Surface composition and depth concentration profile of platinum/tin alloys from combined X-ray photoelectron and Auger spectroscopic data

Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (X-PS) have been combined to study surface enrichment of two platinum/tin alloys, viz. PtSn and Pt₃Sn, effected by reduction in hydrogen at 550°C. By making use of the different information depths of AES and X-PS for this alloy system, as determined by the corresponding mean free paths of inelastic scattering of the emitted characteristic electrons, a rather detailed picture has been obtained of the composition of the topmost atomic layers in these alloys. It is shown that both alloys exhibit phenomena of surface enrichment and depletion of the underlying layers over distances of the order of 10 Å.     

AES studies of palladium films formed on copper and mica

Thin epitaxial films of palladium were grown on epitaxial copper films and cleaved mica in ultra high vacuum. The growth modes of these films were investigated by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), transmission electron microscopy (TEM), and TEM replica techniques. Layer by layer growth of Pd on Cu and mica was observed and inelastic mean free paths of Auger electrons for energies of 60 eV (Cu MMM) and 329 eV (Pd MNN) were calculated. These values were 5.7 and 6.9 Å respectively. The thermal stability of monocrystalline and polycrystalline Pd/Cu bilayer films at 483 K was also investigated by AES and TEM. It was found that Pd agglomerates on the Cu at this temperature to form a Stranski-Krastanov growth morphology. The agglomeration is much more rapid on polycrystalline films, suggesting that high surface diffusivity paths (grain boundaries and possibly other defects) enhance the surface diffusion of Pd on Cu.     

Surface sensitivity of low energy electron Mössbauer spectroscopy (LEEMS) using57Fe

Very low energy electrons (LEE) (E _e ≤15 eV) are produced with high intensity directly by Mössbauerabsorption and conversion in the case of⁵⁷Fe [1, 4, 5]. These electrons should be very surface sensitive due to their very low attenuation length compared to the 7.3 keV K-Conversion electrons of⁵⁷Fe [5, 11]. We have examined the surface sensitivity of these resonant LEE, using nonresonant⁵⁶Fe metal and⁵⁶Fe stainless steel foils coated with about 20 Å and 50 Å⁵⁷Fe, respectively. They were exposed to air after evaporation: The 20 Å samples are found to be fully oxidized [5]. Depth Selective Conversion Electron Mössbauer Spectroscopy (DCEMS), performed with a high transmission orange type magnetic spectrometer [5, 6, 13] reveals a two layer structure of the 50 Å samples. Low Energy Electron Mössbauer Spectroscopy (LEEMS) [5] is found to be significantly more surface sensitive than conventional DCEMS, but not as surface sensitive as Auger Electron Mössbauer Spectroscopy (AEMS) using LMM-Auger electrons of 500–600 eV, as expected due to the different mean free path. But because of the very low intensity of these Auger electrons this mode appears to be not very useful for practical application.     

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.     

Low energy electron attenuation length studies in thin amorphous carbon films

The results of experiments on low energy electrons passing through thin amorphous carbon films are reported. For electron energies between 50 and 3000 eV, electron attenuation lengths were determined by electron transmission measurements through carbon films of thicknesses between 81 and 210 Å. The density of these amorphous carbon films was also obtained by a sink—float method and found to be 1.90 ± 0.05 g cm^?3. The electron attenuation length for inelastic scattering was found to increase monotonically from approximately 10 to 55 Å over the 50 to 3000 eV range. Over the 500–3000 eV energy region, the results are in good agreement with mean free paths calculated using optically measured dielectric functions.     

Characterization of thin films on the nanometer scale by Auger electron spectroscopy and X-ray photoelectron spectroscopy

We describe two NIST databases that can be used to characterize thin films from Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) measurements. First, the NIST Electron Effective-Attenuation-Length Database provides values of effective attenuation lengths (EALs) for user-specified materials and measurement conditions. The EALs differ from the corresponding inelastic mean free paths on account of elastic-scattering of the signal electrons. The database supplies “practical” EALs that can be used to determine overlayer-film thicknesses. Practical EALs are plotted as a function of film thickness, and an average value is shown for a user-selected thickness. The average practical EAL can be utilized as the “lambda parameter” to obtain film thicknesses from simple equations in which the effects of elastic-scattering are neglected. A single average practical EAL can generally be employed for a useful range of film thicknesses and for electron emission angles of up to about 60°. For larger emission angles, the practical EAL should be found for the particular conditions. Second, we describe a new NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to be released in 2004. This database provides data for many parameters needed in quantitative AES and XPS (e.g., excitation cross-sections, electron-scattering cross-sections, lineshapes, fluorescence yields, and backscattering factors). Relevant data for a user-specified experiment are automatically retrieved by a small expert system. In addition, Auger electron and photoelectron spectra can be simulated for layered samples. The simulated spectra, for layer compositions and thicknesses specified by the user, can be compared with measured spectra. The layer compositions and thicknesses can then be adjusted to find maximum consistency between simulated and measured spectra, and thus, provide more detailed characterizations of multilayer thin-film materials. SESSA can also provide practical EALs, and we compare values provided by the NIST EAL database and SESSA for hafnium dioxide. Differences of up to 10% were found for film thicknesses less than 20 Å due to the use of different physical models in each database.     

Surface EXAFS via differential electron yield

Surface‐sensitive analysis via extended X‐ray absorption fine‐structure (EXAFS) spectroscopy is demonstrated using a thickness‐defined SiO₂ (12.4 nm)/Si sample. The proposed method exploits the differential electron yield (DEY) method wherein Auger electrons escaping from a sample surface are detected by an electron analyzer. The DEY method removes local intensity changes in the EXAFS spectra caused by photoelectrons crossing the Auger peak during X‐ray energy sweeps, enabling EXAFS analysis through Fourier transformation of wide‐energy‐range spectral oscillations. The Si K‐edge DEY X‐ray absorption near‐edge structure (XANES) spectrum appears to comprise high amounts of SiO₂ and low Si content, suggesting an analysis depth, as expressed using the inelastic mean free path of electrons in general electron spectroscopy, of approximately 4.2 nm. The first nearest neighbor (Si—O) distance derived from the Fourier transform of the Si K‐edge DEY‐EXAFS oscillation is 1.63 Å. This value is within the reported values of bulk SiO₂, showing that DEY can be used to detect a surface layer of 12.4 nm thickness with an analysis depth of approximately 4.2 nm and enable `surface EXAFS' analysis using Fourier transformation.     

Elastic and inelastic contributions to the auger electron appearance potential spectrum of titanium

The energy distribution of electrons contributing to the L-shell Auger electron appearance potential spectrum of a polycrystalline titanium surface has been measured. The Auger electron appearance potential spectrum is obtained by differentiating the total secondary electron yield of an electron bombarded sample as a function of incident electron energy. At the threshold for scattering from a core level the secondary yield increases. Most of the electrons contributing to this increase have energies below 30 eV, and result from secondary processes following Auger recombination of the core hole. The elastic yield decreases at the threshold, however, due to opening a new channel for inelastic scattering. A comparison of the elastic yield spectrum (DAPS), the total yield spectrum (AEAPS) and the soft X-ray yield spectrum (SXAPS), shows very similar line shapes, but differences in the relative strengths of the lines.     

Atomic structure of Fe {111}

A clean Fe {111} surface was prepared and studied with LEED (low-energy electron diffraction) and AES (Auger electron spectroscopy). A LEED intensity analysis was carried out with a new computational scheme (THIN) specially designed for short interlayer spacings. The results are, for the fust interlayer spacing, d₁₂ = 0.70 ± 0.03 Å and for the inner potential V₀ = 11.1 ± 1.1 eV, the confidence intervals referring to 95% confidence level. Thus, the Fe {111} surface is contracted 15.4% with respect to the bulk (0.827 Å).     

The bonding state of carbon segregated to α-iron surfaces and on iron carbide surfaces studied by electron spectroscopy

Segregated carbon on the Fe(100) surface has been studied by means of X-rayand ultraviolet photoelectron (XPS, UPS), Auger electron (AES) and electron energy loss spectroscopy (ELS). For comparison, the surfaces of polycrystalline graphite and of iron carbides stabilized by chromium or manganese additions have been investigated. On the iron surface, carbon exists as a chemisorbed state or graphitic multilayer. The two states exhibit different energy positions in XPS, and are different in energy positions and lineshapes in AES and ELS. During the transition of graphitic carbon to chemisorbed carbon on Fe(100) a novel coverage-dependent Auger feature is reported. The spectra of graphitic carbon on the iron surface always coincide with those of solid graphite. The carbon Auger transitions of chemisorbed carbon and of iron carbides exhibit very similar lineshapes, but the energy positions of both states differ in AES as well as XPS.     

Combined application of AES and XPS to study carbon diffusion through the selvedge of an Fe(100) surface

Diffusion of carbon from an Fe(100) surface into the bulk, following halocarbon adsorption, is modelled using experimental data from AES and XPS experi electrons (272 eV) in a dense monolayer of halogen atoms (Cl, Br) is found by a variety of experimental methods to be ～3Å, a value substantially sm inferred from the combined information provided by the AES and XPS experiments, the concentration profile of carbon perpendicular to the surface follow function. The importance of accurate data for electron escape depths and of experimental detection limits for quantitative electron spectroscopy of a s     

Interfacial phenomena and magnetic properties of Fe/Al multilayers of different thickness

Fe/Al thin film multilayers, differing in the thickness of Fe films (30÷10 Å, were electron-beam evaporated in ultra-high vacuum. Interdiffusion and reaction phenomena occurring during deposition at interfaces were studied by means of conversion electron Mössbauer spectroscopy and Auger electron spectroscopy depth-profiling. Magnetic behavior was investigated by alternating force gradient magnetometry. The formation of Fe–Al solid solution and intermetallic compound is observed. Multilayers are ferromagnetic with magnetization in the film plane for iron film thickness ?15 Å, while exhibiting a superparamagnetic behavior at 10 Å.     

Electron transmission measurements of electron mean free path in supported thin films from 1–5 keV

Measurements are made of the transmission of medium energy electrons through in vacuo deposited films in order to determine the inelastic electron mean free path as a function of energy. Films of Al, Ge and Au are deposited in small increments on 20–30 Å carbon substrates supported by “holey” carbon films. The no-loss electron current is measured for each thickness as a continuous function of incident energy in the range of 1–5 keV. Although this preliminary experiment does not result in a precise separation of elastic and inelastic scattering effects, the attenuation lengths estimated are in reasonable agreement with measured and calculated in-elastic mean free paths. Elastic scattering cross sections appear to be smaller than estimated by simple theory.     

Quantitative analysis of iron nitrides (γ′-Fe4 and ϵ-Fe2−3N) using auger electron spectroscopy

The investigation and development of tribologically important transition metal nitride surface layers rely on the accurate quantitative analysis of light elements used in conjunction with a suitable depth profiling technique. This paper describes the quantitative AES analysis of iron nitrides (γ′-Fe₄N and ϵ-Fe₂₋₃N) by comparison with reference materials and by applying correction factors for ionization by backscattered primary electrons, atom number density and inelastic mean free paths of the Auger electrons in the matrix. It is shown that the nitrogen contents of these iron nitrides may be determined to within 10% accuracy, and it is also shown that this accuracy depends firstly on the correct calculation of the abovementioned correction factors, and secondly on the correct determination of the Auger electron yield. The Auger electron yield should be determined by measuring the area below the Auger peak on the N(E)E spectrum, after removal of the background electron spectrum to ensure that details of the relatively small nitrogen peaks are not overlooked.     

Quantification of surface-sensitive electron spectroscopies

Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were introduced in late 1960s as routine tools for surface analysis. Despite a long history, both techniques are still very useful in different new areas of surface science. The number of publications involving AES or XPS well exceeds 5000 per year, and is still growing.The present paper compiles recent advances in quantitative applications of both techniques. Due to the considerable volume of published material, stress is put on the determination of surface composition. Three groups of subjects are addressed here. At first, typical experimental procedures for quantitative analysis are outlined. For this purpose, we briefly review the common formalism of AES and XPS. Secondly, information is provided on the correction approach in AES and XPS, similar to electron probe microanalysis (EPMA). Next, methods for determination and sources of the correction parameters are reviewed. Finally, we discuss physical parameters needed for calculation of corrections. Much attention is devoted to the problem of determination of the differential elastic-scattering cross sections for signal electrons. This parameter is of crucial importance for describing the electron trajectories in the solid. We also approach further prospects for improved quantification of AES and XPS.     

Design of an Auger Electron Mössbauer Spectrometer (AEMS) using a modified cylindrical mirror analyzer

We have designed and built an Auger Electron Mössbauer Spectrometer (AEMS) for the detection of resonant ⁵⁷Fe Auger electrons using a modified commercial cylindrical mirror analyzer (CMA). The CMA final aperture was modified intentionally in order to increase electron transmission at the expense of reducing its energy resolution, from an original value of 0.5 % to a value of 11 % after the modification. The Channeltron detector electronics and the pre-amplifier were also modified in order to increase the counting efficiency. The electron energy analyzer is selective in energy in the 30 eV–3000 eV range, so the spectrometer can be used to detect MNN (45 eV) and LMM (600–700 eV) Fe Auger signals, what gives it a high surface sensitivity for Fe containing samples. We have used it to acquire the Fe LMM Auger signals generated from the de-excitation process after γ-Ray resonant nuclear absorption. The spectrometer can be used to study samples non-enriched in ⁵⁷Fe, with acquisition times from 5 to 7 days, what is a big advantage. From electron trajectory Monte Carlo simulations in metallic iron, the mean-escape-depth of the detected Auger signals has been estimated in approximately 1 nm. Fe K conversion electrons and KLL Auger electrons with mean escape depths of 129 nm and 78 nm respectively also contribute to the detected signal although in a lesser proportion.     

Quantitative aspects of Auger electron spectroscopy; On the importance of attenuation of the primary electron beam

Measurements of Auger electron currents at different energies of the primary electrons and at different angles of incidence suggest that attenuation of the primary electron beam in the crystal has a significant influence on the measured Auger currents. This makes it possible to distinguish between a monolayer and a multilayer system, i.e. between impurity atoms in the top atomic layer and impurity atoms dispersed through the surface region. Comparison of AES and ellipsometric measurements of monolayer and multilayer systems on silicon and germanium surfaces shows that AES results can be interpreted to give quantitative information about the number of atoms of the type investigated.     

Diffusion processes in nanoscale two-layer film systems based on Fe and Cu or Fe and Cr

The results of investigations of diffusion processes (condensation-stimulated diffusion (CSD) and thermal diffusion (TD)) in nanoscale Fe/Cu and Fe/Cr Fe/Cutwo-layer film systems by means of Auger electron spectroscopy (AES) are presented. It is established that the effective CSD coefficient is about two orders of magnitude higher than the analogous TD coefficient, which is explained by grain boundary diffusion saturation as early as at the top layer condensation stage.     

Auger electron spectroscopy study on the Cr/Al2O3 interfacial reactions

Interfacial reactions of evaporated chromium with surface has been studied using Auger electron spectroscopy (AES). The results reveal that the interfacial region consists of a mixture, which is a double oxide of Cr and Al or two separated oxides. After annealing, the chromium oxide and the metallic Al produced by reduction of the Al³⁺ ions were easily detected by AES at the interface. We suggest that the interfacial reaction occurs mainly by the charge transfer from the 3d electrons of Cr atoms to O 2p orbitals of the Al₂O₃ substrate. The annealing at higher temperature (973 K) is favourable to promote the interfacial reaction between the surface oxygen and the initial few atomic monolayers of the deposited chromium. The results also showed that the change of the relative Auger peak-to-peak height (APPH(%)) of the Cr LMM group peaks can be used as an index to identify the oxidation states of chromium at the Cr/Al₂O₃ interface.     

Quantitative Auger electron spectroscopy analysis with co-evaporated AuCu films

A method for the quantitative Auger electron spectroscopy (AES) analysis by using a co-evaporation technique is extended to the AuCu system following the previous work. The calibration curves for lower Auger energy have peaks at 60 eV for Cu and at 69 eV for Au, and for higher Auger energy peaks at 239 eV for Au and at 920 eV for Cu. It is found that a simple linear relation does not exist in the results for AES measurements and the bulk analysis by atomic absorption spectroscopy (AAS) because of the back-scattering effect and the overlap of the spectra at lower energies in the Au-Cu system. It is also found that the adsorption of oxygen caused by electron beam bombardment has a significant influence on the AES results. The calibration curves obtained after a correction for oxygen adsorption are successfully applied to the determination of the composition at the surface of a sputtered AuCu alloy.