Aerosol damage to a microchannel plate analysed by X‐ray photoelectron spectromicroscopy

Localised corrosion on a microchannel plate has been studied using X‐ray photoelectron spectromicroscopy. Curve fitting to the spectra at each pixel in the image data set reveals the presence of sodium and carbonate species at the corrosion sites, which optical microscopy suggests originated as droplets. It is proposed that aerosol contamination of the alkali enriched microchannel plate during removal of particulate material using a stream of compressed gas was responsible for the initiation of corrosion. Copyright © 2006 John Wiley & Sons, Ltd.     

X‐ray photoelectron spectroscopy studies of chromium compounds

Photoelectron spectra of a number of chromium oxides and other compounds were studied under high spectral resolution conditions chosen to reduce the possibility of differential charging. Some of the suite of Cr(III) compounds chosen for study produced Cr 2p spectra containing fine structure that could be identified with multiplet splitting. The splitting patterns produced were similar for all trivalent binary and ternary oxides and sulphides whose patterns closely reproduced the splitting predicted for the Cr(III) free ion by Gupta and Sen. The fine structure observed for compounds such as chromium (III) chloride had a distinctly different pattern. A number of other chromium (III) compounds were studied that did not exhibit the fine structure described above; nonetheless, well‐defined line shapes and reproducible peak centroids were obtained by fitting protocols. The use of such information to determine surface chemistry on chromated steels is described, based on the spectral knowledge of chromium (III) oxides and hydroxides and the chromium (VI) oxide systems. Copyright © 2004 John Wiley & Sons, Ltd.     

Germanium carboxylates: the first X‐ray diffraction study of germanium(II) dicarboxylate and germanium(IV) tetracarboxylate

Germanium(II) dipropionate (1) has been synthesized and its crystal structure, as well as that of germanium(IV) tetrapropionate (2), has been determined. By contrast to monomeric 2 with monodentate propionate ligands, compound 1 is associated, forming a cyclotetramer [Ge(O₂CEt)₂]₄ (1a) via intermolecular dative C?O → Ge interactions. Copyright © 2005 John Wiley & Sons, Ltd.     

X‐ray photoelectron microscopic imaging of the chemical bonding state of Si in a rock sample

A microscopic surface analytical technique is desirable for detailed studies of environmental and geochemical surface processes because most of the relevant solid components from natural sources are heterogeneous and have intricate microstructures. Recent advances in XPS instrumentation have allowed chemical mapping of surfaces. This paper demonstrates the imaging of the chemical bonding state of Si in a rock sample (granodiorite) by X‐ray photoelectron microscopy. An Si 2p photoelectron image of the granodiorite was acquired from the boundary between the quartz and biotite phases, and the image was deconvoluted into quartz and biotite components on the basis of the difference (chemical shift) between the Si 2p binding energies of the two minerals. The two phases were clearly distinguishable in the chemical‐bonding‐state images for Si. Copyright © 2004 John Wiley & Sons, Ltd.     

The X‐ray photoelectron spectra of Ir,IrO2 and IrCl3 revisited

The X‐ray photoelectron spectra of metallic iridium and the technologically important iridium compounds, IrO₂ and IrCl₃, have been studied. The results not only improve the accuracy of published data but also expand the binding energy database of other iridium core‐levels. The difference between anhydrous and hydrated materials is explored, and the effect on curve‐fitting is discussed, together with the derivation of suitable line shapes for peak fitting of data acquired from a conventional monochromatic Al K_α X‐ray source. Copyright © 2017 John Wiley & Sons, Ltd.     

Quantitative analysis of saccharides by X‐ray photoelectron spectroscopy

A series of saccharides, including several monohydrates and one amorphous phase, has been investigated by XPS, providing the first database of survey and high‐resolution spectra for this class of compounds. Known stoichiometries and XPS‐determined elemental compositions agree well. XPS has sufficient precision for distinguishing the stoichiometries of mono‐, di‐, and polysaccharides. The C 1s chemical shifts of the acetal and alcohol groups are similar for all samples, albeit with slight binding energy increases in the series from mono‐ to di‐ and polysaccharides. Increasing X‐ray exposure causes a radiation‐induced increase of the aliphatic hydrocarbon emission at 285 eV, concomitant with the appearance of a high binding energy C 1s emission peak at 289.1 eV and a decrease in the O 1s/C 1s emission intensity ratio. Formation of aliphatic hydrocarbon groups is proposed to arise from dehydroxylation, while the increase in the 289.1 eV peak can be attributed to double dehydroxylation at the C₁ position or partial oxidation of an alcohol or acetal group. The rate of radiation damage correlates with previously reported rates of thermally induced caramelization. Copyright © 2009 John Wiley & Sons, Ltd.     

Consequences of x‐ray absorption fine structure for quantitative core‐level photoelectron spectroscopy

The dependence of x‐ray absorption fine structure (XAFS) on the chemical environment implies a corresponding environmental dependence of photoionization cross‐sections. The practical consequences of the XAFS for quantitative core‐level photoelectron spectroscopy have been studied for a number of materials with the help of simulations based on the ab initio FEFF code. The XAFS effects are predicted to be significant only for photoelectron kinetic energies below 250–300 eV. These effects take the form of systematic sensitivity factor variations between different chemical structural environments (e.g. compound materials quantified with reference to elemental standards). Apart from a few exceptions (e.g. the 2p core levels of Zn, Ga, Ge and As in metallic environments), the XAFS should introduce no significant errors when conventional Mg Kα or Al Kα sources are used for excitation. For core‐level spectra excited with synchrotron radiation or He II radiation sources, the quantification errors can readily approach or exceed 10% at room temperature (and are expected to increase at lower temperatures). Copyright © 2003 John Wiley & Sons, Ltd.     

X‐ray photoelectron spectroscopic chemical state quantification of mixed nickel metal,oxide and hydroxide systems

Quantitative chemical state X‐ray photoelectron spectroscopic analysis of mixed nickel metal, oxide, hydroxide and oxyhydroxide systems is challenging due to the complexity of the Ni 2p peak shapes resulting from multiplet splitting, shake‐up and plasmon loss structures. Quantification of mixed nickel chemical states and the qualitative determination of low concentrations of Ni(III) species are demonstrated via an approach based on standard spectra from quality reference samples (Ni, NiO, Ni(OH)₂, NiOOH), subtraction of these spectra, and data analysis that integrates information from the Ni 2p spectrum and the O 1s spectra. Quantification of a commercial nickel powder and a thin nickel oxide film grown at 1‐Torr O₂ and 300 °C for 20 min is demonstrated. The effect of uncertain relative sensitivity factors (e.g. Ni 2.67 ± 0.54) is discussed, as is the depth of measurement for thin film analysis based on calculated inelastic mean free paths. Copyright © 2009 John Wiley & Sons, Ltd.     

Interface characterization of a metal‐oxide‐semiconductor structure by biased X‐ray photoelectron spectroscopy

X‐ray photoelectron spectroscopy (XPS) measurements of a Pt/HfO₂(SiO₂)/Si metal‐oxide‐semiconductor (MOS) structure under a bias voltage applied between the gate metal and the silicon substrate were studied. The binding energy shifts of Pt 4f, Hf 4f, O 1s and Si 2p according to the applied voltage were investigated using the MOS structure. After the influence of measurements on the results was carefully examined under various conditions, the amount of the shifts was analyzed from a viewpoint of band alignment. Based on the experimental results, a new way of interpreting the deviation of the electric properties from the ideal ones in a band diagram was proposed. It was demonstrated that the biased XPS is a very powerful method to understand the origin of the electric properties of MOS. Copyright © 2010 John Wiley & Sons, Ltd.     

X‐ray induced reduction of rhenium salts and supported oxide catalysts

The analysis of Re⁷⁺ compounds has revealed a time‐dependent photoreduction during X‐ray photoelectron spectroscopy (XPS) measurements. Whilst such reduction of metal ions during XPS analysis is not uncommon, this is the first time that cases specifically for rhenium have been identified in the open literature. Copyright © 2016 John Wiley & Sons, Ltd.     

X‐ray photoelectron spectroscopy analysis of the stability of platinized catalytic electrodes in dye‐sensitized solar cells

The stability of platinized catalytic electrodes prepared by thermal decomposition of hexachloroplatinic acid was investigated. The platinum on the electrode did not dissolve in the presence of the electrolyte containing an iodide/triiodide redox couple, even under anodic bias. The electrocatalytic activity of platinized catalytic electrodes sealed in a cell with oxygen‐free electrolyte did not decrease within 23 weeks. However, the charge transfer resistance value of platinized catalytic electrodes increased tenfold when the electrodes were heated at 150° for 15 min in air during the sealing process and doubled when the electrodes were reused. The XPS analysis results showed that part of the platinum catalyst on the surface of the electrode was transformed to Pt[II] and Pt[IV] during the thermal sealing process, which led to the decrease of catalytic activity of the platinized catalytic electrodes for the reduction of triiodide. A large amount of inactive iodine absorbed on the surface of the reused electrode, which was confirmed by XPS, also decreased the electrocatalytic activity of the electrodes. The electrocatalytic activity of reused electrodes can be recovered by heating again at 390 °C or removing the platinum oxide and inactive iodine by the electrochemical method. Copyright © 2004 John Wiley & Sons, Ltd.     

Effects of elastic scattering and analyzer‐acceptance angle on the analysis of angle‐resolved X‐ray photoelectron spectroscopy data

We have made calculations of N 1s, O 1s, Si(oxide) 2p, Hf 4f, and Si(substrate) 2p photoelectron intensities at selected emission angles for films of SiO_1.6N_0.4 and HfO_1.9N_0.1 of various thicknesses on silicon. These calculations were made with the National Institute of Standards and Technology (NIST) Database for Simulation of Electron Spectra for Surface Analysis (SESSA) to investigate effects of elastic scattering and analyzer‐acceptance angle that could be relevant in the analysis of angle‐resolved X‐ray photoelectron spectroscopy (ARXPS) experiments. The simulations were made for an XPS configuration with a fixed angle between the X‐ray source (i.e. for the sample‐tilting mode of ARXPS) and with Al and Cu Kα X‐ray sources. The no‐loss intensities changed appreciably as elastic scattering was switched ‘on’ and ‘off’, but changing the analyzer‐acceptance angle had a smaller effect. Ratios of intensities for each line from the overlayer film for the least realistic model condition (elastic scattering switched ‘off’, small analyzer‐acceptance angle) to those from the most realistic model condition (elastic scattering switched ‘on’, finite analyzer‐acceptance angle) changed relatively slowly with emission angle, but the corresponding intensity ratio for the Si(substrate) 2p line changed appreciably with emission angle. The latter changes, in particular, indicate that neglect of elastic‐scattering effects can lead to erroneous results in the analysis of measured ARXPS data. The elastic‐scattering effects were larger in HfO_1.9N_0.1 than in SiO_1.6N_0.4 (due to the larger average atomic number in the former compound) and were larger with the Al Kα X‐ray source than with the Cu Kα source because of the larger cross sections for elastic scattering at the lower photoelectron energies. Copyright © 2010 John Wiley & Sons, Ltd.     

X‐ray photoelectron spectroscopic study of Tencel treated with a cationic β‐cyclodextrin derivative

The interaction and the durability to laundering of a cationic β‐cyclodextrin derivative applied to Tencel were examined by x‐ray photoelectron spectroscopy (XPS). The N1(s) XPS spectra of the cationic β‐cyclodextrin treated substrates revealed the presence of the applied finish on the fibre surface and that the durability of the applied finish to hand‐wash was good. However, the cationic β‐cyclodextrin derivative showed poor durability to the ISO CO6/C2S wash protocol. Copyright © 2009 John Wiley & Sons, Ltd.     

Oxidation‐State Analysis of Ceria by X‐ray Photoelectron Spectroscopy

Three different methods to determine the oxide‐phase concentration in mixed cerium oxide by hard X‐ray photoelectron spectroscopy are applied and quantitatively compared. Synchrotron‐based characterization of the O 1s region was used as a benchmark to introduce a method based on the weighted superposition of the Ce 3d spectra of the pure Ce³⁺ and Ce⁴⁺ phases, which was shown to lead to reliable and highly accurate determination of the mean oxidation state in mixed cerium oxides. The results obtained reveal a linear relation between the third distinct final state (u′′′) satellite peak intensity of the Ce⁴⁺ phase and the Ce⁴⁺ concentration by proper inclusion of Ce³⁺‐related plasmon satellite peaks, which contradicts previous claims of nonlinear behavior. In contrast, quantitative conventional peak‐fitting procedures were shown to be well suited for the Ce 2p region due to its relatively simple structure. Additional satellite features observed in the Ce 3d spectrum of CeO₂ were proposed to originate from plasmon contributions.     

Evaluation of uncertainties in X‐ray photoelectron spectroscopy intensities associated with different methods and procedures for background subtraction. I. Spectra for monochromatic Al X‐ray

We report uncertainties in X‐ray photoelectron spectroscopy (XPS) intensities arising from commonly used methods and procedures for subtraction of the spectral background. These uncertainties were determined from a comparison of XPS intensities reported by volunteer analysts from 28 institutions and the corresponding intensities expected for a set of simulated XPS spectra. We analyzed peak intensities from 32 sets of data for a group of 12 spectra that had been simulated for a monochromated Al Kα source. Each reported intensity was compared with an expected intensity for the particular integration limits chosen by each analyst and known from the simulation design. We present ratios of the reported intensities to the expected intensities for the background‐subtraction methods chosen by the analysts. These ratios were close to unity in most cases, as expected, but deviations were found in the results from some analysts, particularly if the main peak was asymmetrical or if shakeup was present. We showed that better results for the Shirley, Tougaard, and linear backgrounds were obtained when analysts determined peak intensities over certain energy ranges or integration limits. We then were able to recommend integration limits that should be a useful guide in the determination of peak intensities for other XPS spectra. The use of relatively narrow integration limits with the Shirley and linear backgrounds, however, will lead to measures of peak intensities that are less than the total intensities. Although these measures may be satisfactory for some quantitative analyses, errors in quantitative XPS analyses can occur if there are changes in XPS lineshapes or shakeup fractions with change of chemical state. The use of curve‐fitting equations to fit an entire spectrum will generally exclude the shakeup contribution to the intensity of the main peak, and no account will be taken of any variation in the shakeup fraction with change of chemical state. Published in 2009 by John Wiley & Sons, Ltd. Certain commercial products are identified to specify the formats in which the test spectra were distributed and the software with which the test spectra were analyzed by participants. This identification does not imply that the products are endorsed or recommended by the National Institute of Standards and Technology, or that they are necessarily the most suitable for the purposes described.     

Summary of ISO/TC 201 Standard: ISO 14701:2011 – Surface chemical analysis – X‐ray photoelectron spectroscopy—measurement of silicon oxide thickness

This International Standard specifies several methods for measuring the oxide thickness at the surfaces of (100) and (111) silicon wafers as an equivalent thickness of silicon dioxide when measured using X‐ray photoelectron spectroscopy. It is only applicable to flat, polished samples and for instruments that incorporate an Al or Mg X‐ray source, a sample stage that permits defined photoelectron emission angles and a spectrometer with an input lens that may be restricted to less than a 6° cone semiangle. For thermal oxides in the range 1‐ to 8‐nm thickness, using the best method described in this International Standard, uncertainties at a 95% confidence level around 2% may be typical and around 1% at optimum. A simpler method is also given with slightly poorer, but often adequate, uncertainties. Copyright © 2012 Crown copyright.     

Surface oxidation process of a diamond‐like carbon film analyzed by difference X‐ray photoelectron spectroscopy

Difference X‐ray photoelectron spectroscopy (D‐XPS) revealed the surface oxidation process of a diamond‐like carbon (DLC) film. Evaluation of surface functional groups on DLC solely by the C 1s spectrum is difficult because the spectrum is broad and has a secondary asymmetric lineshape. D‐XPS clarified the subtle but critical changes at the DLC surface caused by wet oxidation. The hydroxyl (C―OH) group was dominant at the oxidized surface. Further oxidized carbonyl (C?O) and carboxyl (including carboxylate) (COO) groups were also obtained; however, the oxidation of C?O to COO was suppressed to some extent because the reaction required C―C bond cleavage. Wet oxidation cleaved the aliphatic hydrogenated and non‐hydrogenated sp² carbon bonds (C―H sp² and C―C sp²) to create a pair of C―OH and hydrogenated sp³ carbon (C―H sp³) bonds. The reaction yield for C―H sp² was superior at the surface, suggesting that the DLC film was hydrogen rich at the surface. Oxidation of aromatic sp² rings or polycyclic aromatic hydrocarbons such as nanographite to phenols did not occur because of their resonance stabilization with electron delocalization. Non‐hydrogenated sp³ carbon (C―C sp³) bonds were not affected by oxidation, suggesting that these bonds are chemically inert. Copyright © 2014 John Wiley & Sons, Ltd.     

Quantitative analysis of complex amino acids and RGD peptides by X‐ray photoelectron spectroscopy (XPS)

The C 1 s, N 1 s, and O 1 s core level binding energies (BEs) of the functional groups in amino acids (glycine, aspartic acid, glutamic acid, arginine, and histidine) with varied side‐chains and cell‐binding RGD‐based peptides have been determined and characterized by X‐ray photoelectron spectroscopy with a monochromatic Al K_α source. The zwitterionic nature of the amino acids in the solid state is unequivocally evident from the N 1 s signals of the protonated amine groups and the C 1 s signature of carboxylate groups. Significant adventitious carbon contamination is evident for all samples but can be quantitatively accounted for. No intrinsic differences in the XP spectra are evident between two polymorphs (α and γ) of glycine, indicating that the crystallographic differences have a minor influence on the core level BEs for this system. The two nitrogen centers in the imidazole group of histidine exhibit an N 1 s BE shift that is in line with previously reported data for theophylline and aqueous imidazole solutions, while the nitrogen and carbon chemical shifts reflect the unusual guanidinium chemical environment in arginine. It is shown that the complex envelopes of C 1 s and O 1 s photoemission spectra for short‐chain peptides can be analyzed quantitatively by reference to the less complex XP spectra of the constituent amino acids, provided the peptides are of high enough purity. The distinctive N 1 s photoemission from the amide linkages provides an indicator of peptide formation even in the presence of common impurities, and variations in the relative intensities of N 1 s were found to be diagnostic for each of the three peptides investigated (RGD, RGDS, and RGDSC). Copyright © 2013 John Wiley & Sons, Ltd.     

Modeling of PEG grafting and prediction of interfacial force profile using X‐ray photoelectron spectroscopy

Poly(ethylene glycol) (PEG)‐grafted Sephadex? derivatives were prepared by a covalent amine conjugation method and characterized using XPS. PEG‐grafting kinetics were studied using both Langmuir and Langmuir–Freundlich isotherm models by correlating fractional C? O intensities obtained from high‐resolution C 1s scans with the grafting period. Theoretical values were compared with experimental results to confirm the reliability of the modeling predictions. Detailed surface characterization of PEG‐grafted Sephadex derivatives was performed using XPS data, and the results were used to predict the interaction free energy and stick force exerted at the matrix interface. Copyright © 2011 John Wiley & Sons, Ltd.     

Studies of degradation behaviors of poly (3‐hexylthiophene) layers by X‐ray photoelectron spectroscopy

Degradation behaviors of poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) layers on NiO in the presence of H₂O at ambient pressure and dark conditions were studied using X‐ray photoelectron spectroscopy (XPS). Upon H₂O exposure at 120 °C, partial oxidation of P3HT together with molecular water incorporation, but with the maintained local ring‐structure, were deduced by XPS. Valence band spectra of XPS evidenced that the partial oxidation of P3HT local structure could alter π‐conjugation systems of P3HT layers, forming additional electronic states close to its original highest occupied molecular orbital. For comparison, P3HT surface was also exposed to O₂, and no change in the S 2p and C 1s spectra was found by O₂ exposure at 120 °C, implying that H₂O plays a major role at the initial stage of P3HT oxidation. Copyright © 2014 John Wiley & Sons, Ltd.