Relationships between electron inelastic mean free paths, effective attenuation lengths, and mean escape depths

The terms inelastic mean free path (IMFP), effective attenuation length (EAL), and mean escape depth (MED) are frequently used to specify the surface sensitivity of Auger-electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). These terms are different conceptually because of the effects of elastic-electron scattering, and generally have different numerical values for a specified material and electron energy. In addition, values of the EAL and MED depend on the instrumental configuration. We give an historical overview of efforts to measure EALs by the overlayer method and of work to investigate elastic-scattering effects in AES and XPS. We then apply an analytical formalism developed from a solution of the kinetic Boltzmann equation within the transport approximation to demonstrate the relationships between the IMFP, EAL, and MED for selected elemental solids and for common measurement conditions. Examples are given to show the magnitude of elastic-scattering effects on MED values for angle-resolved XPS and AES. If XPS or AES data are acquired for emission angles between zero and 60°, the ratio of the MED to that found with elastic scattering neglected is approximately constant (to within 10%), and this ratio can be used to determine an average value for the EAL. This EAL value can then be used to establish the depth scale in the data analysis. Finally, we show ratios of the EAL to the IMFP for XPS from the Au 4s subshell with Mg K X-rays as a function of emission angle and depth; this ratio has a weak dependence on emission angle from zero to 40° but a more pronounced dependence for larger emission angles.     

Characterisation of nickel silicide thin films by spectroscopy and microscopy techniques

This article discusses the formation and detailed materials characterisation of nickel silicide thin films. Nickel silicide thin films have been formed by thermally reacting electron beam evaporated thin films of nickel with silicon. The nickel silicide thin films have been analysed using Auger electron spectroscopy (AES) depth profiles, secondary ion mass spectrometry (SIMS), and Rutherford backscattering spectroscopy (RBS). The AES depth profile shows a uniform NiSi film, with a composition of 49-50% nickel and 51-50% silicon. No oxygen contamination either on the surface or at the silicide-silicon interface was observed. The SIMS depth profile confirms the existence of a uniform film, with no traces of oxygen contamination. RBS results indicate a nickel silicide layer of 114 nm, with the simulated spectra in close agreement with the experimental data. Atomic force microscopy and transmission electron microscopy have been used to study the morphology of the nickel silicide thin films. The average grain size and average surface roughness of these films was found to be 30-50 and 0.67 nm, respectively. The film surface has also been studied using Kikuchi patterns obtained by electron backscatter detection.     

Effective attenuation length dependence on photoelectron kinetic energy for Au from 1 keV to 15 keV

Hard X-ray PhotoElectron Spectroscopy (HAXPES) is an extremely powerful tool for the electronic, compositional, and chemical characterization of bulk materials and buried interfaces. Its success is based on the dramatic increase of the electron effective attenuation length (EAL) with increasing photoelectron kinetic energy. EALs are well established for electrons with kinetic energies up to several keV (below 3 keV). However, few data are available for kinetic energies up to 15 keV. In the present study we have determined the EAL dependency on kinetic energy for gold from 1 keV up to 15 keV. Two different approaches have been used. The first approach consists of following the signal rate from a core level for a fixed kinetic energy as a function of overlayer thickness (overlayer method). The second approach consists of following the signal rate from a core level as a function of the incident photon energy, i.e., electron kinetic energy, for a fixed overlayer thickness (depth profile method). An EAL dependency of EAL (nm) = 0.022 × E_kin (eV)^0.627 has been obtained from both methods. Hence, the EAL, for gold, is 4.7, 7.3 and 9.4 nm for 5 keV, 10 keV and 15 keV electron kinetic energies, respectively. A comparison between the experimental data and the EALs predicted by practical expressions available in the literature is also performed.     

Comparison of the CKLL first-derivative auger spectra from XPS and AES using diamond,graphite, SiC and diamond-like-carbon films

The carbon KLL first-derivative Auger spectra obtained by numerically differentiating the XPS N(E) line gives a better fine-structure fingerprint of the carbon state than conventional AES. The first-derivative of the X-ray excited (XAES) CKLL spectrum from a diamond-like-carbon (DLC) film exhibited almost the same spectrum as both the XAES and AES spectra from natural diamond. However, the AES spectrum of the DLC film indicated a graphite-like structure due to electron beam damage. Comparison of the XAES and AES spectra suggested that the electron beam used in conventional AES partially changed the plasmon loss structure of carbon in diamond, graphite and β-SiC as well.     

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.     

Influence of passive potential on the electronic property of the passive film formed on Ti in 0.1 M HCl solution during ultrasonic cavitation

The influence of the applied passive potential on the electronic property of the passive film formed on Ti at different potentials in 0.1 M HCl solution during ultrasonic cavitation, was investigated by electrochemical impedance spectra (EIS) and Mott–Schottky plot. The influence of the applied passive potential on the structure and composition of the passive film was studied by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The results showed that the applied passive potential can obviously affect the electronic property of the passive film formed on Ti during ultrasonic cavitation. The resistance of the passive film increased, and the donor density of the passive film decreased with increasing the potential. The flat band potential moved to positive direction and the band gap of the passive film moved to negative direction with increasing potential. AES and XPS results indicated that the thickness of the passive film increased evidently with applying passive potential. The passive film was mainly composed of the mixture of TiO and TiO₂. While the TiO₂ content increased with increasing the applied passive potential, and the crystallization of the passive film increased with the increased potential.     

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.     

Low energy (⩽ 100 eV) sputtering of thin molybdenum nitride films

Molybdenum nitride films formed by 100 eV N⁺₂ bombardment to saturation of polycrystalline Mo have been sputtered to high fluence by normally incident 100 eV Ar⁺ and He⁺ and 15 eV Ne⁺ while the surface nitrogen concentration was monitored by Auger electron spectroscopy (AES). The penetration distance of nitrogen atoms during film formation and subsequent sputtering is assumed to be small enough that AES will detect, to some degree, all of the nitrogen in the film. The nitrogen AES signal decays exponentially to unsputterable levels for the 15 eV Ne⁺ and 100 eV He⁺ cases and decays bi-exponentially to near the bulk contamination level for the 100 eV Ar⁺ case. The results are interpreted according to existing concepts, but the kinetics of nitrogen loss is modeled using a two-layer adaptation of the standard model for adsorbate monolayer sputtering kinetics. Fitting our proposed model to the data yields apparent cross-sections which are interpreted as composites of cross-sections for experimentally indistinguishable elementary processes; these elementary cross-sections for each process are geometrical averages on the polycrystalline surface. Processes considered, in addition to nitrogen sputtering, include bombardment-induced transport of nitrogen within the film and sputtering of the Mo lattice itself.     

Ethylene and acetylene adsorption on Cu(111) and Pt(111) studied by Auger spectroscopy

High resolution, electron impact excited, carbon Auger spectra of ethylene and acetylene adsorbed on Cu(111) and Pt(111) are compared. The spectra of ethylene on the two metals provide the first example of the sensitivity of AES to the nature of metal-adsorbate bonding for molecular adsorbates. The acetylene spectra are identical on the two metals. The changes in the carbon Auger spectra resulting from thermal decomposition of the two adsorbates on Pt(111) are discussed in the context of results from electron energy loss spectroscopy.     

Amorphous SiC film formation on Si(100) using electron beam excitation

The effect of electron impact on methylsilane (CH₃SiH₃) conversion to amorphous-Si_0.5C_0.5:H (a-Si_0.5C_0.5:H) films on Si(100) has been studied by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption (TPD), and low energy electron diffraction (LEED). It is found that electron impact greatly enhances CH₃SiH₃ decomposition on Si(100) at both 90 K and 300 K, resulting in a-Si_0.5C_0.5:H thin film formation. Thermal annealing of the film causes hydrogen desorption and amorphous silicon carbide (a-SiC) formation. Upon annealing to temperatures above 1200 K, the a-SiC film became covered by a thin silicon layer as indicated by AES studies. Ordered structures are not produced by annealing the a-SiC up to 1300 K.     

Spin-polarization in ccv Auger electron spectroscopy for transition metals

The contributions of core states and the valence band to spin-resolved ccv Auger electron spectra (AES) are discussed in terms of a relativistic, spin-polarized theory. The influence of the core-state spin polarization and of selecting particular valence bands via cross sections is shown for the surface layer of BCC Fe(1 0 0) as calculated by means of the Screened KKR ab-initio electronic structure method.     

Influence of the matrix on boron detection by auger electron spectroscopy (AES)

The difficulties of boron detection by AES in catalysts containing low concentrations of boron can be partially associated with elastic scattering of Auger electrons. In the present work, the Monte Carlo approach is used to estimate the effects of Auger electron collisions in different matrices. Elastic scattering events are described within the partial wave expansion method. The scattering centres are approximated by the Thomas-Fermi-Dirac potentials. It is found that elastic collisions decrease the boron KLL Auger electron signal by up to 10%. In addition, the sampling depth of AES is strongly decreased. This decrease reaches 35% for medium atomic number elements. The values of parameters correcting for elastic scattering effects are determined for boron embedded in 14 elements. An attempt is also made to interpolate the correcting parameters for matrices not considered in the present work.     

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.     

Continuous X-ray-induced Auger electron spectroscopy

Bremsstrahlung emission from a tungsten anode has been used, for the first time, to obtain X-ray-induced Auger electron spectra (CXAES) in a conventional X-ray photoelectron spectrometer. Auger KLL signal and background intensities obtained from a silicon—aluminium sample have been compared with those obtained un der the same experimental conditions but using a standard aluminium anode. For such an aluminium anode, the respective contributions of the bremsstrahlung and the characteristic radiation to the C_KVV intensity have also been established.     

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.     

Obtaining density of states information from self-deconvolution of Auger band-type spectra

A systematic revision of the techniques to isolate Auger peaks in experimental spectra obtained with LEED/AES analyzers has been carried out: Background subtraction, deconvolution with the elastic peak and inversion of self-convolution. New techniques have been devised and applied to the Auger spectra of graphite, aluminum, magnesium, magnesium oxide and silicon. Self-deconvolution of these spectra leads to a transition density function that has been compared with the density of states of the valence band near the surface, as given by other competitive techniques (XPS, UPS, XES) and by theory. This comparison shows that in those meterials, Auger electron spectroscopy (AES) is a sensitive probe of the electron environment of surface atoms.     

脉冲高能量密度等离子体法制备TiN薄膜及其摩擦磨损性能研究

利用脉冲高能量密度等离子体技术在室温条件下在45号钢基材上制备出了超硬耐磨TiN薄膜.利用XRD，XPS，AES，SEM等手段分析了薄膜的成分及显微组织结构，并测试了薄膜的硬度分布及摩擦磨损性能.结果表明：薄膜主要组成相为TiN，薄膜组织致密、均匀，与基材之间存在较宽的混合界面；薄膜硬度高，在干滑动磨损实验条件下具有优异的耐磨性及较低的摩擦系数. 关键词： 脉冲高能量密度等离子体 TiN膜 显微组织 耐磨性     

Comparison of escape depths between Auger electron and disappearance potential spectroscopy electron

The escape depths of the characteristic electrons of the Auger electron and the quasielastically reflected electron were determined by Auger electron spectroscopy (AES) and disappearance potential spectroscopy (DAPS), respectively, for a Cr overlayer onto Ti and Fe substrates. For the case of Cr on Fe, in-situ measurements of AES and DAPS were carried out. From the results, the mean free paths of 455, 575 and 710 eV electrons through Cr were obtained as 9.6, 13 and 15 Å, respectively. The attenuation length of a 2.5 keV primary electron of AES through Cr was also obtained and the value was 62 Å. In addition, the mean free paths of electrons with the same energy depend on the scattering materials of Cr, Mo and W (material dependence). The phenomena are useful for a quantitative electron spectroscopy of surfaces.     

New improvements in energy and spatial (x,y, z) resolution in AES and XPS applications

This review presents the recent developments published in the literature about the use of Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) at high energy or spatial resolution. The past and present improvements due to technology (analysers, excitation source), and to mathematical procedures are described and discussed. New trends in the application of AES and XPS are related.     

Effect of relaxation and decay of a charge transfer shakeup satellite on Auger-electron spectroscopy spectra and Auger-photoelectron coincidence spectroscopy spectra of adsorbates

An electron excited to an unoccupied part of adsorbate–substrate hybrid states in a chemisorbed molecule by a resonant core electron excitation or charge transfer (CT) shakeup may delocalize on time scale of core-hole decay so that the excited core-hole state relaxes partly or completely to a fully relaxed one. The Auger decay of the fully relaxed core-hole state via the relaxation of the excited one introduces an additional feature in the resonant Auger-electron spectroscopy (RAES) spectrum and the AES spectrum. However, the additional feature in the RAES spectrum is a normal AES spectrum by decay of the fully relaxed core-hole state, whereas the one in the AES spectrum is the AES spectrum by decay of the fully relaxed core-hole state broadened by the photoelectron spectroscopy (PES) CT shakeup satellite weighted by the branching ratio of the relaxation width. The discrepancies between the AES spectrum measured at high above the ionization threshold and the additional feature in the RAES spectrum consist of the symmetric-like part by the decay of the fully relaxed core-hole state via the relaxation of the CT shakeup state and the asymmetric part by the direct decay of the shakeup states. The asymmetric part increases with a decrease in the hybridization strength. This explains the variation with the hybridization strength in the discrepancies between the RAES spectra and the AES spectra of chemisorbed molecules such as CO/Ni, CO/Cu and CO/Ag. A comparison of the singles PES spectrum with the one measured in coincidence with the AES main line of a selected kinetic energy (KE) provides the delocalization rate of the excited electron in the CT shakeup state as a function of photoelectron KE. The coincidence measurement to obtain the partial singles PES spectrum is discussed.