Quantitative analysis of silicon-oxynitride films by EPMA

Thin films of silicon oxynitride with diverse compositions were prepared by de-magnetron sputtering of silicon, utilising oxygen and nitrogen gas flows and the sputtering power to vary the composition. In order to investigate the composition of these films, a method of analysis by electron probe micro analysis with energy dispersive detection was developed and the figures of merit were compared to the wavelength dispersive method used by other authors. The precision and repeatability of the results are evaluated and the accuracy is checked by comparison with Rutherford backscattering and nuclear reaction analysis. Energy dispersive X-ray spectrometry was proven to be applicable to analyse silicon oxynitride films of any composition yielding quantitative results for nitrogen and oxygen as well as silicon. Besides the good analytical performance, electron probe micro analysis with energy dispersive X-ray spectrometry has turned out to be a non-destructive, quick, easy to use and cost effective tool for the routine analysis of light elements in thin films.     

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.     

Quantitative Sputter Depth Profiling of Silicon- and Aluminium Oxynitride Films

 Silicon- and aluminium oxynitride films have gained attention because of their interesting properties in various fields of technology. The specific properties strongly depend on the concentration of oxygen and nitrogen in the films. For the quantitative analysis of homogeneous silicon- and aluminium oxynitride films, EPMA has been proven a very reliable and precise method of analysis. In order to characterise films with graded composition or interface effects between the film and the substrate it is necessary to use sputter depth profiling techniques such as SIMS, hf-SNMS, AES, or hf-GD-OES. Unfortunately, stoichiometric silicon- and aluminium oxynitride films are insulating and therefore charge compensation has to be applied. For the quantification it was necessary to prepare calibration samples which have been analysed by different bulk analytical techniques such as NRA, RBS and EPMA. With these calibration samples, sensitivity factors have been determined and the functional dependence of the sensitivity factors on the composition has been derived. The advantages and disadvantages of the different sputtering techniques and the applicability of the obtained sensitivity functions for the quantitative depth profiling of silicon- and aluminium oxynitride films are discussed.     

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.     

Analysis of Slightly Rough Thin Films by Optical Methods and AFM

 In this paper the analysis of a family of rough silicon single crystal surfaces covered with native oxide layers is performed using a combined optical method based on a multisample treatment of the experimental data obtained using variable angle of spectroscopic ellipsometry and near normal spectroscopic reflectometry. Within this analysis the values of the thicknesses of the native oxide layers are determined together with the values of statistical parameters of roughness, i.e. with the rms values of the heights and the values of the autocorrelation lengths, for all the samples studied. For interpreting experimental data the perturbation Rayleigh–Rice theory and scalar diffraction theory are employed. By means of the results of the analysis achieved using both the theories limitations of the validity of these theories is discussed. The correctness of the values of the statistical parameters determined using the optical method is verified using AFM measurements.     

Study of Thin Oxide Films by Electron, Ion and Synchrotron Radiation Beams

 Titanium oxide and zirconium oxide thin films deposited on silicon substrates were characterised using electron probe microanalysis (EPMA), Rutherford backscattering spectroscopy (RBS), time-of-flight elastic recoil detection analysis (TOF-ERDA) and scanning photoelectron microscopy (SPEM). The composition and mass thickness of the films were determined and the results of different methods compared. It was revealed that the synchrotron radiation used for SPEM studies caused considerable modification of zirconia films grown at low temperatures.     

EPMA and Quantitative MCs+-SIMS of Metal-DLC Coating Materials

 Compositional characterization of metal-DLC (metal-containing diamond-like carbon) hard coatings is carried out by (WDS)-EPMA and MCs⁺-SIMS. EPMA enables accurate (± 5% relative) quantitative analysis including minor concentrations (0.1–10 at%) of N, O and Ar. Under conditions of “near-surface” EPMA (E₀ < 10 keV) the influence of surface oxide films on “pure” metal standards may be a limiting factor in respect of accuracy. Depth profiling of sufficiently “thick” layered structures (film thickness ≥ 2 μm) is carried out by EPMA-line scans along mechanically prepared bevels. The depth resolution is about 0.2 μm. SIMS in the MCs⁺-mode enables high resolution (< 20 nm) depth profiling of metal-DLC layered structures including the determination of H (1–20 at%). MCs⁺-SIMS, i.e. employing Cs⁺ primary ions and monitoring MCs⁺ molecular secondary ions (M is the element of interest) is presented as a promising route towards sufficiently accurate (10–20%) SIMS-quantification. Matrix-independent relative sensitivity factors for MCs⁺-SIMS are derived from homogeneous coating materials defined by EPMA. EPMA proves to be also useful to detect problems related to SIMS of Ar in metal-DLC materials. The combination EPMA-SIMS is demonstrated as an effective analytical strategy for quality control in industrial production and to support the development of metal DLC layered structures with optimum tribological properties.     

Application of Sputter-Assisted EPMA to Depth Profile Analysis

 A common problem in depth profile measurement is the calibration of the depth scale. The new technique of sputter assisted electron probe microanalysis offers the possibility of calculating the composition as well as the depth scale solely from the acquired X-ray intensity data without further information, e.g. sputter rates. To achieve a depth resolution that is smaller than the depth of information of the electron probe, i.e. 0.1–1 μm, special deconvolution algorithms must be applied to the acquired data. To assess the capabilities of this new technique it was applied to a Ti/Al/Ti multilayer on Si under different measurement conditions. Quantitative depth profiles were obtained by application of a deconvolution algorithm based on maximum entropy analysis. By comparison of these profiles with AES depth profiles and AFM roughness measurements, it was shown that the limiting factor to the achievable depth resolution is the occurrence of surface roughening induced by the sputtering process rather than the relatively large depth of information of the electron probe. We conclude that for certain applications sputter-assisted EPMA can be regarded as a valid depth profiling technique with a depth resolution in the nm range.     

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.     

X-Ray Emission from Thin Films on a Substrate – Calculation and Experiments

 Monte Carlo simulation of electron transport in solids is widely used in electron microscopy, spectroscopy and microanalysis. The reliability of physical models incorporated in a Monte Carlo code is usually checked by comparing with experimental results. Elastic or inelastic collisions are usually considered as the basic interactions of electrons with atoms. In our Monte Carlo code the single scattering model is employed for simulation of X-ray emission from thin films of Au on the Si substrate. The electron beam energy was in the range 10–30 keV, the take-off-angle was 40°. The simulated values of X-ray production were calculated in our Monte Carlo code using several models of ionisation cross-sections. For the emitted intensities the depths of inelastic collision and X-ray absorption were taken into account, then the k-ratios were calculated. These data were compared with experimental values of k-ratios calculated from X-ray intensities of Au M and Au L characteristic lines. We followed mainly the dependence of the k-ratios of the film element on film thickness. The film thickness was in the range 0.05–1 μm. Reasonably good agreement was found for dependences of X-ray intensity on film thickness in the whole energy range and for both lines, especially for Powell’s model of the ionisation cross-section.     

Comparative Analysis of a Solar Control Coating on Glass by AES, EPMA, SNMS and SIMS

 A solar control coating was analysed by different methods of surface analysis with respect to the layer sequence and the composition and thickness of each sublayer. The methods used for depth profiling were Auger electron spectroscopy, electron probe microanalysis, secondary neutral mass spectroscopy and secondary ion mass spectroscopy based on MCs⁺. The structure of the coating was unknown at first. All methods found a system of two metallic Ag layers, embedded between dielectric SnO_X layers. Additionally, thin Ni-Cr layers of 1–2 nm were detected on top of the Ag layers. Thus the detected layer sequence is SnO_X/Ni-Cr/Ag/SnO_X/Ni-Cr/Ag/SnO_X/glass. The Ni:Cr ratio in the nm-thin layers could be quantified by every method, the Cr fraction corresponding to less than one monolayer. We compare the capabilities and limitations of each method in routinely investigating this solar control coating. Importance was attached to an effective investigation. Nevertheless, by combining all methods, measuring artefacts could be uncovered and a comprehensive characterisation of the system was obtained.     

Determination of Nb, Ta, Zr and Hf in Micro-Phases at Low Concentrations by EPMA

 Depletion of high field strength elements (HFSE: Nb, Ta, Zr, Hf ) relative to other lithophile trace elements in arc magmas and variations of Nb/Ta and Zr/Hf ratios in mantle-derived rocks can be addressed through studies of minerals, which concentrate and fractionate these elements. The presence of rutile, a common accessory Ti-oxide phase in various mantle rocks, has often been invoked to explain the Nb and Ta depletion in arc lavas because it has the highest HFSE abundances among the known mantle minerals. In this study, we measure the concentrations of Nb, Ta, Zr and Hf (at > 200 ppm) in rutile of two metasomatized mantle lherzolites using a Cameca SX-100 electron microprobe and obtain Nb/Ta ratios with an accuracy of about ± 5%. Mass balance calculations indicate that ≤ 1−5% of Nb and Ta in the rocks reside in major minerals and that the balance is hosted by accessory Ti-oxides. The Nb/Ta ratios vary significantly in nearby rutile grains in both peridotites (17–33, average 23; 12–37, average 21). Therefore, individual rutile grains may not be representative of the total grain population. However, Nb/Ta ratios measured in the bulk rock lherzolites by solution ICP-MS (21 ± 0.3) are within the analytical error of the average Nb/Ta values calculated for 5–7 rutile grains in both samples. These results emphasise that a representative grain selection must be analysed in order to determine trace elements contents of bulk rocks from data on accessory phases.     

Volcanic Quartz Growth Zoning Identified by Cathodoluminescence and EPMA Studies

 Quartz is a common phenocryst in acidic volcanic rocks but rarely contributes to the understanding of the magmatic or eruptive processes due to its apparent chemical homogeneity. Cathodoluminescence studies indicate that volcanic quartz is strongly zoned with respect to the trace elements. The determination of this zoning can help to elucidate the crystallisation history of the magmatic rock. Polished thin sections from rhyolitic and dacitic volcanic rocks were examined by cathodoluminescence mounted on an optical microscope and analysed by electron probe microanalysis. X-ray mapping of the trace elements incorporated in the zoned quartz was also performed. The interpretation of the data obtained from these different analytical methods provides useful information on the chemical zoning of single crystals and therefore on the chemico-physical conditions of the melt from which the quartz crystallised. Quartz from dacitic rock shows a complex cathodoluminescence oscillatory zoning, consisting of large red-brown and blue bands concentric to a resorbed core. Quartz from rhyolite shows simpler cathodoluminescence zoning, consisting of dark to bright blue luminescent bands. The EMPA analyses and the X-ray maps combined with the cathodoluminescence images suggest a clear correlation between the concentrations of some trace element (mainly Al and Ti, acting as activators of luminescence) and the cathodoluminescence colours pattern zoning. The incorporation of these trace elements during the growth of the crystals is linked to small variations in the thermo-chemical properties of the magma such as temperature and chemical composition.     

Examination of the Spatial Distribution of Dyes and Polymers in Thin Films by Two-Photon Microscopy

Summary.  Two-photon absorption induced fluorescence microscopy was used as a tool for the examination of the spatial distribution of a thin dye film. The two-photon absorption induced fluorescence signal is essentially the same as that produced by excitation with a single photon of equivalent energy. When femtosecond pulses are focused into a sample there is an intrinsic spatial selectivity of the two-photon emission signal, since it is dependent upon the square of the light intensity. This has tremendous implications in fluorescence microscopy. Since two-photon absorption is confined in a small region at the focal waist of an objective lens, photodamage and photobleaching of the sample are significantly reduced. In addition, the two-photon signal has inherent z-axis spatial resolution, which facilitates the construction of 3-D images. In the present work an application of this technique to a thin film of a dye is presented. The method can generally be applied to thin films made from photonic polymers. Received June 23, 2000. Accepted (revised) July 31, 2000     

EPMA of Porous Media: A Monte Carlo Approach

 We examine the influence of the sample porosity on the X-ray emission from mesoporous alumina bombarded with kilovolt electrons. Experimental results show that there is a loss of X-rays (Al Kα and O Kα) from those samples when compared to a fully dense mono-crystalline alumina (sapphire), which depends on the X-ray line, the measurement time and the embedding medium. Both geometrical and charging effects may be responsibl e for this signal loss. Monte Carlo simulations of the X-ray intensity emitted from porous alumina, using different models to describe sample porosity, show that the geometrical effect of porosity itself cannot account for the X-ray loss. Charge trapping effect and/or its combination with porosity is therefore expected to be the major cause of the signal loss.     

Application of Thin-Window EPMA to Environmental Problems in Hungary

 The combination of single-particle analysis using thin-window EPMA and a reverse Monte Carlo quantification procedure has been proven to provide semi-quantitative elemental concentrations, including light elements. The capabilities of the method are demonstrated through three different environmental applications in Hungary. Lake Balaton is the largest lake in central Europe. It is suspected that the atmosphere is an important source of environmental deterioration of the Lake, relative to the pollutant supply by rivers and direct discharges. Thin-window EPMA results of around 25,000 individual particles indicated that the composition of the aerosol did not show characteristic seasonal variation, it was more correlated to the daily meteorological circumstances. A serious heavy metal pollution of the river Tisza occurred on 10 March 2000, from a mine-dumping site in Romania. Sediment samples were taken from the main riverbed at six sites, on 16 March 2000. In some of the samples, pyrite type particles were observed in high abundance, revealing their dumping-site origin. Biomass burning for energy production has been increased recently, mostly in households and for space heating. Fly-ash and bottom-ash samples were collected at a 600 kW heating plant at Sződliget during standard winter operation. Most particles contained over 65% of unburned organic substance. The concentrations of major elements were obtained for each individual particle using thin-window EPMA, providing accurate matrix composition for further μ-XRF investigations of the trace element composition.     

EPMA and GDOES in Functional-Gradient Hardmetal Systems

 WDS-EPMA and GDOES measurements were applied for the characterization of the in-situ surface modification process of (Ti, W)C-based hardmetals by in-diffusion of carbon and nitrogen leading to complicated microstructures composed by layers and/or gradients. The calibration of the analytical techniques was performed with chemically characterized specimens prepared by diffusional techniques or hot-pressing. In addition, for the GDOES method, certified reference materials (CRMs) have been used. The work was started from a re-investigation of the W-C and Mo-C systems in order to measure homogeneity regions of the various phases prepared by use of diffusion couples. Subsequently, the metal and non-metal contents of various sequences of layers and/or gradients in functional-gradient hardmetals (FGHs) were measured. Both methods were employed as complementary tools to get information about the element-concentration distribution in FGHs so that a better understanding of the influence of process parameters for fabrication of special hardmetals is possible.     

EPMA analysis of float glass surfaces

This work concentrates on the setting-up of conditions for the quantitative analysis of the composition profiles of major and minor components of float glass surfaces with an electron probe micro-analyser. Since surfaces are modified for depths of 10–50 m, they have been studied both in polished cross-section and perpendicularly to the electron beam by varying its energy to investigate the near-surface region (0–3m). The results demonstrate that combined use of the two methods supplies complete and continuous information on the quantitative distribution from large depths to the first layers of the float surfaces. The experimental conditions, sample preparation, in-depth and lateral resolutions, precision and accuracy of the methods are also investigated.     

Quantitative EPMA of element depth distribution

A new model for the ionization depth distribution function has been proposed. Within the framework of this model full electron flux is considered to be divided into two fluxes propagating in forward and backward directions through a sample. The intensities of these fluxes can be derived on the basis of simple assumptions of electron-solid interactions. The approach can be effectively applied to a system with an arbitrary form of depth concentration profile. The obtained results are in reasonable agreement with Monte Carlo simulations and experimental results. Some mathematical techniques have been presented for quantitative analysis of thin films on substrates and element depth distribution.     

Quantitative analysis of W-C:H coatings by EPMA,RBS (ERD) and SIMS

Several analytical techniques have been used to characterize homogeneous films of tungsten-containing hydrogenated carbon (W-C: H), deposited on Si with a film thickness of 1–1.5 m. Electron probe microanalysis (EPMA) enables one to determine the major components W (3–43 at %) and C, impurities (< 2 at %) of Ar and O, and the mass thickness (300–1800 g/cm²) of the films. The agreement between the results of EPMA and the data (W-content, mass thickness) provided by Rutherford backscattering spectrometry (RBS) is 5–10% relative. Quantitative analysis of hydrogen in W-C:H films (1–16 at %) is carried out by the technique of elastic recoil detection (ERD). A suitable scheme for the determination of H in W-C: H films by SIMS is proposed, based on monitoring the intensity ratio of HCs⁺/CCs⁺ secondary ions.