Adsorption and electron-induced polymerization of methyl methacrylate on Ru(1010)

The adsorption and electron irradiation of methyl methacrylate (MMA) on a Ru(1010) surface have been studied using x-ray photoelectron spectroscopy (XPS), temperature programmed desorption (TPD), and low energy ion scattering. TPD analysis indicates that a monolayer of MMA chemisorbs and dissociates on the Ru(1010) surface. The reaction products observed upon heating include H(2), CO, CO(2), and a small amount of MMA. Physisorbed multilayers of MMA desorb at temperatures around 170 K. Electron irradiation of physisorbed MMA at 140 K leads to a modification of the MMA film: The XPS spectra show an increase in thermal stability of the film with retention of the MMA structure, and indicate that electron irradiation induces polymerization. An increase in the electron bombardment fluence induces a degradation of the formed polymerized species and leads to the accumulation of carbon on the Ru surface. These results are relevant to the accumulation of carbon on surfaces of Ru films that serve as capping layers on MoSi multilayer mirrors used in extreme ultraviolet lithography.     

Ultra-Shallow Chemical Characterization of Organic Thin Films Deposited by Plasma and Vacuum-Ultraviolet, Using Angle- and Excitation Energy-Resolved XPS

Nitrogen (N)-rich organic thin films were deposited using both low-pressure plasma- and vacuum-ultraviolet-based techniques, from mixtures of ammonia (NH₃) and ethylene (C₂H₄). These films were investigated using angle-resolved and excitation energy resolved X-ray photoelectron spectroscopy (ARXPS and ERXPS, respectively) in order to determine their sub-surface chemical profiles. These two techniques enable one to tune the ??XPS 95%?? information depth, z _95%, by varying either the angle or the excitation energy. Using a combination of both techniques, z _95% can be varied continuously from 0.7 to 11 nm. The surface-near chemistry is investigated using both high-resolution C 1s spectra and elemental concentrations derived from elemental peak intensities. Results show that while laboratory XPS, and even ARXPS, suggest homogenous surface chemistries, the novel combination of ARXPS and ERXPS points to the existence of a compositional profile in the extreme outer surface layer. Our conclusions are supported by simulations using SESSA software.     

XPS investigations of ink‐jet printed paper

Different ink‐jet printed paper materials were investigated using X‐ray photoelectron spectroscopy (XPS) yielding the elemental composition of the near‐surface region of the papers. We found significant differences with respect to the detected elements and their atomic concentrations in the different inks studied here. Two different groups of inks could be identified by means of a lower ratio of the O and C atomic concentrations and lower concentrations in specific trace elements like Mg, Na and Si. High‐resolution spectra of C 1s and O 1s core levels allowed a detailed determination of the chemical state of the respective elements. On the basis of a detailed deconvolution of these XPS signals, significant differences between all the investigated ink‐jet printed papers were found, thereby allowing their discrimination. The applicability of the measurements and, more generally, the XPS technique for forensic investigations of paper are discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

Minimum detectable activity, systematic uncertainties, and the ISO 11929 standard

The Currie formulation for minimum detectable activity (MDA) has served for decades as the standard method for estimating radiological detection limits-it is simple and statistically defendable. It does, however, lack a means to account for the effects of systematic uncertainties. In recent years we have seen various efforts to incorporate systematic uncertainties into an MDA framework. Perhaps most notable of these is the recent ISO standard 11929 for the determination of characteristic limits in ionizing radiation measurements. This standard brings a Bayesian perspective to the problem of characteristic limits in radiation measurements that are in many ways both welcome and long overdue. In this paper, however, we note some apparent drawbacks to the ISO 11929 approach. Namely, for small values of the systematic uncertainty the correction it makes to the Currie MDA is negligible, while for large systematic uncertainties the calculated MDA values can become infinite. In between these two extremes, the user has little basis for evaluating the reliability of the result. To address these issues, we consider the problem from a new approach, developing a straightforward phenomenological statistical model of the MDA that treats systematic uncertainties explicitly. We compare predictions from our model with results of the ISO 11929 formulation as well as the traditional Currie approach. Finally, some recommendations for alternative handling of the MDA in the face of significant systematic uncertainties are presented.     

Application of Multivariate curve resolution-alternating least square methods on the resolution of overlapping CE peaks from different separation conditions

Discussed in this paper is the development of a new strategy to improve resolution of overlapping CE peaks by using second-order multivariate curve resolution with alternating least square (second-order MCR-ALS) methods. Several kinds of organic reagents are added, respectively, in buffers and sets of overlapping peaks with different separations are obtained. Augmented matrix is formed by the corresponding matrices of the overlapping peaks and is then analyzed by the second-order MCR-ALS method in order to use all data information to improve the precision of the resolution. Similarity between the resolved unit spectrum and the true one is used to assess the quality of the solutions provided by the above method. 3,4-Dihydropyrimidin-2-one derivatives (DHPOs) are used as model components and mixed artificially in order to obtain overlapping peaks. Three different impurity levels, 100, 20, and 10% relative to the main component, are used. With this strategy, the concentration profiles and spectra of impurities, which are no more than 10% of the main component, can be resolved from the overlapping peaks without pure standards participant in the analysis. The effects of the changes in the components spectra in the buffer with different organic reagents on the resolution are also evaluated, which are slight and can thus be ignored in the analysis. Individual data matrices (two-way data) are also analyzed by using MCR-ALS and heuristic evolving latent projections (HELP) methods and their results are compared with those when MCR-ALS is applied to augmented data matrix (three-way data) analysis.     

高效液相色谱法测定黄浦江表层沉积物中的痕量多环芳烃

建立了高效液相色谱-二极管阵列检测器(PDA)测定上海市黄浦江表层沉积物中16种多环芳烃(PAHs)的方法。在保留时间定性分析的基础上,利用PDA获取的紫外扫描光谱图对目标组分进行了准确的定性,并通过异构体紫外光谱图中特征峰的差异有效地识别了样品中的4种异构体,即苯并［b］荧蒽、 苯并［k］荧蒽、 苯并［a］芘和苯并［e］芘。通过检测波长的优化,减少了干扰物的影响,提高了检测灵敏度;针对分离度较差的两种目标组分(苯并［b］荧蒽和苯并［k］荧蒽)的定量进行了分析讨论。该方法对16种PAHs的检出限(以干基计)介于1.1～18.3 ng/g之间,具有较高的方法灵敏度。黄浦江表层沉积物测定结果表明,除二氢苊外的15种PAHs都被检出,含量为10.1～253.0 ng/g。     

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．     

Evaluation of uncertainties in X‐ray photoelectron spectroscopy intensities associated with different methods and procedures for background subtraction. II. Spectra for unmonochromated Al and Mg X‐rays

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 and the corresponding intensities expected for a set of simulated XPS spectra. We analyzed peak intensities from 16 sets of data (submitted from 15 institutions) for a group of 12 spectra that had been simulated for an unmonochromated Al‐Kα source and similar intensities from 20 sets of data (submitted from 17 institutions) that had been simulated for an unmonochromated Mg‐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 shakeup was present. We showed that better results for the Shirley and Tougaard backgrounds were obtained when analysts determined peak intensities over certain energy ranges or integration limits. We then were able to suggest 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 intensity 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 any variation in the shakeup fraction with change of chemical state will not be taken into account. Published in 2009 by John Wiley & Sons, Ltd.     

Photoluminescent multilayer film based on polyoxometalate and tris(2,2-bipyridine)ruthenium

A photoluminescent multilayer film based on Keggin-type polyoxometalate PMo₁₂O₄₀³⁻ (PMo₁₂) and transition metal complex tris(2,2-bipyridine) ruthenium [Ru(bpy)₃]²⁺ (Ru(bpy)) was prepared by using layer-by-layer assembly(LBL). The formation of multilayer film was monitored by ultraviolet absorption spectra. The absorption intensity of characteristic peaks increase with a four-layer cycle, indicating that the LBL assembly film grow linearly and reproducibly from layer to layer. The composition of the film was measured by X-ray photoelectron spectrum (XPS). The data of XPS confirmed the presence of the expected elements. The film exhibited photoluminescence arising from π^*−t_2g ligand-to-metal transition of Ru(bpy) and redox activity attributing to molybdenum-centered redox processes of PMo₁₂. The surface morphology of multilayer film was characterized by atomic force microscopy (AFM). The result shows that the film had a smooth surface with root-mean-square (rms) roughness ca. 1.363 nm for {PEI/(PSS/PEI/PMo₁₂/Ru(bpy))₃}. The grains are homogeneously dispersed in the substrate and have a rather narrow diameter size distribution.     

Photoemission on gold-55-clusters derived from gold-phosphine AuP(C6H5)3Cl

We measured XPS and UPS spectra of gold clusters with 55 atoms, embedded in an electrically isolating phosphine matrix, and of gold-phosphine, from which the clusters were chemically derived. Compared to the spectra of bulk gold the valence band spectrum and the core level spectra of the clusters showed shifts of the peaks and the fermi level to higher binding energies. The shift of the peaks could qualitatively be interpreted by a final state effect. We succeeded in a separation of bulk and surface contributions to the core level spectra and in a reasonable quantitative analysis of the valence band spectrum of the clusters. The Au 4f core level spectrum of gold-phosphine showed two peaks at 1.5 eV higher binding energies than the corresponding peaks of the clusters.     

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.     

完全重叠色波二维谱的解析新方法

提出一种新的完全重叠色波二维谱解析方法。对于两组分色谱－光谱数据阵，只要在重叠区中存在单组分区，就能解得各组分的纯色谱和纯光谱，这种方法将求解纯谱问题转化为优化问题，再用数值遗传算法寻找最优解．本法用于２，４－二硝基苯酚和３，５－二硝基苯甲酸的合成实验以及四环素的杂质分析都得到满意的结果．     

Analysis and deconvolution of dimethylnaphthalene isomers using gas chromatography vacuum ultraviolet spectroscopy and theoretical computations

An issue with most gas chromatographic detectors is their inability to deconvolve coeluting isomers. Dimethylnaphthalenes are a class of compounds that can be particularly difficult to speciate by gas chromatography – mass spectrometry analysis, because of their significant coelution and similar mass spectra. As an alternative, a vacuum ultraviolet spectroscopic detector paired with gas chromatography was used to study the systematic deconvolution of mixtures of coeluting isomers of dimethylnaphthalenes. Various ratio combinations of 75:25; 50:50; 25:75; 20:80; 10:90; 5:95; and 1:99 were prepared to test the accuracy, precision, and sensitivity of the detector for distinguishing overlapping isomers that had distinct, but very similar absorption spectra. It was found that, under reasonable injection conditions, all of the pairwise overlapping isomers tested could be deconvoluted up to nearly two orders of magnitude (up to 99:1) in relative abundance. These experimental deconvolution values were in agreement with theoretical covariance calculations performed for two of the dimethylnaphthalene isomers. Covariance calculations estimated high picogram detection limits for a minor isomer coeluting with low to mid-nanogram quantity of a more abundant isomer. Further characterization of the analytes was performed using density functional theory computations to compare theory with experimental measurements. Additionally, gas chromatography – vacuum ultraviolet spectroscopy was shown to be able to speciate dimethylnaphthalenes in jet and diesel fuel samples.     

Dual lifetime referenced fluorometry for the determination of doxorubicin in urine

Dual lifetime referencing (DLR) is introduced as a rapid and self-referenced method for measuring the concentration of a fluorescent analyte in solution. The fluorescent cancer chemotherapeutic doxorubicin was chosen as a medically relevant analyte and blended with a reference dye (Ru(dpp)₃) that displays overlapping excitation and emission spectra. The relative contributions of the short-lived (nanoseconds) fluorescent analyte and the long-lived (microseconds) reference dye define the observed lifetime. Measuring this lifetime by both frequency-domain DLR and time-domain DLR yields similar analytical ranges and limits of detection (0.4 μM). To assess the matrix effect of medical samples, the standard addition method was employed to both modes of DLR. Urine was spiked with doxorubicin and recovery rates of ≥97% were obtained.     

Chemical state of Na and K ions in Na10K5 silicate glass under electron irradiation investigated by XPS with the aid of the line shape analysis

The Na? K (Na10K5) silicate glass, unirradiated and electron irradiated (electron dose from 25 to 8239 Cm^?2) is investigated using XPS. The measurements are performed in the angular‐resolved ADES‐400 spectrometer using AlKα X‐ray radiation and an electron beam of energy 2 keV. Owing to surface charging and ambiguity of identification of the atomic oxidized chemical states, the line shapes of selected XPS transitions are analyzed with the aid of the pattern recognition (PR) method. This method is based on a distance measure and deals with spectra representation as vectors in the n‐dimensional space. The algorithm presented, called the fuzzy k‐nearest neighbor (fkNN) rule, allows for identification of ambiguous vectors with the membership vectors described by classes membership probabilities. Under electron irradiation, the Na and K content in a surface region undergoesincrease and then slow systematic decrease. The line shape analysis indicates difficult classification of XPS spectra recorded for unirradiated and irradiated glass, especially for Na 1s transition. The chemical state of Na is a mixture of elemental and oxidized form and remains unchanged for all electron doses. Larger changes in the chemical form are observed for the K atom. In an unirradiated silicate glass, a mixture of elemental and oxide form is observed with increasing content of oxide under irradiation. The alkali atoms, Na and K, exhibit a migration effect. Comparison of PR and fitting results indicates better reliability and accuracy of the PR method. Copyright © 2008 John Wiley & Sons, Ltd.     

Establishment of structure-conductivity relationship for tris(2,2'-bipyridine) ruthenium ionic C(60) salts

Three ionic C(60) salts with [Ru(bpy)(3)](m+) (bpy = 2,2'-bipyridine) as cations were synthesized. The UV-vis-NIR spectra, XPS spectra, and elemental analysis have demonstrated their compositions: [Ru(bpy)(3)](2)(C(60)) (1), [Ru(bpy)(3)](C(60)) (2), and [Ru(bpy)(3)](C(60))(2) (3). Single crystals of polycrystalline compounds 1 and 2 were obtained as solvates. At room temperature, all three salts are semiconducting with the highest four-probe conductivity observed for compound 1 at ～10 S m(-1). The electronic conduction mechanisms can be described appropriately by an electron hopping model in this immobilized polyvalent redox system.     

Surface structural and chemical characterization of Pt/Ru composite electrodes: a combined study by XPS, STM and IR spectroscopy

Electrochemical Ru deposits on Pt(111) surfaces are investigated by STM; the images of the Ru-modified surfaces show islands of monoatomic height and between 2–5 nm in diameter. The density of islands on the surface depends on the Ru deposition potential (observed by STM and XRSD) and the cyclic voltammograms indicate an increasing Ru coverage for lower deposition potentials. The Ru surface coverage is determined by ex-situ XPS measurements and a linear dependence of the Ru coverage on the deposition potential is demonstrated. IR spectra of a monolayer of adsorbed CO on the Ru-modified Pt(111) surfaces show distinct bands for CO adsorbed on Pt and on Ru. For the integrated band intensity of the CO/Ru vibration a linear dependence on deposition potential is found indicating that lateral dipole interactions between CO adsorbed on Pt and Ru are unimportant and that the CO coverage on the Ru islands is constant for the Ru coverages investigated. The possibility of using adsorbate vibrational bands for the determination of the coverage of deposits is discussed. Received: 24 June 1996 / Revised: 6 December 1996 / Accepted: 12 December 1996     

Application of angle-resolved X-ray photon electron spectroscopy for interface and layer growth studies demonstrated on Ti/Ta-based films deposited on SiO2

X-ray photoelectron spectroscopy (XPS) is one of the main methods for elemental and bonding-state characterization in the near-surface region. Applying it as angle-resolved XPS (ARXPS), it is promising for non-destructive depth profiling in the nanometre-thickness range. The challenges for the application of ARXPS are discussed for the early film growth of Ti and Ta on SiO₂ produced by in situ magnetron sputtering. The measurements showed several phase-formation processes at the interfaces, which were used as the basis for the ARXPS data analysis and resulted in different interlayer growth information for Ti and Ta. From a systematic ARXPS data interpretation in combination with simulations, limits of the method are critically discussed.     

Concentration measurements of ozone in the 1200-300ppbv range: an intercomparison between the BNM ultraviolet standard and infrared methods

Simultaneous ultraviolet (UV) and infrared (IR) measurements of ozone concentration in air in the 1200-300 ppbv range have been performed using the ultraviolet absorption in the Hartley band at 0.2537 microm and the infrared absorption of a doublet at 9.507 microm in the nu(3) vibration-rotation band. Infrared concentration measurements were achieved using the tunable diode laser spectrometer of LPMA in Paris with interferometric control of the emitted wavelength while the UV concentration measurements were performed with the 49PS Megatec ozone generator of the Bureau National de Metrologie (BNM). The simultaneous recording of spectra of a reference cell filled with pure distilled ozone and of a low concentration mixture inside a long absorbing path Herriott cell allows to carry out infrared concentration measurements with an accuracy of the same order as the ultraviolet ones and provides the instrumental parameters of the spectrometer corresponding to each concentration measurement, which reduces systematic errors. Within the respective absolute uncertainties proper to the two techniques, no systematic discrepancy was evidenced between the IR and the UV measurements. The ozone ultraviolet absorption coefficient value determined by Hearn (308.3 +/- 4 cm(-1)atm(-1)) and used by the BNM and the National Institute of Standards and Technology (NIST) is confirmed by the present work.