Accuracy of film thickness determination in electron probe microanalysis

The thickness of copper films (100–450 nm) on silicon substrates was determined by electron probe microanalysis (EPMA) applying (z) procedures of Pouchou and Pichoir. Film thickness was calculated from experimental k-ratios analyzed with electron energies between 6 and 30 keV using commercial software (LAYERF distributed by CAMECA). The influence of the incident electron energy and X-ray line chosen for analysis on the results was investigated. Accuracy of film thickness determination was evaluated by comparison with Rutherford backscattering spectroscopy (RBS) and secondary ion mass spectrometry (SIMS). The difference between layer thicknesses determined with EPMA and RBS is in general less than 2%, if EPMA measurements are performed with various electron energies. Layer thicknesses determined with Cu-L are mostly closer to values obtained by RBS than those derived from Cu-K radiation. Preliminary SIMS measurements yielded inconsistent results and, thus, cannot be used in this case to determine the layer thickness of Cu films on Si accurately.     

Characterization of a laser‐nitrided titanium alloy by electron backscattered diffraction and electron probe microanalysis

After a laser gas nitriding treatment of the Ti‐7.5Al (atom %) titanium‐based alloy, we used a combination of electron backscattered diffraction (EBSD) in scanning electron microscope and electron probe microanalysis (EPMA) techniques in order to efficiently characterize the different phases in the resolidified layer. Representative measurements of chemical composition and reliable determination of crystal structure were possible for each phase of the complex microstructure. The reaction zone is formed by a mixture of isostructural TiN phases with dendritic and/or ‘coarse’ needles morphology, fixed into a α′‐Ti matrix (martensite) with a thin needle aspect. The nitrogen solubility was found to remain very low in the α′‐Ti matrix (up to 2–3 atom %), while in the TiN phase, an aluminum solubility as high as 4 atom % was measured, reducing drastically the nitrogen content into a Ti₇₉N₁₇Al₄ chemical composition. Copyright © 2005 John Wiley & Sons, Ltd.     

Characterization of individual atmospheric particles by element mapping in electron probe microanalysis

In this paper procedures for the characterization of individual aerosol particles by element mapping in the electron microprobe are presented. The number, size and qualitative chemical composition of particles is derived from a combination of secondary or backscattered electron images and element distribution maps. Accuracy of the size distribution and reliability of the qualitative analysis procedure were checked with silicate samples. In order to obtain a semi-quantitative estimate of the chemical composition of individual particles the count rates taken from element distribution maps are corrected for matrix and geometric effects using particle ZAF procedures.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Progress in the direct structural characterization of fibrous amphiphilic supramolecular assemblies in solution by transmission electron microscopic techniques

The self-assembly of amphiphilic molecules into fibrous structures has been the subject of numerous studies over past decades due to various current and promising technical applications. Although very different in their head group chemistry many natural as well as synthetic amphiphilic compounds derived from carbohydrates, carbocyanine dyes, or amino acids tend to form fibrous structures by molecular self-assembly in water predominantly twisted ribbons or tubes. Often a transition between these assembly structures is observed, which is a phenomenon already theoretically approached by Wolfgang Helfrich and still focus point in current research. With the development of suitable sample preparation and electron optical imaging techniques, cryogenic transmission electron microscopy (cryo-TEM) in combination with three-dimensional (3D) reconstruction techniques has become a particular popular direct characterization technique for supramolecular assemblies in general. Here we review the recent progress in deriving precise structural information from cryo-TEM data of particularly fibrous structures preferably in three dimensions.     

Quantitative analysis of films by ion microbeam methods. I: RBS,NRA, and channeling

Microchimica Acta - The aim of this review paper is to illustrate the application of the so-called nuclear techniques, i.e. MeV ion beam techniques, to the analysis of thin solid films. First a...     

Measurements and calculations of absorbed dose in electron beam radiation processing

An electron beam current densimeter has been described and used for dose measurement in EB radiation processing. An improved bipartition model of electron transport is applied to calculate the reflection coefficients and energy deposition distributions produced by 0.2–3 MeV electrons in semi-infinite media of Al, C, MAR and nylon, and the energy deposition produced by 2 MeV electrons in the two-layer medium consisting of copper and polystyrene. In addition, the depth dose distribution of 300 keV electrons in Ti-air-nylon composite-layer has been evaluated. The calculation results are in good agreement with the measurement data.     

Spectroscopic imaging techniques for characterization of polymer morphologies: a combination of infrared and electron microscopy

The morphological characterization of polymer blends consisting of polyamide and poly(tetrafluoroethylene) using FT-IR spectroscopy and electron microscopy is described. To enhance the lateral resolution - one of the main limits in infrared spectroscopy - a combination with scanning electron microscopy and analytical electron microscopic methods of a transmission electron microscope was made. The possibilities of electron energy loss spectroscopy and energy filtered transmission electron microscopy (EFTEM) in the area of polymer characterization are outlined.     

The revival of electron beam irradiation curing of epoxy resin—materials characterization and supportive cure studies

Polymeric composite manufacturing is a large, rapidly growing and energy consuming industry, where there is an obvious and compelling need for innovative curing technologies conforming to energy efficiency and environmental protection trends. This has led to many research efforts to consider, or in some cases re‐consider, irradiation curing of polymer composites. However, there is still a stifling lack of knowledge of the fundamental mechanisms to obtain homogeneity in the irradiation curing of composites. The key issue of the irradiation curing process, i.e. homogeneous curing affected by electron beam dose and initiator concentration for an epoxy resin is the focus of this paper. The temperature profiles, microstructure, curing degree gradient, and thermomechanical properties of electron beam‐ irradiated epoxy resin were profiled and analyzed, and the results indicated that curing degree in the epoxy resin showed a relatively steady region and an accelerated decrease along the depth direction. It is revealed that there existed an optimal range of concentration of the initiator for irradiation curing of an epoxy resin system. The inhomogeneity in the irradiation‐induced crosslinking structure could be abated by adopting the properly applied irradiation energy and the matching between the irradiation dose and the concentration of the initiator. It can be deduced that for most of the composite products with large thickness, layer upon layer irradiation or irradiation from two sides could be more efficient to obtain a homogeneous crosslinking structure. Copyright © 2009 John Wiley & Sons, Ltd.     

Solid-State polymerization of the binary mixture of methacrylate and liquid-crystalline compound by electron beam

Solid-state polymerization of a binary mixture of nonliquid-crystalline monomer and liquidcrystalline compound was carried out using electron beam. The monomers were benzoic acid containing 4-[ω-(meth)acryloyloxyalkyloxy] benzoic acids, in which the alkylene spacer was ethylene, hexamethylene, or undecamethylene. The conversion yield of monomer to polymer to a large extent increased with increasing content of a liquid-crystalline compound with a terminal carboxylic group, such as 4-n-alkyloxybenzoic acid, while the addition of a liquid-crystalline compound without terminal carboxylic group did not affect polymerization of the monomer. Phase diagrams of the mixture of monomer and liquid-crystalline compound were examined using cross-polarizing microscopy and differential scanning calorimetry (DSC). All mixtures of monomer and 4-n-alkyloxybenzoic acid or liquid-crystalline compound without terminal carboxylic group showed liquid-crystallinity in a broad composition range. It was concluded that liquid-crystalline compounds with terminal carboxylic acid may form hydrogen bondings with methacrylate or acrylate monomer having terminal carboxylic acid which enhance polymerizability of the mixture. The stereoregularity of polymers determined by NMR depended on increasing irradiation dose and temperature rather than the content of the added liquid-crystalline 4-n-decanoxybenzoic acid.     

Determination of thickness distribution and composition of thin coatings by EPMA: Application in the field of steel sheet production

A new method for the investigation of surface coatings by EPMA is presented. It is based on a physical model which takes into account the X-ray intensity depth distribution, the absorption and the electron backscattering effects at the interface between film and substrate. When combined with the concentration mapping (CM) technique, a two-dimensional film thickness distribution and the film composition can be determined simultaneously. Only bulk standards are required for this method.With some examples in the field of steel sheet production and electrogalvanizing the versatility of the method as well as its high sensitivity are pointed out. Particularly important for practical work is the applicability to almost any combinations of film and substrate materials as well as the wide thickness range from almost the total X-ray emergence depth down to the monolayer range.Dedicated to Professor Günther Tölg on the occasion of his 60th birthday     

Synthesis,characterization, and electrical properties of polypyrrole/multiwalled carbon nanotube composites

Size‐controllable polypyrrole (PPy)/multiwalled carbon nanotube (MWCNT) composites have been synthesized by in situ chemical oxidation polymerization directed by various concentrations of cationic surfactant cetyltrimethylammonium bromide (CTAB). Raman spectra, FTIR, SEM, and TEM were used to characterize their structure and morphology. These results showed that the composites are core (MWCNT)–shell (PPy) tubular structures with the thickness of the PPy layer in the range of 20–40 nm, depending on the concentration of CTAB. Raman and FTIR spectra of the composites are almost identical to those of PPy alone. The electrical conductivities of these composites are 1–2 orders of magnitude higher than those of PPy without MWCNTs. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6449–6457, 2006     

Depth Profile Analysis on the Nanometer Scale by a Combination of Electron Probe Microanalysis (EPMA) and Focused Ion Beam Specimen Preparation (FIB)

Electron probe microanalysis (EPMA) offers high sensitivity and high accuracy in quantitative measurements of chemical compositions and mass coverages. Owing to the low detection limits of the wavelength-dispersive technique, monolayers with mass coverages of about 0.05µgcm^–2 can be detected. Assuming a density of 5gcm^–3 this corresponds to a thickness of 0.1nm. With these advantages in mind, EPMA was extended to depth profile analysis in the sub-micron range using a surface removal technique.The present paper shows how depth profile analysis can be improved by combining EPMA and the focused ion beam (FIB) technique. The focused ion beam system uses a Ga⁺ ion beam. The ion beam allows the milling of defined geometries on the nanometer scale, so that very shallow bevels with exactly defined angles in relation to the surface can be obtained. Low surface damage is expected due to low sputtering effects. Calibrated WDX measurements along the bevel deliver quantitative concentration depth profiles. First results obtained with this new combination of methods will be presented for a multilayered sample used in optical data storage.     

Investigation of the three-dimensional microstructure of Cu-Sn(Pb) diffusion zones by means of ion beam sputtering, scanning electron microscopy and lattice source interferences

On model substances of Cu-Sn(Pb) solders it is shown by the combined use of several physical analytical methods that the intermetallic compounds formed during the annealing process have a crystalline structure, which can be observed also three-dimensionally by ion etching. Moreover, grain boundaries as well as phases become visible, and it is possible to determine the crystallographic orientation of the individual crystals in the Cu starting material and in the diffusion zones by means of the Kossel technique. As a result of the investigations, conclusions can be drawn with respect to the diffusion process, especially also to the crystallographic structure of the diffusion zones and the dendritic growth.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Graft polymerization of acrylamide onto LLDPE film by electron beam pre-irradiation in air and argon. II. Influence of mohr's salt

LLDPE film pre-irradiated by electron beam (EB) in air and argon was grafted in an aqueous acrylamide solution containing Mohr's salt in the concentration range 0.0025–2% The grafting rate and yield were strongly dependent on the Mohr's salt concentration, mainly as a result of chain termination. The exponential grafting rate dependence on the pre-irradiation dose was quite insensitive to a hundred-fold variation in Mohr's salt concentration. © 1995 John Wiley & Sons, Inc.     

Structural and catalytic properties of ultra-dispersed silver powders prepared by metal evaporation with high-power electron beam. 1. Structural properties

Summary Structural properties of ultra-dispersed silver powders synthesized via high-temperature electron-beam evaporation of silver in different gases (Ar, N₂, He) were studied with XRD, TEM, EDX and XRF. The formation of specific oxide-like species on the particle surface of an Ag(Ar) powder was found. It was shown that these particles can contain argon atoms.     

Spectroscopic studies of structural changes in irradiated LDPE and its blends

The low temperature glass transition occurring at low temperature in polyethylene samples was studied using Fourier transform infrared, FT‐Raman spectroscopic techniques, which are known to be sensitive to any structural changes in the investigated samples. Anomalous behavior was obtained in the temperature range (98 K → 383 K) indicating the existence of phase transition occurring at about 98 K and disappearing at about 323 K while heating for unirradiated virgin low density polyethylene (VPE) sample with or without crosslinking agent (trimethylol propane triacrylate, TMPTA). Addition of TMPTA monomer caused severe changes in the temperature dependence of both unirradiated and irradiated polyethylene samples. The results given indicated the occurrence of abnormal temperature dependence, which is thought to be related with low temperature structural change resulting from local crosslinking in scrapped polyethylene (SPE) sample already suffering from high degree of crosslinking. Differential scanning calorimetry (DSC) thermograms confirmed the observed new phase transition observed in both unirradiated and irradiated TMPTA loaded VPE/SPE (50/50 wt %) blend. Irradiation, addition of TMPTA as a crosslinking agent, and blending VPE with SPE were found to affect remarkably the variation of the vibration spectrum of LDPE and consequently the resulting structural changes. The experimental results obtained were discussed and correlated with reorientational disorders of the molecular segments (local crosslinking). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 850–859, 2007     

Structural characterization of modern and fossilized charcoal produced in natural fires as determined by using electron energy loss spectroscopy

Charcoal produced in natural fires is widespread, but surprisingly little is known about its structure and stability. TEM and electron energy loss spectroscopy (EELS) were used to characterize the organized graphite-like microcrystallites and amorphous nonorganized phases of modern charcoal that had been produced in natural fires. In addition, a semiordered structure was identified in two modern charcoal samples. Fossilized charcoal contains fewer graphite-like microcrystallites than modern samples. EELS spectra confirmed that the dominant structure in fossilized charcoal is amorphous carbon. EELS measurements also revealed that only the nonorganized phase contains oxygen, which indicates that the degradation of the fossilized charcoal structure occurs mainly through oxidation processes. The few graphite-like microcrystallites found in fossilized charcoal were composed of onion-like structures that are probably less prone to oxidation owing to their rounded structures.     

Preparation and characterization of a new set of IAEA reference air filters using instrumental neutron activation analysis, proton-induced X-ray emission and Rutherford backscattering

A new set of reference air filters was prepared for proficiency testing of laboratories involved in air pollution studies organized by the International Atomic Energy Agency (IAEA). The set consists of one filter loaded with airborne particulate matter (APM) and one blank filter. Target values and their standard deviations were established using instrumental neutron activation analysis (INAA) and proton induced X-ray emission (PIXE) with proven accuracy. Rutherford backscattering (RBS) was used to help in deriving the necessary corrections in PIXE. Losses of individual elements from APM due to the wet deposition procedure were evaluated.     

Three‐dimensional structural analysis of a block copolymer by scanning electron microscopy combined with a focused ion beam

A three‐dimensional (3D) lamellar structure of a poly(styrene‐block‐isoprene) block copolymer was observed at submicrometer and micrometer levels by scanning electron microscopy combined with a focused ion beam (FIB–SEM). The 3D lamellar structure with an exceptionally large periodicity, about 0.1 μm, was successfully reconstructed, and the size of the reconstructed image by FIB–SEM was 6.0 × 6.0 × 4.0 μm³, which was greater than the transmission electron microtomography data, 3.8 × 3.9 × 0.24 μm³, by a factor of about 40. This result indicates that 3D reconstruction using FIB–SEM is quite useful for direct 3D observations, especially analyses of polymeric materials at the submicrometer and micrometer levels. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 677–683, 2007