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.     

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.     

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.     

Structure and surface layers of Mg-C nanocomposites produced by ball milling

X-ray diffractometry (XRD), X-ray photoelectron spectrometry (XPS), Auger electron spectrometry (AES) and transmission electron microscopy (TEM) were used to investigate the structure and surface layers properties of nanocomposites produced by the mechanical activation (ball milling) of elemental magnesium with carbon materials (amorphous carbon and graphite). Amorphous carbon was synthesized by electric discharge treatment in kerosene. It was shown that ball milling, the allotropic form of carbon materials, and features of hydrogenation have a considerable effect on the structure, surface layer properties, and hydrogen adsorption of a formed composition. XPS and Auger spectroscopy revealed the surface layer of the composite particles to be enriched with carbon. In addition, there were oxide layers on their surfaces due to the particles’ interaction with the environment.     

Characterization and chemical behavior of submonolayer coverages of titania on a Pt foil

The interaction between submonolayer titania coverages and Pt foil has been studied by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), temperature programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). The submonolayer titania can be fully oxidized to TiO₂ at 923 K under 10⁻⁸ Torr O₂, and partially oxidized to TiO_x at lower oxidation temperatures. The oxidized surface can be reduced by annealing to 1000 K or higher, or by heating in H₂ at 823 K, or by interacting with surface carbon formed from acetone decomposition. Under certain conditions (e.g., hydrogen reduction at 923 K), the surface titania can be fully reduced to metallic Ti which diffuses into bulk Pt readily. The reduced metallic Ti can resurface when the surface is oxidized at 923 K. Both XPS and HREELS data indicate the existence of subsurface oxygen, which plays an important role for the diffusion of Ti into and out of the Pt foil. Although no special interfacial active sites were revealed by HREELS studies of adsorbed acetone and CO, some TPD and XPS data suggest the presence of sites active for acetone decomposition.     

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.     

Background subtraction in electron spectroscopy by use of reflection electron energy loss spectra

The use of reflected electron energy loss spectra (REELS) in deconvoluting the inelastic background signal from XPS and AES spectra from homogeneous samples is studied. It is demonstrated that under certain assumptions, the cross section for inelastic electron scattering can be extracted from a REELS spectrum. This cross section is applied to deconvolute an experimental XPS spectrum of aluminium. The method, its limitations and its relation to other methods are discussed.     

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.     

Analysis of mechanism of carbon removal from GaAs(1 0 0) surface by atomic hydrogen

Etching of carbon contaminations from the GaAs(1 0 0) surface by irradiating with atomic hydrogen, which is one of the key reactions to promote high-quality thin films growth by molecular beam epitaxy (MBE), has been investigated by mass spectrometry (MS), Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). It is shown that during the cleaning process at room temperature a total reduction of the Auger carbon signal, accompanied by desorption of methane as major reaction product, can be observed. The reaction pathways as well as the processes responsible for the observed carbon removal are discussed in detail to give a support for etching and growth quality enhancement not only in thin films epitaxy but in all atomic hydrogen promoted gas-phase III-V semiconductor processes.     

Electron spectroscopic studies of tin surface segregation on iron single crystal surfaces

AES, ELS, LEED and XPS investigations of the surface segregation of tin dissolved in a Fe-4wt%Sn alloy were performed in ultra-high vacuum at elevated temperatures. The three low indexed surface orientations (100), (110) and (111) were studied. In all cases, no dependence of the maximum tin surface coverage on temperature was detected within the temperature range from 450 to 650°C. An order-disorder transition was observed by LEED, AES and XPS for the (100) oriented surface during tin segregation. The binding state for the segregated tin atoms abruptly changes at the order-disorder transition as determined by XPS. Similar results were obtained for the (111) surface. A deviating behaviour was observed for the (110) surface orientation, where two different ordered hexagonal surface structures were detected by LEED during tin surface enrichment. The first structure is similar to the diamond structure of pure tin, and the second one corresponds to the formation of a thin layer of the intermetallic compound FeSn on the (110) surface. The electron binding energies of the segregated tin atoms determined by XPS increase with increasing tin coverage on the (110) oriented surface. ELS studies on (100) and (111) oriented surfaces saturated with segregated tin show in comparison with literature data of pure tin a surface plasmon loss peak but no signal for the corresponding bulk loss. An energy loss signal found only for the (110) surface at Sn saturation coverage seems to be characteristic of an intermetallic FeSn surface phase.     

Electron spectroscopy of the interface carbon layer formation on the cleavage surfaces of the layered semiconductor In4Se3 crystals

The results of the quantitative X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) of the interface carbon layer formation on the cleavage surfaces of the layered semiconductor In₄Se₃ crystals are presented. The carbon coating formation occurs as the result of interaction of the air and residual gases atmosphere in ultra high vacuum (UHV) Auger spectrometer chamber with atomic clean interlayer cleavage surfaces of the crystals. The kinetics and peculiarities of interfacial carbon layer formation on the cleavage surfaces of the crystals, elemental and phase composition of the interface have been studied by quantitative XPS, AES and mass-spectroscopy.     

Surface sensitivity of Auger-electron spectroscopy and X-ray photoelectron spectroscopy

A convenient measure of surface sensitivity in Auger-electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) is the mean escape depth (MED). If the effects of elastic-electron scattering are neglected, the MED is equal to the electron inelastic mean free path (IMFP) multiplied by the cosine of the emission angle with respect to the surface normal, and depends on the material and electron energy of interest. An overview is given here of recent calculations of IMFPs for 50–2000 eV electrons in a range of materials. This work has led to the development of a predictive formula based on the Bethe equation for inelastic electron scattering in matter from which IMFPs can be determined. Estimates show, however, that elastic-electron scattering can significantly modify the MED. Thus, for AES, the MED will be reduced by up to about 35%. For XPS, however, the MED can be changed by up to ±30% for common measurement conditions although it can be much larger (by up to a factor of 2) for near-grazing emission angles. Ratios of MED values, calculated with elastic scattering considered and neglected for XPS from the 3s, 3p, and 3d subshells of silver with Mg Kα X-rays are approximately constant (to about 10%) over a range of emission angles that varies from 40° to 60° depending on the subshell and the angle of X-ray incidence. Recommendations are given on how to determine the optimum range of emission angles for satisfactory analysis of angle-resolved XPS (ARXPS) data. Definitions are included of three terms often used for describing surface sensitivity (IMFP, MED, and effective attenuation length (EAL)), and examples are given of the varying magnitudes of these quantities for different analytical conditions.     

Determination of the inelastic mean free path of electrons in GaAs and InP after surface cleaning by ion bombardment using elastic peak electron spectroscopy

The inelastic mean free path (IMFP) of electrons is an important material parameter needed for quantitative AES, EELS and non-destructive depth profiling. The distinction between the terms for IMFP and the attenuation length (AL) has been established by ASTM standards. A practical experimental method for determining values of the IMFP is elastic peak electron spectroscopy (EPES). In this method, experimentally determined ratios of elastically backscattered electrons from test surfaces and from a Ni reference standard are compared with the values evaluated theoretically.The present paper reports systematic measurements of the IMFP by EPES for GaAs and InP. They are carried out in two laboratories using two different electron spectrometers: a CMA in Budapest and DCMA in Warsaw. Prior to measurements, the samples were amorphized by high-energy Ar⁺ ions (100–400 keV), and the surface composition was determined by quantitative XPS. Argon cleaning produces enrichment of samples in the surface layer in Ga (80%) and In (70%), respectively. The experiments refer to a such modified sample surface that was considered in Monte Carlo calculations. The experimental data were analyzed using calibration curves from Monte Carlo calculations which account for multiple elastic scattering events. This approach has been used previously for elemental solids and is now extended to amorphized binary compounds. The experimental values of IMFP obtained in both laboratories exhibited a reasonable agreement with the available literature data in the 0.1–3.0 keV energy range. With respect to the information depth of EPES, the experimental results refer to the bulk composition within a reasonable extent.     

Investigation of ageing characteristics and identification of surface chemical changes on SrGa2S4:Ce display phosphor under electron beam bombardment

Cathodoluminescent ageing characteristics of SrGa₂S₄:Ce³⁺ under prolonged electron beam bombardment was studied and the data are presented. The cathodoluminescent intensity with an increasing Coulomb loading was observed to degrade under different primary electron beam voltages. Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were used to monitor the surface chemical changes during electron beam bombardment and after the degradation process. Auger peak to peak heights monitored during the ageing process suggest a loss in S and C and an initial increase in oxygen concentration on the surface. XPS results indicate the formation of a SrO overlayer due to electron stimulated surface chemical reactions (ESSCRs).     

Determination of adsorbate coverages by leed and XPS

Layers of carbon, oxygen, sulfur and potassium adsorbed on an Fe(100) surface were studied by LEED, AES and XPS. When examined quantitatively by XPS, saturated c(2 × 2)CO(β), c(2 × 2)C and p(1 × 1)O surface structures yielded the C/O ratios expected from surface coverages of 0.25, 0.5 and 1.0 monolayer, respectively. When these results were normalized to the equivalent coverages of 1.0 monolayer, the relative XPS cross-sections obtained for S, O, C and K were found to agree closely with the results of theoretical calculations. The results illustrate the use of these techniques for the quantitative determination of surface coverages.     

Precipitation and re-solution of impurities at the surface of indium on traversing the melting-point

In the course of preparing a clean indium surface for solid-versus-liquid studies, changes in the surface concentrations of sulphur and oxygen were observed by AES and XPS while the metal was heated and cooled through its melting-point. Both impurities disappeared on melting, and reappeared on solidification, over a very narrow temperature range; the disappearance and reappearance were to a certain extent reproducible. The effect was found to be similar in characteristics to that observed for the behaviour of carbon on a nickel surface by Shelton et al., and the same Bragg-Williams model is invoked to explain the sharpness of the impurity concentration changes with temperature. Although the maximum temperature reached by the indium was only 200°C, traces of platinum were also observed on the indium surface after melting, in both the AES and XPS spectra, probably as a result of solution from the platinum boat.     

Decomposition of carbon monoxide on a (110) nickel surface

New investigations of the (110) nickel/carbon monoxide system have been made using low energy electron diffraction (LEED), Auger electron spectroscopy (AES), mass spectroscopy and work function measurements. Room temperature adsorption of CO on the surface was reversible with the CO easily removable by heating in vacuum to 450°K. The CO formed a double-spaced structure on the surface which, however, was unstable at room temperature for CO pressures less than 1×10^?7 torr. Work function changes greater than + 1.3 eV accompany this reversible CO adsorption. Irreversible processes leading to the build-up of carbon, and under certain circumstances oxygen, on the surface were the primary concern of the measurements reported here. These processes could be stimulated by the electron beams used in LEED and AES, or by heating the clean surface in CO. The results of AES investigations of this carbon (and oxygen) build-up, together with CO desorption results could be explained on the basis of two surface reactions. The primary reaction was the dissociation of chemisorbed CO leaving carbon and oxygen atomically dispersed on the surface. The second reaction was the reduction of the surface oxygen by CO from the gas phase. The significance of the dissociation reaction to COdesorption studies is discussed.     

The adsorption of methyl iodide on uranium and uranium dioxide: Surface characterization using X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES)

The adsorption of methyl iodide on uranium and on uranium dioxide has been studied at 25 °C. Surfaces of the substrates were characterized before and after adsorption by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The XPS binding energy results indicate that CH₃I adsorption on uranium yields a carbide-type carbon, UC, and uranium iodide, UI₃. On uranium dioxide the carbon electron binding energy measurements are consistent with the formation of a hydrocarbon, —CH₃-type moiety. The interpretation of XPS and AES spectral features for CH₃I adsorption on uranium suggest that a complex dissociative adsorption reaction takes place. Adsorption of CH₃I on UO₂ occurs via a dissociative process. Saturation coverage occurs on uranium at approximately two langmuir (1 L = 10^?6 Torr s) exposure whereas saturation coverage on uranium dioxide is found at about five langmuir.     

ELECTRONIC STRUCTURE STUDIES OF THE C60 FILM CONDENSED ON 2H-MoS2(0001) SURFACE

The electronic structure and vibrational spectrum of the C₆₀ film condensed on a 2H- MoS₂(0001) surface have been investigated by X-ray photoelectron spectroscopy (XPS), ul-traviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES) and infrared high-resolution electron-energy-loss spectroscopy (HREELS). AES analysis showed that at low energy side of the main transition, C₆₀ contains a total of three peaks just like that of graphite. However, the energy position of the KLL main Auger transition of C₆₀ looks like that of diamond, indicating that the hybridization of the carbon atoms in C₆₀ is not strictly in sp²- bonded state but that the curvature of the molecular surface introduces some sp²pz- bonded character into the molecular orbitals. XPS showed that the C 1s binding energy in C₆₀ was 285.0eV, and its main line was very symmetric and offered no indication of more than a single carbon species. In UPS measurement the valence band spectrum of C₆₀ within 10eV below the Fermi level (E_F) shows a very distinct five-band structure that character-izes the electronic structure of the C₆₀ molecule. HREEL results showed that the spectrum obtained from the C₆₀ film has very rich vibrational structure. At least, four distinct main loss peaks can be identified below 200 meV. The most intense loss was recorded at 66 meV, and relatively less intense losses were recorded at 95, 164 and 197meV at a primary energy of electron beam E_P = 2.0eV. The other energy-loss peaks at 46, 136, 157 and 186meV in HREEL spectrum are rather weak. These results have been compared to infrared spectrum data of the crystalline solid C₆₀ taken from recent literatures.     

H2O adsorption on Fe: Disorder and beam effects

The influence of surface damage on H₂O adsorption on Fe was examined for exposures up to 700 L using X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). In contrast to earlier measurements, the results did not show that the ability of H₂O to form a sub-monolayer protective layer was destroyed by the presence of surface damage created by ion sputtering. The current results in combination with published data indicate that the presence of this semi-protective layer is independent of surface structure. An electron beam was found to cause an enhanced oxidation and breakdown of this protective or “passive” film.