Backscattering correction for quantitative Auger analysis: I. Monte Carlo calculations of backscattering factors for standard materials

The electron backscattering effect which is important for the quantitative interpretation of “matrix effects” in AES is investigated by applying the Monte Carlo calculation technique. The present calculation model is based on the use of a precise elastic scattering cross-section obtained by the partial wave expansion method, as well as on the combined use of Gryzinski's excitation function and Bethe's stopping power for inelastic scattering. Systematic calculations of the backscattering factors were performed for over 25 materials including pure elements, compounds, and alloys, which have been widely used as standard materials for practical Auger analysis. The results should enable the accuracy of quantitative analysis by AES to be improved.     

Measurement of ionization cross-sections and backscattering factors for use in quantitative AES

For the extraction of quantitative information from Auger electron spectra two parameters (apart from a number of instrumental parameters) are of utmost importance: the ionization cross-section and the backscattering factor. The determination of these two parameters is discussed. Ionization cross-section values for L- and M-shells have been determined based on existing values for K-shells from the literature. The backscattering factor for Si is calculated as a function of energy of the primary electrons and compared with absolute measurements of this factor using an adsorbed monolayer of sulfur or oxygen on a Si (100) surface.     

Dependence of the AES backscattering correction factor on the experimental configuration

We present an analysis of the dependence of the backscattering correction factor (BCF) in Auger-electron spectroscopy (AES) on the analyzer acceptance angle. Illustrative BCF calculations are presented for Pd M₅N₄₅N₄₅ Auger electrons as a function of primary-electron energy for primary-electron angles of incidence, θ₀, of 0° and 80° and for various values of the analyzer acceptance angle. It was necessary to generalize the BCF definition for the case of an analyzer with an arbitrarily large acceptance angle; this was done with a new function, the integral emission depth distribution function. BCFs calculated from an advanced model of electron transport in the surface region of the Pd sample varied weakly with analyzer half-cone angle for θ₀ = 0° but more strongly for θ₀ = 80° where there were BCF differences varying between 19% at a primary energy of 1 keV and 6% at a primary energy of 5 keV. These BCF differences are due in part to variations of the BCF with emission angle and in part to variations of the density of inner-shell ionizations within the information depth for the detected Auger electrons. The latter variations are responsible for differences larger than 10% between BCFs from the widely used simplified BCF model and those from the more accurate advanced model for primary energies less than about 5 keV for θ₀ = 80°. For normal incidence of the primary beam, differences greater than 10% between BCFs from the simplified and advanced models were found for primary energies between 1 keV and 4 keV. These BCF differences indicate that the simplified model can provide only approximate BCF values. In addition, the simplified model does not provide any BCF dependence on Auger-electron emission angle or analyzer acceptance angle.     

Quantitative Auger electron spectroscopy analysis of binary alloys with separate matrix correction factors for bulk and surface

A new method which takes into account the separate matrix correction factors for bulk and surface has been tried out for quantitative Auger electron spectroscopy analysis of binary alloys. The calculations use an iteration scheme. It has been applied to the Fe-Cr alloys studied at this Centre and the Auger electron spectroscopy data for the other alloy systems available in literature. The results are now more compatible with the expectation that the surface composition is different from the bulk.     

Low energy Auger electron spectroscopy of titanium nitrides for quantitative analysis

The potential of the low energy (20–30 eV) region of the Auger spectrum of titanium nitrides for quantitative analysis has been examined. Nitride films were prepared by nitrogen ion implantation and adsorption at 300 and 900 K and subject to Auger electron analysis in both the low and high energy regions, The nitrogen concentration of implanted films will be uniform over the analysed depth and could be determined by spectrum simulation of the high energy region, a technique described previously. This method permitted an internal calibration of the low energy Auger spectrum against nitrogen composition. The low energy spectrum contains two major features which vary in intensity, and energy, with x, the N/Ti atom ratio: Peak A, present in the pure Ti spectrum and assigned to the Ti(3p)Ti(3d)Ti(3d) transition, has an intensity which decreases linearly with x, whereas peak B, present in the stoichiometric nitride and attributed to the Ti(3p)Ti(3d)N(2p) cross transition, has an intensity which reaches a maximum at x = 0.05. The linear decrease in peak A intensity was ascribed to the linear decrease in the number of unoccupied octahedral holes with x. Occupied intrahole and occupied-unoccupied inter-hole transitions make a contribution to peak B and the latter will pass through a maximum at x = 0.5. The low energy spectrum calibration permitted depth profiles to be determined for adsorbed films at 300 and 900 K. In the latter case both methods gave the same result because rapid diffusion produces a film uniform over the analysed depth. For adsorbed films produced at room temperature the high and low energy results were quite different, reflecting the increased depth resolution of the low energy electrons.     

Methods of analysis for backscattering from tissues.

Two techniques for tissue characterization by ultrasonic analysis are described. In the first, using narrow-band pulses, the angular variation I (theta) of the ultrasonic intensity back-scattered by vegetal or animal targets is analysed. We examine how it is possible to estimate the surface roughness and the average spatial periodicity d characteristic of the tissues, by calculating the Fourier transform or the autocorrelation function of I (theta). In the second technique the sample is insonified with a broadband pulse at a fixed angle. A value of the mean periodicity can be obtained directly from the frequency spectrum of the echo for tissues of fairly regular structure.     

Quantitative approach of Auger electron spectrometry: II. Experimental part

We illustrate the formalism proposed in part one by two studies: thermal segregation of impurities on the surface of a titanium sample, and chemical depth profiling of a passive film formed on stainless steel. The choice of an Auger transition which does not involve valence electrons is particularly emphasized to obtain a satisfactory quantification, when active species are present on the surface.     

Absolute metabolite quantification by in vivo NMR spectroscopy: V. multicentre quantitative data analysis trial on the overlapping background problem

The goal of this study was to establish the best approach for quantifying nuclear magnetic resonance (NMR) lines, that in the frequency domain are overlapping with broad, unwanted background features. To perform the quantitative data analysis in a controlled way, test signals were designed and utilised, derived from two different real-world in vivo nuclear magnetic resonance signals. One of the main conclusions of the study was that the quantification methods currently available to the biomedical research groups can deliver the correct values of the quantitative parameters, but that great care should be taken in using optimal input parameters for the computer programs concerned.     

Special techniques for the Auger analysis of microelectronic devices

Microelectronic devices are becoming more complex and device features are getting smaller as the level of integration continues to increase. Although scanning Auger microscopy has been applied extensively to the analysis of microelectronic devices with a great deal of success, the analysis of current and future devices is presenting new challenges. The major limitations are (1) features of interest in microelectronic circuits are often comparable in size to the beam diameter of commercial Auger microprobes, and (2) the electron beam tends to drift about on the specimen surface because of mechanical instability and differential thermal expansion of the apparatus. In this paper, we present two different techniques developed to overcome these limitations. In the specimen modulation technique, the modulating signal is applied to the electrically isolatable regions of a device instead of to the electron energy analyzer. This method of modulation permits the detection of only the Auger electrons that are emitted from the modulated region. Spurious contributions from adjacent areas inadvertently illuminated by the analyzing beam are suppressed. In the position modulation technique, the analyzing beam is scanned repetitively across the feature to be analyzed and the Auger signal is synchronously detected at the scan frequency. The resulting Auger signal magnitude is shown to be unaffected by beam drift. This method of signal detection eliminates the error and uncertainty caused by beam instability during long-term depth profiling, but is applicable only to specimens with certain geometries.     

Study of adsorption phenomena on aluminium by interatomic Auger transition spectroscopy: II. CO adsorption onto Al

Adsorption of carbon monoxide on aluminium is studied by the combination of in situ evaporation of Al and the Auger electron spectroscopy. New Auger signals which are attributed to interatomic Auger transitions in Al₄C₃ type AlC bonds are found. It is revealed that two adsorption stages exist in the adsorption process, i.e., that after the formation of the AlC bond takes place, the adsorbed layer consisting of AlC and AlO bonds is formed.     

Method for the phase correction of intense ultrashort laser pulses at Raman backscattering in a plasma

A method for obtaining intense ultrashort laser pulses with a given phase front has been proposed. This method is based on Raman backscattering in a plasma and makes it possible to specify the phase of laser pulses with a duration from 100 fs and an intensity up to one-tenth of the relativistic intensity.     

Results of a joint auger/esca round robin sponsored by astm committee E-42 on surface analysis. Part II. Auger results

We report the results of a round robin involving kinetic-energy (KE) and relative-intensity measurements on high-purity samples of copper and gold by Auger-electron spectroscopy. These results were obtained using 28 different instruments or analyzers manufactured by four companies. We found that the spread in reported KE values ranged from 7 eV at a KE of 60 eV to 32 eV at a KE of ～2025 eV. The total spread in reported intensity ratios ranged from a factor of ～38 for the ～6O eV and ～92O eV peaks of Cu to a factor of $\text{~}\text{?}$120 for the ～70 eV and ～2025 eV peaks of Au. We have analyzed the observed trends in some detail. The systematic error of kinetic-energy measurements increases with kinetic energy for many instruments. Even though all instruments were adjusted with the use of 2 keV elastically scattered electrons, the spread in the reported positions of the ～2025 eV Au peak indicates that the instruments were not adequately calibrated. Examples of erratic response were found in the measurements of relative intensities; it was believed, though not proved, that the more extreme values of intensity ratios were associated with instrumental malfunctions or operator mistakes. As in the similar ESCA round robin (Part I), the spread in reported Auger kinetic energies and relative intensities demonstrates clearly the need for standards (e.g., calibration methods, operating procedures, and data analysis) to ensure that data of known accuracy can be obtained routinely. Until suitable standards are available, interested individuals may find it useful to compare measurements using their own Auger or ESCA instruments with the group results and the trends found in the round-robin results.We have conducted an extensive round robin consisting of AES measurements on high-purity samples of Cu and Au. Participants were asked to measure the kinetic energies and relative intensifies of designated Auger peaks under specified conditions. This round robin was conducted contemporaneously with a similar ESCA round robin, the results of which have already been published [1].The AES round robin had three principal objectives. First, it was intended to assess the overall accuracy of KE and relative-intensity measurements in a relatively straightforward AES measurement. An earlier round robin [2] with catalyst samples demonstrated substantial spreads of reported data, and it was believed that comparisons of data obtained for cleaned metallic samples should give a more accurate picture of the current state-of-the-art. With a larger number of participants in the present round robin than in the catalyst round robin, we in fact find a comparable spread in the raw data. The spread in the reported KE measurements is a function of kinetic energy, and ranges from 7 eV at a KE of 60 eV to 32 eV at a KE of 2 keV. The imprecision of the KE measurements is typically ～1–3 eV. The total spread in the reported intensity ratios ranges from a factor of ～38 for Cu (at an incident energy of 3 keV) to a factor of ～120 for Au (at the same incident energy). The imprecision of the intensity ratios is typically less than 10%.Second, it was desired to determine the variation of AES intensities as a Cu sample was displaced along the analyzer axis with respect to its optimum position. Many of the participants found maxima in the intensities of the Cu ～60 eV and ～920 eV peaks at or very close to that sample position found to be optimum for the 2 keV elastic peak. Other participants found intensity maxima at sample positions up to ～4 mm away from the 2 keV elastic-peak position; these participants found that when the sample was at the optimum position for the 2 keV elastic peak, the intensities of the ～60 eV and ～920 eV Cu peaks could be as low as 50% of the corresponding maximum peak intensities that were found when the sample was displaced.Third, it was intended to measure the Auger KE for the “adventitious” carbon that forms on initially clean samples in the ambient vacuum of each instrument. Few participants made this measurement, although it was observed that the spread of reported energies for the carbon Auger peak was comparable to that found for the low-energy (60–7OeV) peaks in Cu and Au.We have examined the KE and relative-intensity data in some detail. We found it useful to compute deviations of individual KE measurements from the median values of the reported measurements for the selected Auger peaks. These deviations were plotted as a function of kinetic energy and lines were drawn connecting data points obtained using the same instrument. Such plots can be regarded as “error functions” or “calibration curves” based on the use of the group median values as reference data. These curves indicate that for many instruments the error of KE measurements increases approximately linearly with KE (unlike the behavior found in similar plots for binding-energy measurements in the ESCA round robin, in which the error was often nearly constant or slowly varying with binding energy). The large spread (32 eV) in the reported positions of the Au M₅N_6,7N_6,7 peak at a KE of ～2024 eV was considered particularly significant, since most instruments were adjusted and aligned using elastically scattered electrons at an energy of 2 keV. This observation clearly indicates that the working KE scales of the instruments were not adequately calibrated using the elastic-peak method; this problem is believed to be due to the insufficient accuracy of the 2 kV power supplies or the voltmeters used to display the KE scales rather than to any intrinsic deficiencies in the use of the elastic-peak method. There were several examples, however, in which plots of the intensities of the ～60 eV and ～920 eV Cu peaks as a function of sample position had maxima for both peaks at a position different from that found optimum for the 2 keV elastic peak. These observations indicate that sample alignment by the elastic-peak method was not done with sufficient accuracy in some laboratories. Finally, while the imprecision in the locations of the elastic peak and of Auger peaks in the round robin was typically 1–3 eV, the overall inaccuracy of the KE measurement was usually substantially larger.Most participants found that ratios of peak heights for the low-energy and high-energy transitions in Cu and Au decreased slowly as the incident electron energy was increased from 3 keV to 8 keV. Some participants, however, obtained qualitatively different dependences on incident energy; these results were attributed to mistakes, instrument malfunctions, or to inadequate alignment. Our experience in the ESCA round robin indicated that operator mistakes or instrumental problems were responsible for most of the outliers in comparisons of measured intensity ratios. We suspect (although we have not proved) that the more extreme values of peak-height ratios in the AES round robin have a similar origin. The AES intensity data were analyzed to search for mechanisms that could account for the large range of reported intensity ratios. We considered several possible origins for the more extreme data values. First, we examined the reported peak-height ratios for Cu and Au, to search for possible variations of the instrumental transmission functions from their “ideal” values. Second, we considered whether relatively large amounts of residual surface carbon could account for the observed intensity ratios. Third, we tested whether the instruments which exhibited “non-ideal” behavior (probably because of significant stray magnetic fields or inadequate sample alignment) when the samples were translated parallel to the analyzer axis were also the ones which gave the more extreme peak-height ratios. Fourth, we investigated whether probable variations in the amplitude of the modulation voltage applied to the analyzers would modify significantly the ratios of the observed intensities. Fifth, we considered the effects of the differing energy resolutions of the analyzers in the round robin. Finally, we considered effects due to variations in surface roughness caused by the different ion-sputtering conditions used for initial cleaning of the samples. None of these factors alone could account for the more extreme variations of the peak-height ratios, although it is possible that some of these factors could affect certain specific instruments while a different combination of the factors could be important in other cases. Although we were unable to demonstrate conclusively the nature of instrumental artifacts or possible operator mistakes in the various intensity measurements, we believe that the spread in the reported intensity ratios is associated with specific measurement problems in particular individual laboratories. A variety of factors have been identified here to account for the more modest but nevertheless distressing range of intensity ratios (a factor of ～2 for Cu and of ～5 for Au) for the majority of the participants.The spreads in the energies and relative intensities of Auger and photoelectron peaks in this AES and the previous ESCA round robin indicate clearly that improved calibration and operating procedures are required for both Auger and ESCA measurements. Published data, for example, are of little value unless credible statements of accuracy can be associated with the numerical results. We hope that the standards needed for improved measurements can be developed by the ASTM Committee E-42 on Surface Analysis together with other interested parties.     

The Ti/c-Si solid state reaction : II. Additional measurements by means of RBS, XPS and AES

In a previous paper [Appl. Surface Sci. 40 (1990) 333], we have reported the results of a spectroscopic ellipsometric study of the c-Si/Ti solid state reaction. For this purpose we have grown and heated thin (≈10nm) Ti films on a clean c-Si substrate. The investigation revealed that already at moderate temperatures a metastable silicide (≈350°C), probably a monosilicide, and disilicide (≈450°C) are formed. These two metastable transition states, denoted by state I and II respectively, and the final disilicide (state III, ≈700°C) are additionally studied by means of a number of quantitative techniques, such as RBS, XPS and AES. The results reveal a Si-enriched monosilicide state I, Si: Ti = 1.2 and a stoichiometric but Si segregated disilicide state II; surface composition approximately TiSi₃. The finally obtained disilicide (III) has recrystallized into probably large, flat islands embedded in a c-Si matrix.     

On the semi-empirical elemental sensitivity factors for AES: ionization cross-section and electron mean free path

Two important parameters in semi-empirical theories of elemental sensitivity in Auger electron spectroscopy are the electron-impact ionization cross-section and the electron mean free path. This paper compares the Gryziński, Lotz, and Casnati et al. theories of ionization cross-section, as well as the Seah and Bench empirical theory and the Szajman et al. dielectric theory of electron mean free path, by matching the elemental sensitivity factors calculated with these parameters to experimental AES elemental sensitivities. Electron mean free paths, calculated with the dielectric theory, are presented, for the Auger electron energies of interest, for most elements in the periodic table. The best match between the semi-empirical and experimental sensitivities (with a standard deviation of 56%) was for the combination of the Casnati et al. ionization cross-section and the dielectric theory electron mean free path.     

Mössbauer backscattering spectrometer for mineralogical analysis of the mars surface

A Mössbauer spectrometer for the mineralogical analysis of the Mars surface is under development. This instrument will be installed on a Mars-Rover, included in the Soviet Union Mars-94/96 Mars mission. Due to power and mass restrictions the electromechanical drive and the electronic components have been extremely miniaturized in comparison to standard systems. Solid state detectors (PIN-diodes) are used for γ- and x-ray detection. The whole spectrometer is controlled by a microprocessor (transputer). An additional application as x-ray fluorescence spectrometer is proposed.     

Optical fibre attenuation measurement by the backscattering method: effect of noise

The backscattering method is now a well-established technique for the measurement of attenuation in multimode optical fibres. In this paper the effect of noise is evaluated in order to optimize the precision of the measurement, its dynamic range and the time required to collect the data. An experimental set-up is described and the experimental results reported.     

Absolute metabolite quantification by in vivo NMR spectroscopy: II. a multicentre trial of protocols for in vivo localised proton studies of human brain

We have performed a multicentre trial to assess the performance of three techniques for absolute quantification of cerebral metabolites using in vivo proton nuclear magnetic resonance (NMR). The techniques included were 1) an internal water standard method, 2) an external standard method based on phantom replacement, and 3) a more sophisticated method incorporating elements of both the internal and external standard approaches, together with compartmental analysis of brain water. Only the internal water standard technique could be readily implemented at all participating sites and gave acceptable precision and interlaboratory reproducibility. This method was insensitive to many of the experimental factors affecting the performance of the alternative techniques, including effects related to loading, standing waves and B₁ inhomogeneities; and practical issues of phantom positioning, user expertise and examination duration. However, the internal water standard method assumes a value for the concentration of NMR-visible water within the spectroscopic volume of interest. In general, it is necessary to modify this assumed concentration on the basis of the grey matter, white matter and cerebrospinal fluid (CSF) content of the volume, and the NMR-visible water content of the grey and white matter fractions. Combining data from 11 sites, the concentrations of the principal NMR-visible metabolites in the brains of healthy subjects (age range 20–35 years) determined using the internal water standard method were (mean ± SD): [NAA] = 10.0 ± 3.4 mM (n = 53), [tCho] = 1.9 ± 1.0 mM (n = 51), [Cr + PCr] = 6.5 ± 3.7 mM (n = 51). Evidence of system instability and other sources of error at some participating sites reinforces the need for rigorous quality assurance in quantitative spectroscopy.     

Auditive and cognitive factors in speech perception by elderly listeners. II: Multivariate analyses

In part I of this study [van Rooij et al., J. Acoust. Soc. Am. 86, 1294-1309 (1989)], the validity and manageability of a test battery comprising auditive (sensitivity, frequency resolution, and temporal resolution), cognitive (memory performance, processing speed, and intellectual abilities), and speech perception tests (at the phoneme, spondee, and sentence level) were investigated. In the present article, the results of a selection of these tests for 72 elderly subjects (aged 60-93 years) are analyzed by multivariate statistical techniques. The results show that the deterioration of speech perception in the elderly consists of two statistically independent components: (a) a large component mainly representing the progressive high-frequency hearing loss with age that accounts for approximately two-thirds of the systematic variance of the tests of speech perception and (b) a smaller component (accounting for one-third of the systematic variance of the speech perception tests) mainly representing a general performance decrement due to reduced mental efficiency, which is indicated by a general slowing of performance and a reduced memory capacity. Although both components are correlated with age, it was found that the balance between auditive and cognitive contributions to speech perception performance did not change with age.     

Investigations on the oxidation of zirconium nitride films in air by nuclear reaction analysis and backscattering spectrometry

The thermal oxidation of dc magnetron sputter deposited thin ZrN films in air in the temperature range of 100-475 °C has been studied by depth profiling N using nuclear reaction analysis (NRA) involving ¹⁵N(¹H,αγ)¹²C resonance reaction and O using 3.05 MeV ¹⁶O(α,α)¹⁶O resonant scattering. The structural and morphological changes accompanying the process have also been investigated. NRA/backscattering spectrometry measurements show that oxidation results in the formation of ZrO_1.8±0.1 at the surface. An interface consisting of Zr, O and N is also formed underneath the surface oxide. For an isothermal annealing, oxide layer as well as interface exhibits parabolic growth with the duration of annealing. The diffusion of oxygen through the already grown oxide layer (D = 5.6 × 10⁻¹⁴ cm² s⁻¹ at 475 °C) forms the rate-controlling step of oxidation. The diffusion may be facilitated by the high concentration of oxygen vacancies in the oxide layer. Glancing incidence X-ray diffraction (GIXRD) measurements indicate that zirconia films formed are phase-singular (monoclinic) and are textured in (2 0 0) and (3 1 1) orientations. Examination by scanning electron microscopy (SEM) reveals the formation of blisters on sample surfaces on prolonged oxidation. The blistering can be attributed to intrinsic growth stress arising due to the larger molar volume of zirconium oxide in comparison to zirconium nitride, a fact demonstrated by the depth profile measurements as well.