematic for constituents present at minor (0.01≤C≤0.1) and trace (C<0.01) levels. “Problem elements” subject to misidentification as major constituents are even more vulnerable to misidentification when present at low concentrations in the minor and trace ranges. Additional misidentifications attributed to trace elements include minor X‐ray family members associated with major constituents but not assigned properly, escape and coincidence peaks associated with major constituents, and false peaks owing to chance groupings of counts in spectra with poor counting statistics. A strategy for robust identification of minor and trace elements can be based on application of automatic peak identification with careful inspection of the results followed by multiple linear least‐squares peak fitting with complete peak references to systematically remove each identified major element from the spectrum before attempting to assign remaining peaks to minor and trace constituents. SCANNING 31: 91–101, 2009. Published by Wiley Periodicals, Inc.     

Imaging connected porosity of crystalline rock by contrast agent‐aided X‐ray microtomography and scanning electron microscopy

We set out to study connected porosity of crystalline rock using X‐ray microtomography and scanning electron microscopy with energy dispersive X‐ray spectroscopy (SEM‐EDS) with caesium chloride as a contrast agent. Caesium is an important radionuclide regarding the final deposition of nuclear waste and also forms dense phases that can be readily distinguished by X‐ray microtomography and SEM‐EDS. Six samples from two sites, Olkiluoto (Finland) and Grimsel (Switzerland), where transport properties of crystalline rock are being studied in situ, were investigated using X‐ray microtomography and SEM‐EDS. The samples were imaged with X‐ray microtomography, immersed in a saturated caesium chloride (CsCl) solution for 141, 249 and 365 days and imaged again with X‐ray microtomography. CsCl inside the samples was successfully detected with X‐ray microtomography and it had completely penetrated all six samples. SEM‐EDS elemental mapping was used to study the location of caesium in the samples in detail with quantitative mineral information. Precipitated CsCl was found in the connected pore space in Olkiluoto veined gneiss and in lesser amounts in Grimsel granodiorite. Only a very small amount of precipitated CsCl was observed in the Grimsel granodiorite samples. In Olkiluoto veined gneiss caesium was found in pinitised areas of cordierite grains. In the pinitised areas caesium was found in notable excess compared to chloride, possibly due to the combination of small pore size and negatively charged surfaces. In addition, elevated concentrations of caesium were found in kaolinite and sphalerite phases. The findings concerning the location of CsCl were congruent with X‐ray microtomography.     

Aberration‐corrected STEM for atomic‐resolution imaging and analysis

Aberration‐corrected scanning transmission electron microscopes are able to form electron beams smaller than 100 pm, which is about half the size of an average atom. Probing materials with such beams leads to atomic‐resolution images, electron energy loss and energy‐dispersive X‐ray spectra obtained from single atomic columns and even single atoms, and atomic‐resolution elemental maps. We review briefly how such electron beams came about, and show examples of applications. We also summarize recent developments that are propelling aberration‐corrected scanning transmission electron microscopes in new directions, such as complete control of geometric aberration up to fifth order, and ultra‐high‐energy resolution EELS that is allowing vibrational spectroscopy to be carried out in the electron microscope.     

New pathways for improved quantification of energy‐dispersive X‐ray spectra of semiconductors with multiple X‐ray lines from thin foils investigated in transmission electron microscopy

Theoretical approaches to quantify the chemical composition of bulk and thin‐layer specimens using energy‐dispersive X‐ray spectroscopy in a transmission electron microscope are compared to experiments investigating (In)GaAs and Si(Ge) semiconductors. Absorption correctors can be improved by varying the take‐off angle to determine the depth of features within the foil or the samples thickness, or by definition of effective k‐factors that can be obtained from plots of k‐factors versus foil thickness or, preferably, versus the K/L intensity ratio for a suitable element. The latter procedure yields plots of self‐consistent absorption corrections that can be used to determine the chemical composition, iteratively for SiGe using a set of calibration curves or directly from a single calibration curve for InGaAs, for single X‐ray spectra without knowledge of sample thickness, density or mass absorption coefficients.     

Characterising the surface and interior chemistry of core-shell nanoparticles using scanning transmission electron microscopy

A method for extracting core and shell spectra from core-shell particles with varying core to shell volume fractions is described. The method extracts the information from a single EELS spectrum image of the particle. The distribution of O and N was correctly reproduced for a nanoparticle with a TiN core and Ti-oxide shell. In addition, the O distribution from a nanoparticle with a Cu core and a Cu-oxide shell was obtained, and the extracted Cu L_2,3-core and shell spectra showed the required change in EELS near edge fine structure. The extracted spectra can be used for multiple linear least squares fitting to the raw data in the spectrum image. The effect of certain approximations on numerical accuracy, such as treating the nanoparticle as a perfect sphere, as well as the intrinsic detection limits of the technique have also been explored. The technique is most suitable for qualitative, rather than quantitative, work.     

Chemical and morphological evaluation of enamel and dentin near cavities restored with conventional and zirconia modified glass ionomer subjected to erosion‐abrasion

Microenergy dispersive X‐ray fluorescence (μ‐EDXRF) spectroscopy and scanning electron microscopy (SEM) were used to test the hypothesis that zirconia modified glass ionomer cement (GIC) could improve resistance to erosion‐abrasion to a greater extent than conventional cement. Bovine enamel (n = 40) and dentin (n = 40) samples were prepared with cavities, filled with one of the two restorative materials (GIC: glass‐ionomer cement or ZrGIC: zirconia‐modified GIC). Furthermore, the samples were treated with abrasion‐saliva (AS) or abrasion‐erosion cycles (AE). Erosive cycles (immersion in orange juice, three times/day for a duration of 1 min over a 5 day period) and/or abrasive challenges (electric toothbrush, three times/day for a duration of 1 min over a 5 day period) were performed. Positive mineral variation (MV%) on the enamel after erosion‐abrasion was observed for both materials (p < 0.05), whereas a negative MV% on the dentin was observed for both materials and treatments (p < 0.05). The SEM images showed clear enamel loss after erosion‐abrasion treatment and material degradation was greater in GIC_AE compared to those of the other groups. Toothbrush abrasion showed a synergistic effect with erosion on substance loss of bovine enamel, dentin, GIC, and ZrGIC restorations. Zirconia addition to the GIC powder improved the resistance to abrasive‐erosive processes. The ZrGIC materials may find application as a restorative material due to improved resistance as well as in temporary restorations and fissure sealants.     

Accuracy and precision of quantitative energy-dispersive x-ray spectrometry in the environmental scanning electron microscope

The accuracy and precision of quantitative energy-dispersive x-ray spectrometry in the environmental scanning electron microscope have been estimated using a series of copper / gold alloys of known composition. The mean values (five to six replicate experiments) had relative errors within +/- 5%, and most were within +/- 3.5%. All relative standard deviations were < 5% and most were < 3%. Since the standard specimens were large (approximately 500 microm) in diameter, electron scattering in the 2 torr of water vapor above the specimen did not affect the results. This level of accuracy and precision was possible only by using a novel specimen surface charge neutralization scheme.     

Visualization and characterization of engineered nanoparticles in complex environmental and food matrices using atmospheric scanning electron microscopy

Imaging and characterization of engineered nanoparticles (ENPs) in water, soils, sediment and food matrices is very important for research into the risks of ENPs to consumers and the environment. However, these analyses pose a significant challenge as most existing techniques require some form of sample manipulation prior to imaging and characterization, which can result in changes in the ENPs in a sample and in the introduction of analytical artefacts. This study therefore explored the application of a newly designed instrument, the atmospheric scanning electron microscope (ASEM), which allows the direct characterization of ENPs in liquid matrices and which therefore overcomes some of the limitations associated with existing imaging methods. ASEM was used to characterize the size distribution of a range of ENPs in a selection of environmental and food matrices, including supernatant of natural sediment, test medium used in ecotoxicology studies, bovine serum albumin and tomato soup under atmospheric conditions. The obtained imaging results were compared to results obtained using conventional imaging by transmission electron microscope (TEM) and SEM as well as to size distribution data derived from nanoparticle tracking analysis (NTA). ASEM analysis was found to be a complementary technique to existing methods that is able to visualize ENPs in complex liquid matrices and to provide ENP size information without extensive sample preparation. ASEM images can detect ENPs in liquids down to 30 nm and to a level of 1 mg L^?1 (9×10⁸ particles mL^?1, 50 nm Au ENPs). The results indicate ASEM is a highly complementary method to existing approaches for analyzing ENPs in complex media and that its use will allow those studying to study ENP behavior in situ, something that is currently extremely challenging to do.