X射线光电子能谱

X射线光电子能谱（X-ray photoelectron spectroscopy，XPS）技术也被称作用于化学分析的电子能谱（electron spectroscopy for chemical analysis，ESCA）．XPS属表面分析法，它可以给出固体样品表面所含的元素种类、化学组成以及有关的电子结构重要信息，在各种固体材料的基础研究和实际应用中起着重要的作用．文章简要介绍了XPS仪器的工作原理和分析方法，并给出了XPS在科学研究工作中的应用实例．     

X射线光电子能谱

X射线光电子能谱（X-ray photoelectron spectroscopy, XPS）技术也被称作用于化学分析的电子能谱（electron spectroscopy for chemical analysis,ESCA）.XPS属表面分析法,它可以给出固体样品表面所含的元素种类、化学组成以及有关的电子结构重要信息,在各种固体材料的基础研究和实际应用中起着重要的作用.文章简要介绍了XPS仪器的工作原理和分析方法,并给出了XPS在科学研究工作中的应用实例.     

Characterization of plasma fluorinated zirconia for dental applications by X-ray photoelectron spectroscopy

This paper discusses fluorination of biomedical-grade yttria-stabilized zirconia (YSZ) by sulfur hexafluoride plasma treatment and characterization of near-surface chemistry products by X-ray photoelectron spectroscopy (XPS). Deconvolution of the Zr 3d and Y 3d XPS core level spectra revealed formation of both ZrF₄ and YF₃. In addition, seven-coordinate ZrO₂F₅ and/or ZrO₃F₄ phases were deconvolved, retaining similar atomic coordination as the parent oxide and believed to have formed by substitutional displacement of oxygen by fluorine. No additional components attributed to yttria oxyfluoride were deconvolved. Argon ion sputter depth profiling determined the overlayer to be ∼4.0 nm in thickness, and angle resolved XPS showed no angle dependence on component percentages likely due to fluorination extending into the grain boundaries of the polycrystalline substrates. Importantly, the conversion layer did not induce any apparent change in zirconia crystallinity by inspection of Zr-O 3d_5/2,3/2 peak positions and full-width-at-half-maximum values, important for retaining its desirable mechanical properties.     

Influence of surface structure of SiC nano-sized powder analyzed by X-ray photoelectron spectroscopy on basic powder characteristics

SiC nano-sized powder with high specific surface area is potentially of considerable interest to form fully dense SiC ceramics at lower sintering conditions (temperature/pressure). Surface structure of six kinds of commercially available SiC nano-sized powders produced by three different venders was analyzed in detail by X-ray photoelectron spectroscopy (XPS). The overall XPS spectra of all nano-sized powders detected O-based bond (O1s peak), C-based bond (C1s peak) and Si-based bond (Si2s and Si2p peak). Surface structure of nano-sized powders included one of three impurity phases: (1) free carbon, (2) silica and (3) silicon oxycarbide. Furthermore, the influences of surface structure by XPS were systematically investigated on basic powder characteristics, such as chemical composition, morphology, particle density and primary particle size. It was revealed that the basic powder characteristics had a close relationship to the surface structure of nano-sized powder each impurity.     

Prediction of protein interaction behaviour with PEG-grafted matrices using X-ray photoelectron spectroscopy

Due to the considerable scientific and commercial interest in poly(ethylene glycol) (PEG) grafted solid surfaces for biomedical applications, it is important to characterize the properties and behaviour of these modified surfaces. In this study, we applied a unique method to predict the magnitude of interactive forces exerted between a globular protein and PEG-grafted matrices. Carboxyl functionalized solid matrices were covalently grafted with PEG-amine derivatives at varying PEG surface concentrations and layer thicknesses by controlling the grafting reaction parameters. X-ray photoelectron spectroscopy was used to characterize these PEG-grafted matrices using the standard overlay model. A detailed and systematic correlation between PEG layer thickness and the distance between the grafted PEG chains resulted in valuable information regarding protein interactions with these PEG-grafted matrices. Finally, this predicted interaction behaviour was validated with fluorescent images obtained from fluorescein isothiocyanate-labelled Cytochrome c-conjugated solid matrices using confocal laser scanning microscopy.     

X-ray photoelectron spectroscopic analysis of the surface chemistry of silica nanowires

A thorough analysis of the surface chemistry of silica nanowires has been performed by X-ray photoelectron spectroscopy to investigate unexpected surface changes. Examination of the Si 2p, O 1s, and C 1s core level states before and after exposure of the nanowires to various liquid media showed that silica nanowires are capable of much higher surface hydroxyl concentrations than planar native oxides. It is further demonstrated that the nanowire surface hydroxyl concentration corresponds to the pH of the aqueous media to which the nanowires are exposed. Spectral feature changes due to water exposure similar to those observed for fibronectin binding suggests that fibronectin binding is competitively inhibited by slow changes in surface chemistry resulting from water exposure.     

Pressure effects on aluminium oxidation kinetics using X-ray photoelectron spectroscopy and parallel factor analysis

The effects of water vapour pressure on oxidation kinetics of aluminium have been studied using X-ray photoelectron spectroscopy (XPS) and three-way parallel factor analysis (PARAFAC). While the first technique is a powerful experimental tool for surface oxidation studies, the PARAFAC technique is a sophisticated analytical tool for analysing XPS data. The XPS Al(2p) and O(1s) core level have been used to follow the oxide film growth on clean surfaces at room temperature as a function of oxidation time (ranging from 1 to 60 min) and pressure of water vapour (ranging from 2.0×10⁻⁶ to 6.5×10⁻⁴ Pa). The growth of thin oxide films on aluminium surfaces has been found to follow the Cabrera–Mott inverse logarithmic law in all pressure ranges studied. The pressure effects have shown that the defect formation reaction at the oxide film/gas interface is the rate determining process in the aluminium oxidation. The pressure dependence of oxidation kinetics can be explained on the basis of metal vacancies in the defect structure of thin aluminium oxide films.     

Investigations of CdS and Ag-CdS nanoparticles by X-ray photoelectron spectroscopy

In the present report, CdS and Ag-CdS nanoparticles were synthesized using cysteine as a capping agent. Surface properties CdS and Ag-CdS nanoparticles were studied by X-ray photoelectron spectroscopy (XPS). XPS study of CdS nanoparticles was carried out as a function of pH and for a refluxed sample at pH 11.2. Effect of dopant concentration on surface properties of Ag-CdS nanoparticles was also studied for as prepared samples as well as for annealed sample at 2% doping. Effect of pH, dopant concentration, and effect of particle size on different sulfur species present in the system was studied. Features of Cd 3d, S 2p and Ag 3d core level have been discussed in detail.     

Secondary electron emission control in X-ray photoelectron spectroscopy

Secondary electron emission (SEE) is a major player in surface charging during X-ray photoelectron spectroscopy (XPS); its characteristics and applicability as a current source for electrical measurements are studied. We employ sample biasing and a top retarding grid to control the photoelectron current, and further compare their I–V characteristics with direct spectroscopy of the secondary electrons. Using silica-coated gold substrates, the effect of sample work function on the emitted secondary electrons is shown and fine control over the surface potential gradients, in the range of 10–100 meV, is achieved. XPS-based chemically resolved electrical measurements (CREM) can thus be extended to the positive current regime.     

Near surface composition of some alloys by X-ray photoelectron spectroscopy

Chemical compositions of the alloys of CuNi (Cu_0.10Ni_0.90, Cu_0.30Ni_0.70, Cu_0.70Ni_0.30) and BiSb (Bi_0.80Sb_0.20, Bi_0.64Sb_0.34, Bi_0.55Sb_0.45) are determined by X-ray photoelectron spectroscopy. The stoichiometries are determined and are compared with the bulk compositions. Possible sources of systematic errors contributing to the results are discussed. Errors arising out of preferential etching in these alloys have been investigated. It has been inferred from such studies that the preferential etching does not enrich the surface composition with a particular component for the two systems reported here. Quantitative results of CuNi system indicate that the surface regions of the Cu_0.70Ni_0.30 alloy is Cu-rich, although no such evidence is observed in case of BiSb system.     

X-ray photoelectron spectroscopy characterization of stain-etched luminescent porous silicon films

The surface and in-depth chemical nature of the photoluminescent stained Si layer obtained with a novel procedure based on HF/HNO₃ is presented. Oxide-free porous Si surfaces result from controlled preparation, storing and handling of samples, as revealed by parallel X-ray photoelectron spectroscopy and X-ray-induced Auger electron spectroscopy measurements, coupled with Ar⁺ ion sputtering. The present findings support the model for the porous layer of oxidized samples of Si grains embedded in a silica gel matrix.     

X-ray photoelectron spectroscopy of boron implanted 4145 steel surface

The near-surface region of 4145 steel following boron implantation was investigated by x-ray photoelectron spectroscopy (XPS). The steel surface was implanted with¹¹B⁺ ions to a constant dose of 1.0×10¹⁷ ions cm^–2 at energies of 30 and 135 keV. The XPS spectrum of the implanted surface showed a shift in the B(1s) level towards the higher binding energy. The observed 188.0 eV binding energy of the B(1s) level was found to be in good agreement with the characteristic binding energy of the B(1s) level corresponding to iron boride (Fe₂B). Hence the increase in surface hardness reported previously is related to the formation of an iron boride layer in the near-surface region known for its hardening capabilities.     

X-ray photoelectron spectroscopy study of Pd oxidation by RF discharge in oxygen

The low-temperature oxidation of polycrystalline palladium by RF oxygen plasma was studied via X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Detailed information about the electronic states of palladium and oxygen was obtained based on the XPS curve fitting analysis of Pd3d and Pd3p + O1s lines. The results showed that Pd oxidation by oxygen plasma was different from Pd oxidation in pure O₂ at high temperature. SEM shows well-structured submicron PdO particles result from oxidation in pure O₂, whereas plasma oxidation results in the predominant formation of two-dimensional PdO structures covering the initial crystallites of the Pd foil. Further oxidation to a three-dimensional PdO phase occurs under prolonged treatment with oxygen plasma. The formation of a PdO_x (x > 1) species, characterized by a E_b(Pd3d_5/2) = 338.0–338.2 eV value that is close to the Pd⁴⁺ oxidation state, was also observed. This PdO_x species was found to have low thermal stability (T < 400 K). It is proposed that the PdO_x species can be localized within the boundaries of crystallites.     

A photoelectron spectroscopic study of the carburization of MoO3

MoO₃ and Mo samples containing copper were treated with different hydrocarbon/hydrogen gas mixtures. The formation of Mo₂C was followed by X-ray photoelectron spectroscopy (XPS). Spectra taken in the Mo 3d, C 1s, O 1s, Cu 2p and Cu KLL regions demonstrated that the treatment with the hydrocarbon/hydrogen gas mixtures led to the formation of Mo₂C. From the comparison of the effects of various hydrocarbons on the XP spectra of Mo 3d we can state that the reduction of MoO₃ starts at the lowest temperature for C₂H₆/H₂ (600 K) followed by CH₄/H₂ (700 K) and C₄H₁₀/H₂ (723 K). Binding energies of Mo 3d_5/2 characteristic for Mo₂C are measured in the range of 227.7-228.0 eV. These values were attained at 900 K for CH₄/H₂, at 800 K for C₂H₆/H₂ and at 873 K for C₄H₁₀/H₂. Addition of copper to MoO₃ catalyzed its reduction and promoted the carburization process.     

Lab-based ambient pressure X-ray photoelectron spectroscopy from past to present

Chemical interactions which occur at a heterogeneous interface between a gas and substrate are critical in many technological and natural processes. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) is a powerful spectroscopy tool that is inherently surface sensitive, elemental and chemical specific, with the ability to probe sample surfaces in the presence of a gas phase. In this review, we discuss the evolution of lab-based AP-XPS instruments, from the first development by Siegbahn and coworkers up through modern day systems. A comprehensive overview is given of heterogeneous experiments investigated to date via lab-based AP-XPS along with the different instrumental metrics that affect the quality of sample probing. We conclude with a discussion of future directions for lab-based AP-XPS, highlighting the efficacy for this in-demand instrument to continue to expand in its ability to significantly advance our understanding of surface chemical processes under in situ conditions in a technologically multidisciplinary setting.     

Evolution of steel surface composition with heating in vacuum and in air

X-ray photoelectron spectroscopy (XPS) has been used to investigate the changes in surface composition of three steels as they have undergone heating. The steels were mild steel, and two austenitic stainless steels, commonly designated 304 and 316 stainless steels. XPS measurements were made on the untreated samples, and then following heating for 30 min in vacuo and in a 1 × 10⁻⁶ Torr partial pressure of air, at temperatures between 100 °C and 600 °C.Mild steel behaves differently to the two stainless steels under the heating conditions. In mild steel the iron content of the surface increased, with oxygen and carbon decreasing, as a function of increasing temperature. The chemical state of the iron also changed from oxide at low temperatures, to metallic at temperatures above 450 °C.In both stainless steels the amount of iron present in the surface decreased with increasing temperature. The decrease in iron at the surface was accompanied by an increase in the amount of chromium at the steel surface. At temperatures above 450 °C the iron in both 304 and 316 stainless steels showed significant contributions from metallic iron, whilst the chromium present was in an oxide state. In 316 stainless steel heated to 600 °C there was some metallic chromium present in the surface layer.The surfaces heated in air showed the least variation in composition, with the major change being the loss of carbon from the surfaces following heating above 300 °C. There was also a minor increase in the concentration of chromium present on both the stainless steels heated under these conditions. There was also little change in the oxidation state of the iron and chromium present on the surface of these steels. There was some evidence of the thickening of the surface oxides as seen by the loss of the lower binding energy signal in the iron or chromium core level scans.The surfaces heated in vacuum showed a similar trend in the concentration of carbon on the surfaces, however the overall concentration of oxygen decreased throughout the heating of these steels. There were also significant changes in the oxidation state of the iron and chromium on these surfaces with significant amounts or iron and chromium present in the metallic form following heating up to 600 °C.It appears that the carbon contamination on the surfaces plays an important role in the fate of the surface oxide layer for all of the steels heated in a vacuum environment.     

Electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy study of the corrosion behaviour of galvanized steel and electroplating steel

The efficiency of a formula containing 2-{(2-hydroxyethyl)[(4-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amino}ethanol (tolyltriazole) and decanoic acid as corrosion inhibitor for galvanized steel and electroplating steel in aqueous solution have been determined by electrochemical impedance spectroscopy (EIS) techniques. The experimental data obtained from this method show a frequency distribution and therefore a modelling element with frequency dispersion behaviour, a constant phase element (CPE) has been used. The corrosion behaviour in the presence of different concentration of decanoic acid (DA) in the formula was also investigated by EIS. Results obtained reveal that, the formula is a good inhibitor for galvanized steel and electroplating steel in aqueous solution, the better performance was obtained in the case of galvanized steel. The ability of the inhibitor to be adsorbed on the surface was dependent on the nature of metal. X-ray photoelectron spectroscopy surface analysis with inhibitor shows that it's chemisorbed at the galvanized and electroplating steel/aqueous solution interface.     

Valence band offset of GaN/diamond heterojunction measured by X-ray photoelectron spectroscopy

XPS was used to measure the energy discontinuity in the GaN/diamond heterostructure. The valence band offset (VBO) was determined to be 0.38 ± 0.15 eV and a type-II heterojunction with a conduction band offset (CBO) of 2.43 ± 0.15 eV was obtained.     

A method for the study of surface segregation in multicomponent alloys

A simple algorithm for the determination of segregation profiles in multicomponent systems based on a mean field formalism and a quantum approximate method for the energetics is introduced. The method is described and applied to two ternary systems, concentrating on the changes in segregation patterns relative to the corresponding binary cases.     

Influence of CrN surface compound on the initial stages of high temperature oxidation of ferritic stainless steel

Segregation phenomena and formation of surface compounds on Fe-17Cr (ferritic stainless steel) were studied at temperatures up to 800 °C upon annealing and kinetically controlled oxidation by photoelectron spectroscopy and inelastic electron background analysis. The results revealed the formation of a chromium nitride surface compound during annealing in ultrahigh vacuum at temperatures exceeding 527 °C. Surface enrichment of P, As, and other trace elements became more prominent at higher temperatures approaching 800 °C. It was found that nitrogen was buried below the surface oxide layer during oxygen exposure, yet it had little effect on the rate of oxidation. However, the formation of CrN surface compound promoted the selective oxidation of Cr initially, which is of great importance in processing and application environments involving high temperature and controlled atmosphere conditions.