Topmost-surface-sensitive Si-2p photoelectron spectra of clean Si(1 0 0)-2 × 1 measured with photoelectron Auger coincidence spectroscopy

Topmost-surface-sensitive Si-2p photoelectron spectra of a clean Si(1 0 0)-2 × 1 surface have been measured using Si-2p photoelectron Si-L₂₃VV Auger coincidence spectroscopy (Si-2p–Si-L₂₃VV PEACS). The escape depth of the PEACS electrons is estimated to be ～1.2 Å. The results support the assignments of the Si up-atoms, the Si down-atoms, the Si 2nd-layer, and the Si bulk proposed in previous researches. The Si-2p component with a binding energy of ?0.23 eV relative to the bulk Si-2p_3/2 peak, is shown to originate mainly from the topmost surface. Site selectivity of PEACS is indicated to be achieved to some degree by carefully selecting the kinetic energy of the Auger electrons. Since PEACS can be applied to any surface, the present study opens a new approach to identify PES components.     

The origin of narrowing of the Si 2p coincidence photoelectron spectroscopy main line of Si(1 0 0) surface

The Si 2p photoelectron spectroscopy (PES) main line of Si(1 0 0) surface measured in coincidence with the singles (noncoincidence) Si L_2,3-VV Auger-electron spectroscopy (AES) elastic peak is calculated. The agreement with the experiment is good. The present work is the first many-body calculation of the experimental coincidence PES spectrum of solid surface. The narrowing of the coincidence Si 2p PES main line compared to the singles one is due to the mechanism inherent in the coincidence PES. The inherent mechanism is explained by a many-body theory by which photoemission and Auger-electron emission are treated on the same footing.     

Many-body effect in the coincidence L3 and M3 photoelectron spectroscopy spectra of Cu metal

The coincidence L₃ and M₃ photoelectron spectroscopy (PES) main lines of Cu metal are calculated by a many-body theory. There is no peak-energy shift between the singles PES main line and the coincidence one. The asymmetric narrowing of the coincidence PES main line on the low kinetic energy (KE) side is very small. This is in accord with recent experimental findings. In Cu metal, the shakeup satellite intensity is small and the main-line satellite separation energy is much larger than the core–hole lifetime width. The interference via the final-state interaction is negligible. In the PES main line, the imaginary part of the self-energy by shakeup excitations, which is very small compared to the core–hole lifetime width, decreases very slowly in linear with photoelectron KE. The branching ratio of Auger decay of a single hole state then increases very slowly in linear with photoelectron KE so that the deviation of the coincidence PES main line from the singles one is very small. The 939 eV structure seen only in the coincidence L₃ PES spectrum of Cu metal is attributed to the enhancement of the inelastic peak of a smaller energy loss due to electrons of a smaller average emission depth measured in coincidence with the elastic Auger peak. The structure will not be enhanced in the singles PES spectrum. The background subtraction in the coincidence spectrum cannot be the same as that in the singles one. Such consideration is necessary before we can conclude about the asymmetric narrowing on the low KE side. A unique capability of APECS by which one can determine the photoelectron KE dependent part of the imaginary part of the self-energy is pointed out.     

ELS study on initial oxidation of Ni(100) surfaces

Electron energy loss spectra of clean and oxygen-covered Ni(100) surfaces were observed with concomitant measurements of LEED, work function change, and Auger peak height ratio O(KL_{2, 3}L_{2, 3})/Ni(L_{2, 3}VV). The observed electronic transitions are interpreted on the basis of primary election energy dependence, and of comparison with the loss spectrum for a UHV-cleaved NiO(100) surface and optical data of Ni. The observed loss peaks at 9.1, 14, and 19 eV in the clean surface spectrum are ascribed to the bulk plasmon of the 4s electrons, the surface plasmon, and the bulk plasmon of the coupled 3d + 4s electrons, respectively, and the weak but sharp peak at 33 eV is tentatively attributed to the localized many-body effect in the final state. Three oxygen-derived peaks at 6.0, 8.0, and 10.3 eV in the low oxygen exposure region (?4 L) are ascribed to the O 2p(e) → Ni 3d, O 2p(a₁) → Ni 3d, and O 2p → Ni 4s transitions, respectively. In the high oxygen exposure region (?50 L), the spectra become quite similar to that of the UHV-cleaved NiO(100) surface. The oxidation process consistent with LEED, Auger peak height ratio and work function change measurements is discussed.     

Investigating the structure of the Tin M45N45N45 auger spectrum using auger photoelectron coincidence spectroscopy

Auger photoelectron coincidence spectroscopy (APECS) data were collected for the M₄₅N₄₅N₄₅ Auger peak in coincidence with the 3p_3/2, 3d_3/2 and 3d_5/2 photoelectron lines of Tin. Model spectra were created to fit the APECS data from sets of Gaussian curves defined by Parry-Jones et al., J. Phys. C: Solid State Physics, 12 (1979) 1587. These models were then combined using information about the relative intensities of the peaks from the aforementioned paper to produce a model of the Auger peak which proved a good comparison to high resolution AES spectra. The APECS data revealed satelite structure in the M₅N₄₅N₄₅ peak in coincidence with the 3d_5/2 photoelectron line (M₅N₄₅N₄₅:3d_5/2) due to the Mg Kα₃ line of the X-ray source. There was evidence of a small Coster–Kronig component in the M₄N₄₅N₄₅:3d_3/2 data and the M₄₅N₄₅N₄₅:3p_3/2 data showed intensity in the M₄N₄₅N₄₅ and M₅N₄₅N₄₅ regions also arising from Coster–Kronig processes. The contribution of the M₄N₄₅N₄₅ plasmon was included in each of the APECS models and was reflected in the high resolution AES spectra. Slight oxidation of the surface of the sample during each 24-h period produced a 0.7 eV shift of the singles Auger peak to lower kinetic energies. The shift was not reflected in the coincidence peak which produced a spectrum of a clean surface due to the nature of the coincidence experiment.     

Comparative AES and RHEED study of the formation of Pd silicide on clean and oxide covered Si(100) and (111) surfaces

The formation and epitaxial orientation of Pd silicide on clean and native oxide covered Si(100) and (111) surfaces was studied by Auger electron spectroscopy (AES) and reflection high energy electron diffraction (RHEED). Pd was vapor deposited in UHV on to the substrates up to thicknesses of about 6 nm. On clean Si substrates, ultra-thin Pd deposits reacted to form Pd₂Si already at room temperature, as detected by a characteristic splitting of the Si LVV Auger peak. However, a polycrystalline structure with very small crystallite sizes was indicated by diffuse ring patterns in RHEED. When the initial thickness of the Pd deposit exceeded about 3 nm, the diffraction ring pattern of unreacted metal developed. During annealing of room temperature deposits of Pd, the (100) and (111) substrates behaved differently. Larger crystallites formed on Si(100), but the films remained polycrystalline, though textured. On Si(111), virtually perfect epitaxial re-orientation of the silicide was found. When the substrates were initially covered with native oxide of about 2 nm thickness, silicide formation started at about 200°C, resulting in polycrystalline, but strongly textured Pd₂Si. Upon further annealing at temperatures up to 600°C, an additional phase of epitaxially oriented Pd₂Si developed on Si(111), similar to that on clean Si(100). In all experiments, extended annealing at temperatures above 250°C caused segregation of Si to the surface. This was accompanied by the development of an additional peak in the Auger electron spectra at about 313 eV, which we assign to a plasmon loss of δE = 17 eV in the Si overlayer, being excited by Pd Auger electrons of energy 330 eV.     

Determination of the intrinsic bulk and surface plasmon intensity of XPS spectra of magnesium

Separation of intrinsic and extrinsic intensity contributions to plasmon peaks in X-ray photoelectron spectra of free-electron like metals (Me) such as Be, Na, Mg, Al and semiconductors as Si and Ge, necessary for the accurate determination of the thickness of overlayers in the range of a few nanometers, and their composition, is difficult because of their more or less coincident energies. The intrinsic bulk and surface plasmon contributions to Me 2p spectra can be determined separately from the intensities of the metallic and oxidic main peak as obtained from a series of spectra recorded from the unoxidised metal and the oxidised metal with different oxide-film thicknesses. In the present work, this method was applied to XPS Mg 2p spectra. It was shown that the method is very sensitive to deviations in the measured data, and therefore a careful error analysis is required, which has been developed in this work. Furthermore, an alternative method based on the same theory was proposed. This method yielded values of 0.17 and 0.06 for the intrinsic bulk and surface plasmon contributions to the Mg 2p spectrum relative to the Mg 2p main peak for a detection angle of 45°. It was demonstrated that the values obtained for the intrinsic bulk and surface excitation contributions determined according to both methods depend on the oxide-thickness range investigated. This observation indicates that commonly applied simplifying assumptions for the oxidation behaviour of Mg, like a layer-by-layer growth mechanism and/or the development of a homogeneous oxide with bulk MgO properties, as for composition and band gap values, do not hold. The pronounced effect of neglect of the intrinsic plasmon intensity contributions on the thickness values determined for MgO films on Mg was shown.     

用可调探测深度电子能量损失谱与俄歇电子能谱研究Pb/Ni(001)界面

本工作用可调探测深度电子能量损失谱(ELS)与俄歇电子能谱(AES)研究Pb在Ni(001)表面的生长过程。发现Pb是一层一层地在表面生长的,即按Franck-van der Merwe(F-M)模式生长。当Pb的覆盖度大于1单层(ML)时,Pb的6s能带对应的电子能量损失峰开始出现,当Pb的覆盖度为3ML时,Pb的体等离激元的损失峰已相当明显。在Pb的蒸镀过程及随后的整个退火过程中,Pb的体等离激元峰,6s能带峰和Ni的3p能带峰的峰位与峰宽均保持与纯金属相同的值,也没有出现新的体等离激元峰。由此说明P     

The Ba/Si(100)-2 × 1 interface I. XPS and XAES studies of silicide formation

In two complementary papers we present the results and analysis of an extended study of the Ba/Si(100)−2 × 1 interface. In this paper, we will discuss X-ray excited Auger electron spectroscopy- and X-ray photoelectron spectroscopy chemical shifts, as well as plasmon losses, which have been studied to answer the question whether silicide formation occurs at this interface. It is found that no silicide formation takes place at room temperature. Two Ba-Si phases are detected as reaction products upon annealing the Ba/Si(100) system at ˜ 550 K.     

Analysis of the Auger-photoelectron coincidence spectroscopy (APECS) spectra of metallic Pd,Ag, and Sn

The M45-level photoelectron spectrum of Ag metal measured in coincidence with the M45–VV(¹G) Auger-electron line is analyzed by taking into account the possibility of the M4–M5–VV Coster–Kronig (CK)-transition preceded Auger transition. We denote the atomic shells Mx(Mxy) and Nxy (x, y = 4,5) by MX(MXY) and V, respectively. The M4–M5 CK-transition rate is very small. The M45–VV Auger-electron spectra of metallic Pd and Sn measured in coincidence with the M4 (or M5)-level photoelectron line are analyzed. The M4–M5 CK-transition rates are also very small in metallic Pd and Sn. The coincidence Auger-electron line previously interpreted as the M4–M5–VV (or M4–M5V–VVV) Auger-electron line is largely due to the inelastically scattered M5-level photoelectron background beneath the M4-level photoelectron line. The APECS spectrum of Pd metal shows the first evidence of the M5V–VVV transition of the localized M5V shakeup two-hole state. The intensity ratio of the inelastically scattered Auger-electron background to the M5–VV Auger-electron main line of Ag metal measured in coincidence with the inelastically scattered M5-level photoelectron background beneath the M4-level photoemission line increases, as compared to that measured in coincidence with the M5-level photoelectron main line. This is because when the probability of the photoelectron being inelastically scattered increases, that of the Auger electron emitted by the same ionized atom, being inelastically scattered increases. In other words the photoelectrons and the Auger electrons are originated from the deeper atomic sites (longer pathlength).     

High resolution Auger electron spectroscopy of metallic copper

Part of the LMM Auger spectrum from metallic copper has been studied in a high resolution X-ray photoelectron spectrometer. Fine structure not earlier reported has been observed. The main L₃M_4,5M_4,5 peak is very narrow, 1.0 eV, although the valence band is involved in the transition. The agreement between experimental and calculated Auger electron energies is very good. Since fine structure is found to be an intrinsic property in Auger spectra the interpretation of “satellite” peaks as due to electron—plasmon interactions should be used with care. The L₃M_4,5M_4,5 peak is very sensitive to the copper surface conditions. Surface oxygen affects the peak in a characteristic way.     

Anomalous natural linewidth in the 2p photoelectron spectrum of SiF4

The silicon 2p photoelectron spectra for SiH4, SiF4, and SiCl4 have been analyzed to give the natural linewidths of the Si 2p hole states, which reflect the Auger decay rates of the states. For SiH4 the measured width of 38 meV is in approximate agreement with the prediction of the one-center model (32 meV), but that for SiF4 of 79 meV is more than 5 times the value of 14 meV predicted by this model. Approximate theoretical calculations indicate that valence electrons from the fluorine atoms of SiF4 play an important role in the Auger decay via interatomic processes.     

Many-electron effects in the Auger-photoelectron coincidence spectroscopy spectra of the late 3d-transition metals

The valence hole created by the L2–L3 M45 Coster–Kronig (CK) transition may hop away from the ionized atomic site before the L3-hole decays. Then when the third (Auger) electron emitted by the L3-hole decay is measured in coincidence with the photoelectron emitted by the initial L2-level electron ionization, the coincidence spectrum becomes similar or identical to the singles spectrum of the secondary (Auger) electron emitted by the L3-hole decay as if it decayed as an initial single core hole. Thus the coincidence spectrum is essentially governed by the valence-hole dynamics of both the intermediate states and the final states of the L2–L3 (M45) CK-transition preceded Auger transition. In the present paper the Auger-photoelectron coincidence spectroscopy (APECS) spectra of Fe, Co, and Ni metals reported by C.P. Lund et al. (Phys. Rev. B55 (1997) 5455) are analyzed in light of the delocalization and localization of the valence hole(s) created by the CK transition or the CK-transition preceded Auger transition.     

Characteristic energy losses on carbon contaminated layers correlated with secondary electron,auger electron emission and contrasts in scanning microscope

The secondary electron (SE) spectrum (0 < E < 50 eV) has been analysed by means of a CMA. Samples were clean aluminum, aluminum becoming carbon contaminated, sintered graphite powder, electro chemically deposited polymer on platinum and monocrystals of silicon carbon contaminated. When the clean Al surface is becoming carbon contaminated a quick decrease of surface plasmon and bulk plasmon losses is observed whereas a main characteristic energy loss peak (ELS) at 20 eV and a secondary electron peak at 20 eV appear simultaneously. Both peaks are very sensitive general features of carbon contaminated surfaces. The main loss peak is attributed to the excitation of the carbon-carbon bounds (σ → σ¹) as already proposed in the transmission ELS. The few eV change of the loss peak energy of various carbon compounds may correspond to slightly different carbon-carbon distances. The 20 eV secondary electrons could be produced by the relaxation of the excited state (σ¹ → σ transition) via an Auger process. The cross section for molecular electronic excitation is higher than that of atomic ionization for inner level. The loss peak is as intense as the SE peak and higher by more than two orders of magnitude than the C KLL Auger peak. The modification of secondary emission under carbon contamination has been observed on a silicon sample by Scanning Electron Microscopy (SEM) in the Secondary Electron Image (SEI) mode.     

Electron spectroscopy of graphite,graphite oxide and amorphous carbon

Core-level and valence-band photoelectron spectra and Auger spectra for the basal plane of highly ordered graphite, the edge plane of highly ordered graphite, the basal plane of graphite oxide, and for the basal plane of disordered graphite are compared in an effort to determine spectral features that may be used to identify these chemical species in carbon-rich specimens. The photoelectron spectra were recorded using 1253.6 eV X-ray excitation. The Auger spectra were obtained using both X-ray (1253.6 eV) and electron (3 keV) excitation. The differential X-ray excited C-KVV spectra were the most useful in distinguishing the different types of carbon. In particular, the plasmon structure and the energy separation between the two major excursions were very sensitive to changes in the surface chemistry and structure. Changes in peak position and peak width observed in the valence band and C(1s) photoelectron spectra were also very helpful in distinguishing the pristine, structurally damaged, and the oxidized graphite surfaces. Much of the structural and chemical information apparent in the X-ray excited C-KVV spectra was lost upon electron beam exposure. Differences in the C-KVV Auger lineshapes for X-ray and electron excitation were attributed to both structural and chemical changes induced by electron beam exposure.     

Electronic transitions on UHV-cleaved Si (111) adsorbed with oxygen

The electron energy loss spectra have been measured of oxygen-adsorbed Si (111) surfaces at the primary energies of 10–200 eV. The observed peaks are at the loss energies of 2.9, 3.6, 4.8, 5.7, 6.9, 8.2, 9.6, 12.0, and 13.0 eV. All the peaks are attributed to the one-electronic transitions related to the adsorbed oxygen, except for the 9.6 eV peak which could possibly be due to the relaxed surface plasmon excitation. It is shown that the “splitting” of surface plasmon reported by Ibach and Rowe does not exist.     

Surface valence band and plasmon features on clean cleaved silicon

The L₁L_2,3V Auger transition from vacuum cleaved surfaces of silicon has been studied in detail. Features in the distribution which are not due to plasmon losses are shown to correspond with primary features in the valance band density of states. However, effects of transition probability energy dependence apparently smear the structure, which may also be due in part to particular surface region properties. Bulk plasmon losses up to 9 in number are clearly resolved and the relative intensities compared with simple theory. A mean free path for bulk plasmon emission is deduced which is approximately twice the m.f.p. for other loss processes. Background contamination produces a new peak at approximately 4.5 eV.     

Electron spectroscopic study of the iron surface and its interaction with oxygen and nitrogen

The interaction of oxygen and nitrogen with a clean polycrystalline iron surface was investigated using Auger electron spectroscopy, photoelectron spectroscopy and electron energy loss spectroscopy. Further evidence for the dissociative nature of adsorbed nitrogen on iron is shown by the photoelectron spectroscopy data in conjunction with preliminary thermal desorption work. The first electron energy loss data for the nitrided iron surface is presented and shown to be very similar to that for the clean and oxidized surfaces.     

Background removal in auger electron spectroscopy: a new experimental approach

A review of the main available methods of background removal in Auger electron Spectroscopy and X-ray photoelectron Spectroscopy is given. The major features, assumptions and results of theoretical works, which form the basis of the present method, are presented. This method uses a convolution technique of the experimental spectrum with the single event loss function. It has been applied to Auger electron spectra (Si, Ag, Fe, Ni, Cu, Al). When Auger energy is sufficiently low (Si, Ag), it has been assumed that Auger electrons act as a secondary electrons source within a multiplet energy range. In every case results are satisfactory.     

Coster-kronig decay of the ar2s hole observed by auger-threshold photoelectron coincidence spectroscopy

The Coster-Kronig lines associated with Ar2s decay have been resolved within the natural linewidth of the 2s hole for the first time. This was possible by a new spectroscopic technique, relying on resonance enhanced double photoionization, Auger-threshold photoelectron coincidence spectroscopy. Contrary to standard Auger spectroscopy, this technique can filter out weak components in Auger spectra corresponding to a well-defined inner-shell state and, furthermore, can achieve a resolution no longer limited by the lifetime of the inner-shell hole.