Experimental derivation of Auger transition probabilities from X-ray excited Auger electron spectra in XPS

Auger transition probabilities were experimentally derived from dominant XAES and related XPS peaks observed in XPS spectra. Some values of derived probabilities were higher than 1, because of addition or subtraction of background signal from the XAES or/and XPS peak intensity. However, the probabilities obtained are recognized to be useful for practical quantification by XAES and AES. Received: 6 April 1999 / Revised: 25 June 1999 / Accepted: 6 July 1999     

ESCA studies on copper-cobalt based catalysts

The copper-cobalt catalysts for alcohol synthesis were prepared and studied by ESCA techniques (XPS and XAES) and TPR. The valence states of the surface elements were investigated for Co–Cu–Y based catalysts, and it was found that there were some reoxidation during the reaction. From the XPS and XAES results, strong interactions between copper and cobalt in the samples were presented, in agreement with the TPR experiments. The interacted copper-cobalt units could be the active sites for higher alcohol synthesis.     

用XPS和XAES分析电化学沉积的DLC膜

采用电化学沉积方法，以甲醇溶剂作碳源，直流电压作用下在单晶硅表面沉积得到碳薄膜。通过研究石墨、金刚石和样品薄膜的XPS和XAES谱图特征，证明了此方法沉积得到的是DLC薄膜;利用曲线拟合技术在C_1s电子能谱图中拟合出sp³峰与sp²峰，并计算出样品薄膜中sp³碳的相对含量为55%;研究石墨、金刚石和样品薄膜的一阶微分XAES谱图，用线性插入法估算出样品薄膜中sp³碳的相对含量为60%。     

Quantitative surface analysis by Auger and x-ray photoelectron spectroscopy

Recent developments in quantitative surface analysis by Auger (AES) and x-ray photoelectron (XPS) spectroscopies are reviewed and problems relating to a more accurate quantitative interpretation of AES/XPS experimental data are discussed. Special attention is paid to consideration of elementary physical processes involved and influence of multiple scattering effects on signal line intensities. In particular, the major features of core-shell ionization by electron impact, Auger transitions and photoionization are considered qualitatively and rigorous approaches used to calculate the respective transition probabilities are analysed. It is shown that, in amorphous and polycrystalline targets, incoherent scattering of primary and signal Auger and photoelectrons can be described by solving analytically a kinetic equation with appropriate boundary conditions. The analytical results for the angular and energy distribution, the mean escape depth, and the escape probability as a function of depth of origin of signal electrons as well as that for the backscattering factor in AES are in good agreement with the corresponding Mote Carlo simulation data. Methods for inelastic background subtraction, surface composition determination and depth-profile reconstructions by angle-resolved AES/XPS are discussed. Examples of novel techniques based on x-ray induced photoemission are considered.     

Electronic structure of the doped SnO_2

SnO2 doped with La, Ce, Sm, Zn, Ca, Al and Sb was prepared by sol-gel technique and characterized by TEM, BET, XPS and XAES. The effect of the dopants on the grain sizes of SnO2 was described and especially the effect of dopants on the distribution of the electronic state density (DESD) of Sn4d orbital was studied deeply by using X-ray-induced Auger electron spectros-copy (XAES). It was observed that the dopants could influence not only the grain sizes of SnO2 but also electronic structure of SnO2, as well as the stability of the doped SnO2 samples. The experiment results indicated that the structure and stability of SnO2 film could be improved by the chemical modification of the dopants.     

Land-ocean interaction in modern delta formation and development: A case study of the Pearl River delta,China

SnO₂ doped with La, Ce, Sm, Zn, Ca, Al and Sb was prepared by sol-gel technique and characterized by TEM, BET, XPS and XAES. The effect of the dopants on the grain sizes of SnO₂ was described and especially the effect of dopants on the distribution of the electronic state density (DESD) of Sn4d orbital was studied deeply by using X-ray-induced Auger electron spectroscopy (XAES). It was observed that the dopants could influence not only the grain sizes of SnO₂ but also electronic structure of SnO₂, as well as the stability of the doped SnO₂ samples. The experiment results indicated that the structure and stability of SnO₂ film could be improved by the chemical modification of the dopants.     

Land-ocean interaction in modern delta formation and development: A case study of the Pearl River delta,China

SnO₂ doped with La, Ce, Sm, Zn, Ca, Al and Sb was prepared by sol-gel technique and characterized by TEM, BET, XPS and XAES. The effect of the dopants on the grain sizes of SnO₂ was described and especially the effect of dopants on the distribution of the electronic state density (DESD) of Sn4d orbital was studied deeply by using X-ray-induced Auger electron spectroscopy (XAES). It was observed that the dopants could influence not only the grain sizes of SnO₂ but also electronic structure of SnO₂, as well as the stability of the doped SnO₂ samples. The experiment results indicated that the structure and stability of SnO₂ film could be improved by the chemical modification of the dopants.     

C 1s and Au 4f7/2 referenced XPS binding energy data obtained with different aluminium oxides, -hydroxides and -fluorides

A number of partially catalytically active aluminium compounds characterised by powder XRD have been investigated by XPS and XAES using a new method for static charge referencing [1, 2]. In detail, α-Al₂O₃, γ-Al₂O₃, boehmite γ-AlO(OH), bayerite α-Al(OH)₃, hydrargillite γ-Al(OH)₃, α-AlF₃, β-AlF₃, and AlF_2.3(OH)_0.7· H₂O and a hexa-fluoropropylene oxide (HFPO) modified γ-Al₂O₃ are examined. Well defined and chemically inert 20 nm gold particles are deposited as a nearly statistical distribution on the sample surface avoiding large coagulation effects. This procedure allows a determination of gold referenced XPS and XAES data sets. Binding energies (BE) of Al 2p, Al 2s, O 1s and F 1s photoelectron peaks as well as kinetic energies (KE) of Al KLL and F KLL Auger electron emission peaks are presented in relation to the Au 4f_7/2 BE reference. XPS and XAES data found in literature are, in most cases, C 1s referenced and scatter in a broad range. BE differences Δ between the C 1s charge reference BE and Au 4f_7/2 charge reference BE obtained with our samples are monitored by using the Al 2p orbital. These BE differences Δ clearly suggest that the chemical state of carbon observed in this study is not as uniform as required for reliable static charge referencing. Received: 24 June 1996 / Revised: 12 December 1996 / Accepted: 14 December 1996     

CO2加H2合成甲醇Cu－Zn－O催化剂表面化学态研究

应用XRD、ESR、URDS、XPS及XAES等手段研究了CO₂加H₂合成甲醇Cu-Zn-O催化剂在还原后和反应状态下的表面化学状态,结果表明,在还原及反应状态下,催化剂表面仅能检测到Cu⁰,而未发现稳定的Cu²⁺和Cu⁺存在;ZnO被部分还原产生低价锌Zn^2-δ(0<δ<2).关联活性测试结果认为,Cu⁰/Zn^(2-δ)+O构成CO₂加H₂合成甲醇反应的活性中心。     

XPS光电子峰和俄歇电子峰峰位表

在长期从事XPS分析测试的经验基础上,搜集了有关文献中的大量数据,编制了XPS光电子峰和俄歇电子峰峰位表,用于正确识别各种样品XPS谱图中的电子峰,达到快速、正确分析各种样品元素组成和化学组成的目的．本峰位表对于从事XPS测试的分析人员和应用XPS的科技人员具有很好的实用价值．     

XPS and XAES of polyethylenes aided by line shape analysis: The effect of electron irradiation

X-ray photoelectron spectroscopy (XPS) and X-ray induced Auger electron spectroscopy (XAES) have been used to investigate different polyethylene surfaces, i.e. low density polyethylene (PELD), high density polyethylene (PEHD) and polyethylene of ultra high molecular weight (PEUHMW). The ratio of Csp²/sp³ was evaluated from (i) fitting of XPS C 1s spectra, (ii) the width of XAES C KLL spectra (parameter D) and (iii) line shape analysis by the pattern recognition (PR) method using the fuzzy k-nearest neighbors (fkNN) rule. The proposed approaches investigate: (i) the differences between various polyethylene surfaces, (ii) their surface changes and degradation due to electron irradiation under various doses and (iii) their stability under electron beam irradiation.The results of proposed approaches, i.e. C 1s fitting, C KLL width evaluation and PR line shape analysis applied to C 1s and C KLL transitions, are qualitatively consistent. The unirradiated polyethylenes indicate nearly Csp³ hybridizations. Under an electron dose a rapid decrease of Csp³ is observed, starting at a dose of 100 Cm⁻². The quantitative differences observed between results obtained from analyses using the C KLL and C 1s spectra, can be explained with a smaller average information depth of C KLL transition. However, quantitative discrepancies between results of various approaches using the same electron transition, i.e. C KLL or C 1s, are smaller. The surface degradation due to X-ray irradiation was negligible in comparison to electron beam irradiation. The PR method was efficient in identifying the polyethylene surfaces under various electron doses. The largest stability under an electron beam is exhibited by the PEUHMW.     

AMT在铜表面形成保护膜的STM研究

5一氨基七一流基一1、3、各喀二隆（AMT不仅是一种有效的感光材料和分析试剂，同时作为重要的中间体被广泛应用于农药、医药生产中间，但作为铜腐蚀抑制剂的应用还远不如苯并三氯哩．实验表明［'－'l，AMT在酸性、中性及碱性介质中对铜及其合金均具有较好的缓蚀作用，经AMT处理     

Oxidation‐induced nanostructures on Cu{100}, Cu(Ag) and Ag/Cu{100} studied by photoelectron spectroscopy

Initial surface oxidation and nanoscale morphology on Cu{100}, Cu(Ag) and Ag/Cu{100} have been investigated in situ by X‐ray photoelectron spectroscopy (XPS), X‐ray induced Auger electron spectroscopy (XAES) and the inelastic electron background analysis as a function of oxygen exposure at 3.7 × 10^?2 and 213 mbar pressures at a surface temperature of 373 K. Relative Cu₂O concentrations have been quantified by analysis of the peak shape of the XAES Cu LMM transition. The surface morphology of Cu₂O islands and the Ag layer has been characterized by inelastic electron background analysis of XAES O KLL and Ag 3d transitions. Oxygen‐induced segregation of Cu, as well as the subsequent Cu₂O island formation on Cu(Ag) and Ag/Cu{100} surfaces, has been investigated quantitatively. Our results indicate that Ag has a clear inhibitive effect on the initial oxidation and Cu₂O island formation on Cu(Ag) and Ag/Cu{100} surfaces. The Cu₂O islands are also observed to remain highly strained on Ag/Cu{100} even at higher O₂ exposures. The results suggest that strained Cu₂O islands eventually penetrate through the buried Ag layer, and in conjunction with segregating Cu atoms enable the oxidation to proceed at a similar rate to or even faster than on the unalloyed Cu surface. Copyright © 2007 John Wiley & Sons, Ltd.     

掺氮石墨烯-铜基催化剂的制备及催化性能

采用水热法合成掺氮石墨烯(N/GN),通过超声辅助等体积浸渍法制备掺氮石墨烯-铜基催化剂(Cu-N/GN)。通过XRD、SEM、TEM、N2吸附脱附、XPS和XAES对催化剂的微观结构、形貌及元素组成进行表征,并考察Cu-N/GN对乙炔氢氯化反应的催化性能。结果表明:在催化剂中铜颗粒尺寸较小、均匀分布于N/GN片层上,且铜含量较低(3.6%);Cu-N/GN对乙炔氢氯化反应的催化效果良好,乙炔转化率为68%,氯乙烯选择性为99%。     

An X-ray photoelectron spectroscopic study of novel SiON glasses

Novel SiON glasses obtained by melting mixtures of crystalline α-SiO₂ and α-Si₃N₄ were investigated by means of X-ray photoelectron spectroscopy (XPS). The incorporation of nitrogen into the SiO₂ network was recently proved by ²⁹Si-MAS-NMR (magic-angle spinning nuclear magnetic resonance) and Si K-XANES (X-ray absorption near edge structure). The Si 2p XPS and the Si KLL XAES (X-ray excited Auger electron spectroscopy) studies of the SiON glasses confirm the formation of mixed structural units (SiO_xN_4-x) by the presence of an additional spectral component energetically located between SiO₂- and Si₃N₄-like signals. The N 1s and O 1s XPS spectra support the conclusion about the incorporation of nitrogen into the SiO₂ network.     

The chemical state of arsenic in minerals of environmental interest--an XPS and an XAES study

A systematic analytical study using X-ray photoelectron spectroscopy (XPS) and X-ray induced Auger electron spectroscopy (XAES) has been carried out to characterize the chemical state of arsenic in complex environmental samples. The conventional approach, which relies on the chemical shift of the core levels As3d, provides ambiguous results in determining the chemical environment of arsenic. A more accurate approach, based on the Auger parameter and on the Wagner (Chemical State) plot, which combines AsLMM kinetic energy and As3d binding energy, was adopted. This novel method for determining the chemical state of arsenic was employed to completely characterize arsenic in complex environmental samples.     

Thermal and Microchemical Characterisation of Sol-Gel SiO2, TiO2 and xSiO2–(1–x)TiO2 Ceramic Materials

Amorphous SiO₂, TiO₂ and xSiO₂–(1–x)TiO₂ ceramic materials with selected values of x 0.5, 0.7 and 0.9, have been prepared via sol-gel process using silicon tetraethoxysilane (TEOS) and titanium tetraisopropoxide Ti(OPri)₄. By means of the combined use of differential thermal analysis (DTA),thermogravimetry (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM),X-ray photoelectron spectroscopy (XPS) and X-ray induced Auger electron spectroscopy(XAES), the surface microchemical structure and morphology of the sol-gel materials have been studied as a function of thermal treatments carried out in air up to 1200°C. In the range of temperature from 50 to 450°C, DTA-TG results evidence a remarkable mass loss due to the evaporation of organic solvents entrapped in the sol-gel materials and of the remnant organic components of the precursor metal alkoxides. In the range of temperature from 400 to about 1000°C, by means of the combined use of DTA, XRD, XPS and XAES techniques as a function of temperature and of chemical composition, it is possible to evidence the formation of crystalline phases such as quartz, anatase and rutile. Furthermore, line shape analysis of O1s XPS peak allows to distinguish between single O–Ti and O–Si bonds and also to disclose the presence of cross linking Si–O–Ti bonds, that act as bridges between SiO₂and TiO₂ moieties. As a function of temperature, Si–O–Ti bonds are broken and the formation of new Ti–O and Si–O bonds as in TiO₂ and SiO₂takes place as well as a silica segregation phenomenon. This revised version was published online in July 2006 with corrections to the Cover Date.     

X-ray and electron induced Auger processes for I2 adsorption on uranium

The accurate determination of the kinetic energy of X-ray induced Auger electrons, which is necessary in XPS experiments, e.g. for calculating the Auger parameter, is sometimes hampered by peak interferences or by the high secondary electron background. The latter is of special importance for low kinetic energy electrons like e.g. the U(OPV) and U(OVV) Auger electrons. These problems can be circumvented by using electron induced Auger transitions (AES). However, since XPS and AES use different reference points for the energy scales, both scales have to be matched. This can be done by measuring the kinetic energy of an appropriate Auger transition in XPS and relating this value to the maximum of the second derivative of the same peak in AES.     

Surface oxidation kinetics of SiC powders in wet and dry air studied by x‐ray photoelectron spectroscopy and bremsstrahlung‐excited Auger electron spectroscopy

Silicon carbide powder samples were heated at temperatures between 600 °C and 850 °C in wet and dry air to investigate the effect of moisture on the oxidation kinetics. Equations were derived to calculate the surface oxide thickness from both the Si 2p XPS spectra and from the Si KLL bremsstrahlung‐excited Auger spectra. The oxide film growth rates are shown to be parabolic. The film thickness formed during oxidation in wet air was larger than that in dry air for the same temperature and heating time. The activation energy for wet oxidation was found to be significantly lower than that for dry oxidation within this temperature range. Copyright © 2003 John Wiley & Sons, Ltd.     

X‐ray photoelectron spectroscopy and the pattern recognition method—their application to surface studies in CoPd alloys

In the present work, polycrystalline CoPd alloys in varying range of bulk atomic percent composition (Co30Pd70, Co50Pd50 and Co70Pd30) are investigated by means of X‐ray photoelectron spectroscopy (XPS). The results of conventional XPS quantitative multiline (ML) approach are compared to the results obtained on the basis of XPS lines shape analysis, where the selected XPS or X‐ray induced Auger electron (XAES) transitions, are processed using the pattern recognition method known as the fuzzy k‐nearest neighbour (fkNN) rule. The fkNN rule is applied to the following spectra line shapes: Pd MNV, Co 2p, Co LMM, Pd 3d and valence band, analysing electrons in a varying range of selected kinetic energies. Both methods showed the surface segregation of Pd in Co30Pd70 and Co50Pd50 alloys. The results of the ML, the binding energy shift (ΔBE) analysis and the fkNN rule remained in agreement. Discrepancies in quantitative results obtained using different approaches are discussed within the accuracy of the applied methods, differences due to mean escape depth (MED) of electrons in considered transitions, their depth distribution function, the sensitivity of electron transition line shape on the environmental change (weaker effect for the inner shell transitions, and stronger effect for the outer shell transitions and Auger electron spectroscopy (AES) electrons transitions) and the non‐uniform depth profile concentrations. Copyright © 2005 John Wiley & Sons, Ltd.