Modification of a Field Emission Source SEM For Quantitative X-Ray Microanalysis

Abstract

We have modified a field emission source SEM in an attempt to obtain a quantitative x-ray microanalysis capability. This report describes how emission current instabilities, characteristic of cold field emission cathodes, were effectively circumvented. The technique involves integrating the electron beam current and terminating x-ray data acquisition at a selected value of integrated current.

Working well in the current ranges available on most electron beam instruments, the scheme may be universally applicable to any charged beam instrument in which some event is, or can be made, dependent on the integrated beam current.     

Investigations of precipitates in heat treated AgPd30/CuSn6 layers

The subject of the investigations are precipitation zones, which grew as a result of chemical diffusion in AgPd30/CuSn6 bimetals. These precipitation zones have been characterized by metallography, electron probe microanalysis and x-ray diffraction. The growth of precipitation zones in the plating layer and in the substrate layer in dependence on time have been determined. The use of x-ray diffraction alone for the identification of the precipitates could not supply satisfying results in every case. This problem was solved by the application of electron probe microanalysis using a correction method, which allows the estimation of the chemical composition of small particles.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday     

Monte Carlo Simulation of Electron Transport and X-Ray Generation. II. Radiative Processes and Examples in Electron Probe Microanalysis

Theoretical models for Monte Carlo simulation of radiative processes, i.e. bremsstrahlung and characteristic x-ray emission, are presented. Possible strategies for simulating electron transport are briefly described. For mechanisms involving energy loss and angular deflections, difficulties for strict implementation of accurate numerical differential cross sections still remain due to the strong correlations between these variables. Practical solutions for the case of inelastic collisions and bremsstrahlung emission are described. Comparisons of simulation results with experimental data for several problems of interest in electron probe microanalysis are presented.     

Combined EPMA and AES depth profiling of a multilayer Ti-Al-O-N coating

In order to compare thin-film electron probe microanalysis (EPMA) and Auger electron spectroscopy (AES) regarding reliability in quantifying chemical compositions of Ti-Al-O-N coatings with depth, a multilayer was prepared on a silicon wafer by using reactive ionized cluster beam deposition technique. Within a total thickness of about 25 nm the composition of the multilayer varied step by step from Ti-Al-O-N at the bottom to Al-O at the top. AES and, as an innovation, EPMA crater edge profiling was applied to measure the composition with depth. For quantification special thin-film EPMA techniques based on Monte Carlo simulations were applied. The chemical binding states of Al and Ti with depth were analysed using a high resolution energy analyser (MAC 3) for the AES investigations working in the direct mode. According to the deposition procedure the concentration profiles of the components varied with depth for both AES and EPMA measurements. AES provided a better depth resolution than EPMA. To get a true calibration of the depth scale an in-situ measurement method like an optical interferometry will be required. Assuming that the relative sensitivity factors are available AES depth profiling delivers concentration profiles with good accuracy. The new EPMA application provided quantitative depth profiles concerning concentration and coverage. For EPMA crater edge profiling the coating needs to be deposited on a foreign substrate because depth distributions of elements being present in both the layer and the substrate cannot be resolved.The combination of AES-depth profiling with EPMA crater edge profiling techniques is a powerful tool to analyse heterostructures quantitatively.     

X-Ray Microanalysis of Real Materials Using Monte Carlo Simulations

Monte Carlo simulations have been used to obtain new results that aid in the microanalysis of sample types frequently encountered in practical analytical situations such as rough surfaces and embedded inclusions. It is shown that the hypothesis that the peak to background is constant on a rough surface is not always true, especially for x-ray lines of low energy and that the peak to background ratio is very sensitive to the electron probe diameter. It is also shown that for embedded inclusions that the shape of the (z) curves differs significantly from the (z) curves of bulk homogeneous materials.     

Surface holography with LEED electrons

The present status of surface holography using low energy electron diffraction intensities is described. It is shown that diffuse intensity distributions appearing with disordered adsorption on a crystalline substrate can be interpreted in a holographic sense by the single adatom acting as a beam splitter for the primary electron beam. We demonstrate that intensities taken at many energies need to enter the reconstruction integral in order to retrieve well resolved atomic images. We also show that the method can be extended to use also discrete superstructure spot intensities instead of diffuse maps, so opening the field to ordered superstructures. The power and applicability of the method is discussed.     

Fast Detection Allows Analysis of the Electronic Structure of Metalloprotein by X-ray Emission Spectroscopy at Room Temperature

The paradigm of "detection-before-destruction" was tested for a metalloprotein complex exposed at room temperature to the high x-ray flux typical of third generation synchrotron sources. Following the progression of the x-ray induced damage by Mn Kβ x-ray emission spectroscopy, we demonstrated the feasibility of collecting room temperature data on the electronic structure of native Photosystem II, a trans-membrane metalloprotein complex containing a Mn(4)Ca cluster. The determined non-damaging observation timeframe (about 100 milliseconds using continuous monochromatic beam, deposited dose 1*10(7) photons/μm(2) or 1.3*10(4) Gy, and 66 microseconds in pulsed mode using pink beam, deposited dose 4*10(7) photons/μm(2) or 4.2*10(4) Gy) is sufficient for the analysis of this protein's electron dynamics and catalytic mechanism at room temperature. Reported time frames are expected to be representative for other metalloproteins. The described instrumentation, based on the short working distance dispersive spectrometer, and experimental methodology is broadly applicable to time-resolved x-ray emission analysis at synchrotron and x-ray free-electron laser light sources.     

Electron and positron pair emission by low energy positron impact on surfaces

The emission of electron pairs from surfaces has the power to reveal details about the electron–electron interaction in condensed matter. This process, stimulated by a primary electron or photon beam, has been studied both in experiment and theory over the last two decades. An additional pathway, namely positron–electron pair emission, holds the promise to provide additional information. It is based on the notion that the Pauli exclusion principle does not need to be considered for this process.We have commissioned a laboratory based positron source and performed a systematic study on a variety of solid surfaces. In a symmetric emission geometry we can explore the fact that positron and electron are distinguishable particles. Following fundamental symmetry arguments we have to expect that the available energy is shared unequally among positron and electron. Experimentally we observe such a behavior for all materials studied. We find an universal feature for all materials in the sense that on average the positron carries a larger fraction of the available energy. This is qualitatively accounted for by a simplified scattering model. Numerical results, which we obtained by a microscopic theory of positron–electron emission from surfaces, reveal however that there are also cases in which the electron carries more energy. Whether the positron or the electron is more energetic depends on details of the bound electron state and of the emission geometry. The coincidence intensity is strongly material dependent and there exists an almost monotonic relation between the singles and coincidence intensity. These results resemble the findings obtained in electron and photon stimulated electron pair emission. An additional reaction channel is the emission of an electron pair upon positron impact. We will discuss the energy distributions and the material dependence of the coincidence signal which shows similar features as those for positron–electron pairs.     

Determination of the depth profiles of ion-implanted impurities by electron probe x-ray microanalysis

The aim of this paper is to demonstrate the suitability of electron probe x-ray microanalysis (EPMA) for nondestructive determination of the depth profiles of ion-implanted impurities. The intensities of the characteristic x-ray emission of impurity atoms (P and As) were measured (on a WDX spectrometer) on the implanted specimens and references (GaP and GaAs) at three values of primary electron energy E_P. The range distribution of the implanted impurity as a first approximation is given by a Gaussian distribution. A two-parameter fitting has been developed for the determination of Gaussian parameters R_P and ΔR_P of the profiles, which give a minimal difference between the experimental and calculated x-ray intensities at different E_P. The dose of the implanted impurity is a third parameter that can be obtained here. The results were compared with those of depth profiles from AES (for P) and SIMS (for As) and good agreement is observed. A new method for the determination of the depth distribution of x-ray production for the characteristic x-rays of impurity atoms is also presented.     

Microcalorimeter Detectors and Low Voltage SEM Microanalysis

The development of the microcalorimeter energy-dispersive X-ray spectrometer (µ-cal EDS) offers a significant advancement in X-ray microanalysis, especially for electron beam instruments. The benefits are especially pronounced for low voltage (5kV) X-ray microanalysis in the field emission scanning electron microscope (FE-SEM) where the high energy resolution of the µ-cal EDS minimizes the peak overlaps among the myriad of K, L, M and N lines in the 0–5keV energy range. The availability of L- and M-shell X-ray lines for microanalysis somewhat offsets the absence of X-ray lines traditionally used above 5keV energy. The benefits and challenges of the µ-cal EDS will be discussed, including P/B ratio for characteristic X-rays, collection angle, count rate capability and the impact of polycapillary X-ray optics on microanalysis.     

Study of the Interface Microstructures of CVD Diamond Films by TEM

 The characteristics of the interface microstructures between a CVD diamond film and the silicon substrate have been studied by transmission electron microscopy and electron energy loss spectroscopy. The investigations are performed on plan-view TEM specimens which were intentionally thinned only from the film surface side allowing the overall microstructural features of the interface to be studied. A prominent interfacial layer with amorphous-like features has been directly observed for CVD diamond films that shows a highly twinned defective diamond surface morphology. Similar interfacial layers have also been observed on films with a <100> growth texture but having the {100} crystal faces randomly oriented on the silicon substrate. These interfacial layers have been unambiguously identified as diamond phase carbon by both electron diffraction and electron energy loss spectroscopy. For the CVD diamond films that exhibit heteroepitaxial growth features, with the {100} crystal faces aligned crystallographically on the silicon substrate, such an interfacial layer was not observed. This is consistent with the expectation that the epitaxial growth of CVD diamond films requires diamond crystals to directly nucleate and grow on the substrate surface or on an epitaxial interface layer that has a small lattice misfit to both the substrate and the thin film material.     

A high-resolution near-edge x-ray absorption fine structure investigation of the molecular orientation in the pentacene/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) pentacene/system

We present x-ray photoemission spectroscopy and highly resolved near-edge x-ray absorption fine structure spectroscopy measurements taken on pentacene thin films of different thicknesses deposited on a spin coated poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) substrate. Thin films of pentacene were prepared by using organic molecular beam deposition in situ using strictly controlled evaporation conditions. Our investigations show that pentacene thin films on PEDOT:PSS are characterized by upright standing molecules. Due to the strong dichroic behavior, the calculated values of the molecular orientation give a clear indication not only of the real molecular arrangement in the films but also of a high orientational order. This high degree of molecular orientation order is a characteristic already of the first layer. The films show the tendency to grow on the PEDOT:PSS substrate following an island-fashion mode, with a relatively narrow intermixing zone at the interface between the pentacene and the polymer blend. The peculiarity of the growth of pentacene on PEDOT:PSS is due to the fact that the substrate does not offer any template for the nucleated films and thus exerts a lateral order toward the crystal structure arrangement. Under these conditions, the upright orientation of the molecules in the films minimizes the energy required for the system stability.     

Growth feature of PTFE coatings on rubber substrate by low‐energy electron beam dispersion

Polytetrafluoroethylene (PTFE) coatings were prepared on Si and acrylonitrile‐butadiene rubber substrates by low‐energy electron beam dispersion. The effects of substrate nature, distance of target to substrate (d_ts) and coatings thickness on the surface morphology, structure, and tribological properties of the coatings were investigated. The results showed that substrate nature affects the shape and size distribution of surface conglomerations of PTFE coatings due to the interaction process of active dispersion particles with underlying polymer layer. Surface energy of PTFE coatings decreases first with the coatings thickness increases to 1.25 µm and then slowly increases with the thickness. Structure defects (pore, interstice, and so on) in the coatings increase with the thickness increases but reduce significantly with the d_ts increases. PTFE coating prepared at the d_ts of 20 cm had a higher intensity of the amorphous absorption bands. Friction experiment indicated that the destroyed area of the coatings in the friction region decreases with increases the coatings thickness but increases with the d_ts. The rubber modified by PTFE coatings with spherical structure possesses a higher stability in the friction process and a lower coefficient of friction. Copyright © 2015 John Wiley & Sons, Ltd.     

Resistivity and Field Electron Emission of Nanowires Formed by Electron Beam Induced Chemical Vapor Deposition

"Self-standing iron nanowires were fabricated at the apex of a tungsten needle tip by electron beam induced deposition. This sharp needle tip which adhered to the nanowire can be moved with a stepping motor and piezo-driving device, and was attached inside a specially designed transmission electron microscope pecimen holder. A copper conductor substrate, with which the approaching nanowires will build up a closed electric circuit, was set on the holder. The tungsten needle tip accompanied with the EBICVD nanowires made contact with the substrate and then a voltage was applied between the two electrodes. Resistivity values of the examined nanowires, by a devised Lock-in-Amplifier circuit, range from 0.1 -m to 10-3 -m. Our investigation might have implications in the fabrication and characterization of nano-electronics device. Precursor with phenanthrene (C4H10) was used and the deposition experiment was done using a scanning electron microscope at room temperature. It was found that the surface structure at the top of the nanorod, such as a small protrusion within only several nanometers scale, has significant influence on the field emission property. An emission current of several tens of nano-ampere flowing through this nanorod could induce resistance heating. In several minutes, this thermal energy could transform the original amorphous carbon into a graphite-like structure embedded with fullerenes. The turn-on voltage of the graphite-like nanorod was about 11 V less than that of the original amorphous case."     

Measuring the electronic structure of disordered overlayers by electron momentum spectroscopy: the Cu/Si interface

The Cu? Si interface was studied by electron momentum spectroscopy. A thick disordered interface is formed if one material is deposited on the other. Electron momentum spectroscopy measures intensity as a function of binding energy and target electron momentum. Momentum resolution is demonstrated to be very helpful in interpreting the data, even for these disordered interfaces. The interface layer has a well‐defined electronic structure, different from either Si or Cu, and consistent with silicide formation. Information is obtained about the total bandwidth of the interface compound, effective Brillouin zone size and Fermi radius. No clear differences are observed in the electronic structure of the interface layer for Si deposited on Cu or Cu deposited on Si. Copyright © 2006 John Wiley & Sons, Ltd.     

Use of monte carlo modeling to aid interpretation and quantification of the low energy-loss electron yield at low primary energies

Experimental low-loss electron (LLE) yields were measured as a function of loss energy for a range of elemental standards using a high-vacuum scanning electron microscope operating at 5 keV primary beam energy with losses from 0 to 1 keV. The resulting LLE yield curves were compared with Monte Carlo simulations of the LLE yield in the particular beam/sample/detector geometry employed in the experiment to investigate the possibility of modeling the LLE yield for a series of elements. Monte Carlo simulations were performed using both the Joy and Luo [Joy, D.C. & Luo, S., Scanning 11(4), 176988 (2005)] to assess the influence of the more recent stopping power data on the simulation results. Further simulations have been conducted to explore the influence of sample/detector geometry on the LLE signal in the case of layered samples consisting of a thin C overlayer on an elemental substrate. Experimental LLE data were collected from a range of elemental samples coated with a thin C overlayer, and comparisons with Monte Carlo simulations were used to establish the overlayer thickness.     

Epitaxy‐like orientation of nanoscale Ag islands grown on air‐oxidized Si(110)‐(5 × 1) surfaces

Growth of Ag islands under ultra‐high vacuum condition on air‐oxidized Si(110)‐(5 × 1) surfaces has been investigated by in situ reflection high energy electron diffraction and ex situ scanning electron microscopy and cross‐sectional transmission electron microscopy. A thin oxide is formed on Si via exposure of the clean Si(110)‐(5 × 1) surface to air. The oxide layer has a short range order. Deposition of Ag at different thicknesses and at different substrate temperatures reveal that the crystalline qualities of the Ag film are almost independent of the thickness of the Ag layer and depend only on the substrate temperature. Ag deposition at room temperature leads to the growth of randomly oriented Ag islands while preferred orientation evolves when Ag is deposited at higher temperatures. For deposition at 550 °C sharp spots in the reflection high energy electron diffraction pattern corresponding to an epitaxial orientation with the underlying Si substrate are observed. The presence of a short range order on the oxidized surface apparently influences the crystallographic orientation of the Ag islands. Copyright © 2011 John Wiley & Sons, Ltd.     

Design and characterization of a metal-ion beam and nitrogen-radical beam source PVD system with in-situ AES constitution and HEED structure analysis

The construction and the operation mode of an ultrahigh vacuum PVD system with integrated electron spectroscopic surface analysis is described. It consists of two metal-ion beam sources and a nitrogen radical beam source. High-energy electron diffraction (HEED) with grazing incidence of the electron beam is applied in-situ to determine the crystallographic data, as texture and structure of the growing layer. Chemical composition and bonding states of the components of the layer are determined also in-situ using an Auger electron spectrometer (AES). In-situ is taken to mean that analysis takes place during deposition of the layer. This work shows that the information depth of HEED with grazing incidence of the beam (theta< 1 degrees ) is of the same order of magnitude as the information depthof AES i.e. a few atom layers. This enables constitution and structure of the near-surface region of the growing layer to be directly determined as a function of the PVD parameters. In the initial experiments Cu/Al bilayers, homogeneous Cu(3)N and heterogeneous Cu/Cu(3)N layers were deposited. The influence of the Cu-ion energy and of the radical portion in the nitrogen reactive gas on the formation of the homogeneous Cu(3)N layer was investigated.     

Development and characterization of thermosetting-thermoplastic polymer blends for applications in damage-tolerant composites

Compatibility or miscibility of polyethersulfones (ICI: Victrex 100P and 300P) and a tetrafunctional epoxy (Ciba-Geigy: MY-720), cured with an aromatic anhydride, has been studied using scanning electron microscopy, x-ray microanalysis, and dynamic mechanical spectroscopy. Fracture toughness of epoxy and blends of an epoxy and polyethersulfones has been measured using three-point bend tests (ASTM: E-399–81), and the energy release rate (G_IC) for the three materials has been compared as a function of test temperature. Fracture surfaces were examined by x-ray microanalysis for detecting concentration of sulfur, present in polyethersulfones, in the matrix and precipitated phase. The influence of morphology of epoxy/polyethersulfone blends on its fracture toughness and toughening mechanism has been studied. A toughening criterion is proposed.     

In situ investigation of the early stage of TiO2 epitaxy on (001) SrTiO3

We report on a systematic study of the growth of epitaxial TiO(2) films deposited by pulsed laser deposition on Ti-terminated SrTiO(3) (001) single crystals. By using in situ reflection high energy electron diffraction, low energy electron diffraction, x-ray photoemission spectroscopy, and scanning probe microscopy, we show that the stabilization of the anatase (001) phase is preceded by the growth of a few nanometers thick pseudomorphic Sr(x)TiO(2+y) (x, y < 1) intermediate layer. The data demonstrate that the formation of this intermediate phase is related to the activation of a long range Sr migration from the SrTiO(3) substrate into the film. Our results enrich the phase diagram of the Sr-Ti-O system under epitaxial strain opening a route for the study of the electronic and dielectric properties of the reported Sr-deficient SrTiO(3) phase.