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

Abstract 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 ~ 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 M5N6,7N6,7 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.