Quantitative Analysis of Ti-Si-Ge/Si-Ge/Si Structures by EDS and AES

 A method for quantitative analysis of Ti-Si-Ge/Si-Ge/Si structures with submicron thick layers by energy dispersive spectroscopy (EDS) in transmission electron microscopy (TEM) and Auger electron spectroscopy (AES) was developed. Quantitation of the results of both AES and EDS techniques was performed on the basis of a single reference specimen for the Ti-Si-Ge system comprising a uniform layer of the Ti(Si_0.85Ge_0.15)₂ phase on a silicon substrate. The reference sample was prepared by the same procedure as the samples used in the study, and was thoroughly characterized by X-ray diffractometry, transmission electron microscopy and energy dispersive spectroscopy in scanning electron microscopy. Using this reference sample the elemental sensitivity factors relative to Si were found for both techniques, which enable us to obtain the elemental depth distributions for the studied samples. Good agreement between the results obtained by EDS/TEM, AES and supplementary techniques was found.     

EFTEM and EELS Analysis of a Pt/NiO Interface

 Energy-filtering transmission electron microscopy (EFTEM) is more and more becoming an important nanoanalytical technique in both materials science and biology. The main advantage of the method lies in the possibility to obtain two-dimensional chemical information from large specimen areas as well as from features on a nanometer scale. Due to its excellent lateral resolution it is perfectly suited for the investigation of nanometer sized features (e.g. interfaces). In this paper we will show how EFTEM can be used to characterize the interface between a Pt layer and a NiO crystal as part of a coulometric titration cell. In addition to elemental distribution maps electron energy-loss spectra (EELS) across the interface (EELS linescans) have been acquired to obtain quantitative compositional profiles. By employing these methods the following interfacial layers could be identified, all of which containing Pt, Ni and O in different proportions: 13 nm Pt-rich, 32 nm Ni-rich and 29 nm Pt-rich. The origin of these is discussed in terms of displacement reactions.     

Multianalytical Study of Patina Formed on Archaeological Metal Objects from Bliesbruck-Reinheim

 Patinas naturally formed on archaeological bronze alloys were characterized using light microscopy (LM), micro energy dispersive X-ray fluorescence analysis (μ-EDXRF), time of flight secondary ion mass spectrometry (TOF-SIMS) and scanning electron microscopy in combination with energy dispersive X-ray microanalysis (SEM/EDX). The examinations carried out on cross-sections of samples have shown that in all samples the copper content in the corrosion layer is lower than in the bulk, while an increase of tin and lead could be observed. Two different types of corrosion were found: first type, a corrosion formation leading to a three layer structure was observed on lead bronze. The outer layer consists mainly of Cu(II) compounds and soil material, followed by a fragmented layer of cuprous oxide and the surface layer of the alloy, where a depletion of copper and an enrichment of tin and high amounts of Cl could be detected. The second type of corrosion is characterized by a two layer structure on the tin bronze sample consisting of an outer layer with copper containing corrosion products and a layer with cracks, which reveals a depletion of copper whereas tin and lead are enriched. Also high amounts of Si were detected in this surface layer.     

Applications of Electron Microbeam Analysis in the Earth Sciences

 Naturally formed geological materials are not constrained in the number of elements which may be present and a wide range of concentrations can be expected. Oxides are a frequent component and water may be present. The particular problems posed for quantitative analysis in some representative applications are described and solutions suggested. Critical testing of the results for consistency with mineral formulae and for repeatability provides confidence in those results. Examples of applications of quantitative analysis of minerals are used to show the variety of problems encountered in electron microbeam analysis and how the analytical results can be used to determine the conditions (time, pressure, temperature) of the minerals or the rocks in which they occur.     

Nanoscale Co/Cu Multilayers Investigated by Analytical TEM and AES

 Concentration profiles of sputtered and pulsed laser deposited nanoscale Co/Cu multilayers have been measured by EDXS and EELS line scans in scanning mode at electron microscopic cross section foils and by AES depth profile analysis. The interpretation of the results has been supported by model calculations. After deposition, the pulsed laser deposited multilayers are stronger mixed than the sputtered layers. They decompose during annealing.     

Chemical Composition and Microstructure of Plasma-Nitrided Aluminium

 Detailed examinations were made by AES depth profiling, SEM, TEM and electron diffraction to get information about the relation between treatment conditions and the state of plasma-nitrided aluminium. The chemical composition and the elemental depth distribution were proofed to be depending on gas phase mixture, pressure and temperature during plasma treatment. The admixture of hydrogen during presputtering for surface cleaning and during nitriding results both in an improved nitriding behaviour and in a reduction of the formation of conical-shaped particles at the surface. The microstructure of the nitride layer isn’t depending on tested process conditions significantly. Surface and interface between layer and substrate are roughly in a scale of a few ten nanometers owing to sputtering effects. The main phase inside the layer is nanocrystalline AlN of the known hexagonal modification. In addition, some crystallites of remaining aluminium are present as a second phase. In contrast to nitrogen-implanted aluminium no preferred lattice orientation of the AlN phase was evident.     

Quantitative Trace Analysis by Wavelength-Dispersive EPMA

 “Trace” elements may be defined as elements whose concentrations are of a similar order to the detection limit. In WD analysis the detection limit is a function of the ‘figure of merit’ P²/B, where P is the pure-element peak intensity and B the background intensity. With normal analysis conditions detection limits of ∼100 ppm are typical, but substantial improvements can be achieved by using higher values of accelerating voltage and beam current. Long counting times are also advantageous, but should preferably be divided into relatively short alternating peak and background measurements to minimise the effect of instrumental drift. Using separate routines for trace and major element analysis is desirable owing to their different requirements. As the statistically defined detection limit is reduced, errors due to background nonlinearity and interferences (overlaps) from other elemental peaks become more probable. Spectrum simulation is useful for optimising background offsets and choice of crystal to minimise interferences, and estimating interference corrections when these are necessary. ‘Blank’ standards containing none of the trace elements of interest are also useful for quantifying background nonlinearity.     

Effect of Oxide Coverage on the Growth of Amorphous Al2Pt Phase on an Al Surface

 In the present experiments the high temperature successive deposition (HTSD) of Al and Pt and the half shadowing technique producing wedge shaped area with increasing quantity of deposited Pt are applied for studying the initial stages of solid phase reaction producing amorphous Al₂Pt phase. The nucleation of Al₂Pt phase results in a decoration pattern which could be related to the characteristic local oxide coverage of the Al crystal surface developing by kinetic segregation of oxygen species during the Al film deposition. In the area of larger amount of deposited Pt, where the Al₂Pt phase is continuous Kirkendall voids are present. The samples were investigated in plane by transmission electron microscopy (TEM) and selected area electron diffraction (SAED) and analysed by energy dispersive X-ray spectroscopy (EDX).     

Sites are Separable in Garnets with ALCHEMI

 It is shown in this paper that – in contrast to the accepted belief in the literature – it is possible to determine if a minority component is located on the dodecahedral, octahedral or tetrahedral sites in a garnet single crystal. Previous literature regarded the dodecahedral sites indistinguishable form the tetrahedral sites. Our prediction about the separability is based upon dynamical Bloch-wave calculations and proved experimentally in a transmission electron microscope (TEM) on two different natural garnets (almandine and grossular). The crystallographic positions of the minority components are determined in an ALCHEMI experiment that makes use of the channeling of electrons in special directions of a single-crystal sample.     

Infrared Spectroscopic Analysis of Plasma-Treated Si(100)-Surfaces

 Infrared reflection spectroscopy (specular reflection, attenuated total reflection) has been applied in combination with spectroscopic ellipsometry and electron microscopy to analyze the surface structure of plasma-treated Si(100) surfaces. It is shown that plasma treatments in oxygen and fluorine or chlorine-containing gases cause the formation of a thin surface layer having thicknesses of a few nanometers. The layer was identified to consist of SiO₂ for treatments in an oxygen plasma. Analyses of layers formed by treatments in a fluorine-containing plasma do not confirm the generally assumed model. Different Si-F vibration modes were identified in the surface layer caused by a SF₆ plasma. They correlate, however, with SiF and SiF₂ molecules. There are no indications of the existence of the generally assumed SiF₄. Neither has SiOF₂ been proven in layers produced by etching in a SF₆/O₂ plasma.     

Multiple Electron Beam Analyses Applied to Eclogite from the Western Alps

 The occurrence of compositional and microtextural relics within metamorphic rocks can provide useful information on the pressure-temperature history of the host rock. The grain-size of these microstructures, such as coronitic reaction microtextures, is mostly too fine to be detected by optical microscopy. Therefore, a more detailed analytical approach is needed. In this paper multiple electron beam techniques including the acquisition of X-ray multi-element maps, micro and nano-analysis performed by SEM/EDS and TEM/STEM-EDX systems were applied to a specific petrological problem related to metamorphism. Fine-grained decompressional reaction microtextures of an eclogitic sample (Mt. Rosa Nappe, Western Alps) are described and discussed.     

Exploratory Analysis of Micrographic Teflon Images

 Some analytical techniques are able to produce images, making if possible to obtain a large amount of information. Working with images, the pixels can be treated like objects in a data matrix. In this way, a multi-way PCA of micrograph images was applied to the internal surface of a Teflon coil used for microwave sample digestion. This Teflon coil was used for 120 h and had been attacked with different acids. It was cut into 3 pieces (namely: initial, medium and central portions) in order to obtain 7 micrographs (2 for initial, 2 for medium and 3 for the central part). A micrograph of a piece from a new Teflon coil was used for comparison. With these 8 micrographs, it was possible to establish a three-dimensional arrangement. After multi-way PCA was applied to the Teflon surface images, was possible to group a great amount of information and to characterise different parts of this coil. Received March 3, 2000. Revision July 28, 2000.     

EPMA Major and Trace Element Analysis in Garnet and its Petrological Application

 A comparison between major and trace element concentrations in garnet performed by electron microprobe (EPMA) technique is reported. Quantitative spot analyses and X-ray maps of major elements (Fe, Mg, Mn, Ca) and the trace element yttrium in garnets from metamorphic rocks are presented. The selected garnet samples come from meta-pelitic and meta-basic specimens belonging to the tectonic unit of the Monte Rosa Nappe (Western Alps). In the metapelites, the quantitative Y distribution maps display a prominent increase at the core, the Y abundance varying by over two orders of magnitude, from about 80 ppm (rim) to over 2100 ppm (core). The Y profiles show well defined patterns with sharp features that do not correlate with major element distributions. A roughly comparable pattern can be supposed only with Mn. The Y distribution suggests that the diffusion of Y through the garnet is very slow compared to the major elements, thus the Y results are suitable for geothermometric estimates. In the metabasites, the Y spatial distribution is characterised by an increasing content from the core to the rim, displaying a zoning pattern opposite to the metapelite garnet. Quantitative EPMA analyses range from 1100 ppm at the rim to values lower than the detection limit at the core. Therefore, the Y content in the garnet can be related to several chemical and physical variables such as the bulk rock composition and the phase assemblage. In particular, in the xenotime-bearing metapelitic system the Y distribution seems to be correlated with metamorphic peak temperature.     

Influence of Pickling High Alloyed CrNi-Steels and Nickel Base Alloys with Citric Acid on the Composition of their Tarnish Oxides

 Extra-ordinary mechanical features and high corrosion resistance are essential qualities of CrNi-steels and nickel base alloys. The corrosion resistance of these materials fundamentally depends on their surface conditions. Tarnish colours and welding scale, formed during thermal treatment or joining, are removed by pickling components made of these alloys with sulphuric acid, nitric acid and hydrofluoric acid as well. By this kind of surface refinement several million tons per annum of aggressive waste waters are produced, that cause high environmental risks and not acceptable employee endangerings. Therefore, a project was promoted by the DECHEMA e.V. to replace hydrofluoric acid by organic complexing agents. The related surface analytical examinations are reported in this publication.     

Determination of Thiosemicarbazones by Means of the Induced Iodine-Azide Reaction

 The iodine-azide reaction induced by eight thiosemicarbazones was investigated. Inducing properties of thiosemicarbazones are different and depend on the parent carbonyl compound used for synthesis. The inductor coefficients of the examined thiosemicarbazones vary from 61 to 176. Optimum conditions for the determination of microamounts of thiosemicarbazones are given. The detection limit for the determination by the back-titration method depends on the inducing activity and is 0.9 μg for phenyl-thiosemicarbazones and 2 μg for diethyl-thiosemicarbazone in a 5-mL sample, and this corresponds to a concentration of 0.9 × 10⁻⁶ mol/L and , respectively. The automatic titration with the diluted iodine solution decreases the detection limit to about 50 ng in a 10-mL sample. Received October 28, 1998. Revision April 9, 1999.     

Structural and Chemical Analysis of Materials with High Spatial Resolution

 An understanding of the correlation between microstructures and properties of materials require the characterization of the material on many different length scales. Often the properties depend primarily on the atomistics of defects, such as dislocations and interfaces. The different techniques of transmission electron microscopy allow the characterization of the structure and of the chemical composition of materials with high spatial resolution to the atomic level: high resolution transmission electron microscopy allows the determination of the position of the columns of atoms (ions) with high accuracy. The accuracy which can be achieved in these measurements depends not only on the instrumentation but also on the quality of the transmitted specimen and on the scattering power of the atoms (ions) present in the analyzed column. The chemical composition can be revealed from investigations by analytical microscopy which includes energy dispersive X-ray spectroscopy, mainly quantitatively applied for heavy elements, and electron energy-loss spectroscopy. Furthermore, the energy-loss near-edge structure of EELS data results in information on the local band structure of unoccupied states of the excited atoms and, therefore, on bonding. A quantitative evaluation of convergent beam electron diffraction results in information on the electron charge density distribution of the bulk (defect-free) material. The different techniques are described and applied to different problems in materials science. It will be shown that nearly atomic resolution can be achieved in high resolution electron microscopy and in analytical electron microscopy. Recent developments in electron microscopy instrumentation will result in atomic resolution in the foreseeable future.     

Assessment of Four Inter-Comparison Exercises in Organic Elemental Analysis

 Four inter-comparison exercises on organic elemental analysis were carried out between 1997 and 2001 by the Department of Analytical Chemistry of the University of Barcelona, together with the Microanalysis Service and the Institute of the Marine Sciences, which both belong to the CSIC in Barcelona, and the University of A Coru?a. More than sixty laboratories participated in these exercises. Here we describe the design and characteristics of the trials, the samples and the homogeneity tests applied. We report the results obtained for the analysis of carbon, hydrogen, nitrogen, sulphur and oxygen, their statistical analysis, and the most relevant aspects of the technical discussion meetings. Received December 20, 2001; accepted March 18, 2002; published online July 22, 2002     

Light Element Analysis of Individual Microparticles Using Thin-Window EPMA

 The determination of the concentration of light elements, such as carbon, nitrogen and oxygen, in e.g. atmospheric aerosol particles is important to study the chemical behaviour of atmospheric pollution. The knowledge of low-Z element concentrations gives us information on the speciation of nutrients (species having nutritional value for plants) and toxic heavy metals in the particles. The capability of the conventional energy-dispersive EPMA is strongly limited for the analysis of low-Z elements, mainly because the Be window in the EDX detector hinders the detection of characteristic X-rays of light elements such as C, N, O and Na. WDS is suitable for analysis of light elements, but the measurement of beam sensitive microparticles requires the minimisation of the beam current and the measurement time. A semi-quantitative analytical method based on EPMA using an ultra-thin window EDX detector was developed. It was found that the matrix and geometric effects that are important for low-energy X-rays can be reliably evaluated by Monte Carlo calculations. Therefore, the quantification part of the method contains reverse Monte Carlo calculation done by iterative simulations. The method was standardised and tested by measurements on single particles with known chemical compositions. Beam-sensitive particles such as ammonium-sulphate and ammonium-nitrate were analysed using a liquid nitrogen cooled sample stage. The shape and size of the particles, which are important for the simulations, were determined using a high-magnification secondary electron image. Individual marine aerosol particles collected over the North Sea by a nine-stage Berner cascade impactor were analysed using this new method. Preliminary results on five samples and 4500 particles show that the method can be used to study the modification of sea-salt particles in the troposphere.     

Spectral Interferences in Light Element Analysis

 Interferences (overlaps) occurring when lines of other elements affect either peak or background measurements can cause errors in quantitative WD analysis, but may be minimised by suitable choices of analysis conditions such as spectrometer crystal, background offsets, and pulse-height analyser settings. Computer spectrum-simulation is much more effective than reference to wavelength tables for investigating interferences. The ‘Virtual WDS’ simulation program developed by the present authors, hitherto applied only to ‘ordinary’ elements (Z ≥ 11), has been extended to light elements for which evaporated multilayers are used in place of true crystals. ‘Virtual WDS’ utilises experimentally recorded light-element K spectra and L and M spectra of heavier elements in the same wavelength range. It is impractical to record all high-order peaks, so computed line profiles are used, with widths and intensities interpolated from a limited set of observations. The relative positions of first and higher order peaks are affected significantly by the refractive index of the multilayer, requiring modification of the Bragg equation. Suppression of high orders by pulse-height analysis is less effective than for ‘normal’ wavelengths, owing to the breadth of the pulse-height distribution for low X-ray energies. Simulation using a Gaussian expression aids optimisation of threshold and window-width settings.     

Determination of the Stoichiometric Composition of High-Temperature Superconductors by ICP-OES for Production Control

 A procedure to dissolve and analyse different types of high-temperature superconducting materials in order to determine their stoichiometric com- position is described. As sample materials Y-Ba-Cu-O and (Pb)Bi-Sr-Ca-Cu-O were analysed. They were dissolved with hydrochloric acid and analysed by simultaneous ICP-OES, which fits best for this analytical task because of its multielement capacity, its high precision of determination and accuracy. Each of the relevant metals (Pb, Bi, Sr, Ca, Y, Ba, Cu) could be determined successfully. The precision of the determination was found to be better than 2% relative standard deviation and usually even below 1%. The sample preparation and determination procedure described allows a high sample throughput, which is essential for production control. Also precursors of the superconducting materials (e.g. nitrate solutions) could be analysed by the procedure described.