Layer uniformity in glucose oxidase immobilization on SiO 2 surfaces

NASA Astrophysics Data System (ADS)

Libertino, Sebania; Scandurra, Antonino; Aiello, Venera; Giannazzo, Filippo; Sinatra, Fulvia; Renis, Marcella; Fichera, Manuela

2007-09-01

The goal of this work was the characterization, step by step, of the enzyme glucose oxidase (GOx) immobilization on silicon oxide surfaces, mainly by means of X-Ray photoelectron spectroscopy (XPS). The immobilization protocol consists of four steps: oxide activation, silanization, linker molecule deposition and GOx immobilization. The linker molecule, glutaraldehyde (GA) in this study, must be able to form a uniform layer on the sample surface in order to maximize the sites available for enzyme bonding and achieve the best enzyme deposition. Using a thin SiO 2 layer grown on Si wafers and following the XPS Si2p signal of the Si substrate during the immobilization steps, we demonstrated both the glutaraldehyde layer uniformity and the possibility to use XPS to monitor thin layer uniformity. In fact, the XPS substrate signal, not shielded by the oxide, is suppressed only when a uniform layer is deposited. The enzyme correct immobilization was monitored using the XPS C1s and N1s signals. Atomic force microscopy (AFM) measurements carried out on the same samples confirmed the results.

Transcription analysis of pilS and xpsEL genes from Xylella fastidiosa.

PubMed

Coltri, Patricia P; Rosato, Yoko B

2005-04-01

Xylella fastidiosa is a xylem-limited phytopathogen responsible for diseases in several plants such as citrus and coffee. Analysis of the bacterial genome revealed some putative pathogenicity-related genes that could help to elucidate the molecular mechanisms of plant-pathogen interactions. In the present work, the transcription of three genes of the bacterium, grown in defined and rich media and also in media containing host plant extracts (sweet orange, 'ponkan' and coffee) was analyzed by RT-PCR. The pilS gene, which encodes a sensor histidine kinase responsible for the biosynthesis of fimbriae, was transcribed when the bacterium was grown in more complex media such as PW and in medium containing plant extracts. The xps genes (xpsL and xpsE) which are related to the type II secretion system were also detected when the bacterium was grown in rich media and media with 'ponkan' and coffee extracts. It was thus observed that pilS and xpsEL genes of X. fastidiosa can be modulated by environmental factors and their expression is dependent on the nutritional status of the growth medium.

Surface Analysis of 4-Aminothiophenol Adsorption at Polycrystalline Platinum Electrodes

NASA Technical Reports Server (NTRS)

Rosario-Castro, Belinda I.; Fachini, Estevao R.; Contes, Enid J.; Perez-Davis, Marla E.; Cabrera, Carlos R.

2008-01-01

Formation of self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) on polycrystalline platinum electrodes has been studied by surface analysis and electrochemistry techniques. The 4-ATP monolayer was characterized by cyclic voltammetry (CV), Raman spectroscopy, reflection absorption infrared (RAIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) experiments give an idea about the packing quality of the monolayer. RAIR and Raman spectra for 4-ATP modified platinum electrodes showed the characteristic adsorption bands for neat 4-ATP indicating the adsorption of 4-ATP molecules on platinum surface. The adsorption on platinum was also evidenced by the presence of sulfur and nitrogen peaks by XPS survey spectra of the modified platinum electrodes. High resolution XPS studies and RAIR spectrum for platinum electrodes modified with 4-ATP indicate that molecules are sulfur-bonded to the platinum surface. The formation of S-Pt bond suggests that ATP adsorption gives up an amino terminated SAM. Thickness of the monolayer was evaluated via angle-resolved XPS (AR-XPS) analyses. Derivatization of 4-ATP SAM was performed using 16-Br hexadecanoic acid.

Novel applications of X-ray photoelectron spectroscopy on unsupported nanoparticles

NASA Astrophysics Data System (ADS)

Kostko, Oleg; Xu, Bo; Jacobs, Michael I.; Ahmed, Musahid

X-ray photoelectron spectroscopy (XPS) is a powerful technique for chemical analysis of surfaces. We will present novel results of XPS on unsupported, gas-phase nanoparticles using a velocity-map imaging (VMI) spectrometer. This technique allows for probes of both the surfaces of nanoparticles via XPS as well as their interiors via near edge X-ray absorption fine structure (NEXAFS) spectroscopy. A recent application of this technique has confirmed that arginine's guanidinium group exists in a protonated state even in strongly basic solution. Moreover, the core-level photoelectron spectroscopy can provide information on the effective attenuation length (EAL) of low kinetic energy electrons. This contradictory value is important for determining the probing depth of XPS and in photolithography. A new method for determining EALs will be presented.

A first-principles core-level XPS study on the boron impurities in germanium crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamauchi, Jun; Yoshimoto, Yoshihide; Suwa, Yuji

2013-12-04

We systematically investigated the x-ray photoelectron spectroscopy (XPS) core-level shifts and formation energies of boron defects in germanium crystals and compared the results to those in silicon crystals. Both for XPS core-level shifts and formation energies, relationship between defects in Si and Ge is roughly linear. From the similarity in the formation energy, it is expected that the exotic clusters like icosahedral B12 exist in Ge as well as in Si.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, Laura; Harvey, Stephen P.; Teeter, Glenn

We demonstrate the potential of X-ray photoelectron spectroscopy (XPS) to characterize new carrier-selective contacts (CSC) for solar cell application. We show that XPS not only provides information about the surface chemical properties of the CSC material, but that operando XPS, i.e. under light bias condition, can also directly measure the photovoltage that develops at the CSC/absorber interface, revealing device relevant information without the need of assembling a full solar cell. We present the application of the technique to molybdenum oxide hole-selective contact films on a crystalline silicon absorber.

Combined PIXE and XPS analysis on republican and imperial Roman coins

NASA Astrophysics Data System (ADS)

Daccà, A.; Prati, P.; Zucchiatti, A.; Lucarelli, F.; Mandò, P. A.; Gemme, G.; Parodi, R.; Pera, R.

2000-03-01

A combined PIXE and XPS analysis has been performed on a few Roman coins of the republican and imperial age. The purpose was to investigate via XPS the nature and extent of patina in order to be capable of extracting PIXE data relative to the coins bulk. The inclusion of elements from the surface layer, altered by oxidation and inclusion, is a known source of uncertainty in PIXE analyses of coins, performed to assess the composition and the provenance.

Upgrade of the Surface Spectrometer at NEPOMUC for PAES, XPS and STM Investigations

NASA Astrophysics Data System (ADS)

Zimnik, S.; Lippert, F.; Hugenschmidt, C.

2014-04-01

The characterization of the elemental composition of surfaces is of great importance for the understanding of many surface processes, such as surface segregation or oxidation. Positron-annihilation-induced Auger Electron Spectroscopy (PAES) is a powerful technique for gathering information about the elemental composition of only the topmost atomic layer of a sample. The upgraded surface spectrometer at NEPOMUC (NEtron induced POsitron source MUniCh) enables a comprehensive surface analysis with the complementary techniques STM, XPS and PAES. A new X-ray source for X-ray induced photoelectron spectroscopy (XPS) was installed to gather additional information on oxidation states. A new scanning tunneling microscope (STM) is used as a complementary method to investigate with atomic resolution the surface electron density. The combination of PAES, XPS and STM allows the characterization of both the elemental composition, and the surface topology.

Surface analysis characterisation of gum binders used in modern watercolour paints

NASA Astrophysics Data System (ADS)

Sano, Naoko; Cumpson, Peter J.

2016-02-01

Conducting this study has demonstrated that not only SEM-EDX but also XPS can be an efficient tool for characterising watercolour paint surfaces. We find that surface effects are mediated by water. Once the powdered components in the watercolour come into contact with water they dramatically transform their chemical structures at the surface and show the presence of pigment components with a random dispersion within the gum layer. Hence the topmost surface of the paint is confirmed as being composed of the gum binder components. This result is difficult to confirm using just one analytical technique (either XPS or SEM-EDX). In addition, peak fitting of C1s XPS spectra suggests that the gum binder in the commercial watercolour paints is probably gum arabic (by comparison with the reference materials). This identification is not conclusive, but the combination techniques of XPS and SEM shows the surface structure with material distribution of the gum binder and the other ingredients of the watercolour paints. Therefore as a unique technique, XPS combined with SEM-EDX may prove a useful method in the study of surface structure for not only watercolour objects but also other art objects; which may in future help in the conservation for art.

13C NMR and XPS characterization of anion adsorbent with quaternary ammonium groups prepared from rice straw, corn stalk and sugarcane bagasse

NASA Astrophysics Data System (ADS)

Cao, Wei; Wang, Zhenqian; Zeng, Qingling; Shen, Chunhua

2016-12-01

Despite amino groups modified crop straw has been intensively studied as new and low-cost adsorbent for removal of anionic species from water, there is still a lack of clear characterization for amino groups, especially quaternary ammonium groups in the surface of crop straw. In this study, we used 13C NMR and XPS technologies to characterize adsorbents with quaternary ammonium groups prepared from rice straw, corn stalk and sugarcane bagasse. 13C NMR spectra clearly showed the presence of quaternary ammonium groups in lignocelluloses structure of modified crop straw. The increase of nitrogen observed in XPS survey spectra also indicated the existence of quaternary ammonium group in the surface of the adsorbents. The curve fitting of high-resolution XPS N1s and C1s spectra were conducted to probe the composition of nitrogen and carbon contained groups, respectively. The results showed the proportion of quaternary ammonium group significantly increased in the prepared adsorbent's surface that was dominated by methyl/methylene, hydroxyl, quaternary ammonium, ether and carbonyl groups. This study proved that 13C NMR and XPS could be successfully utilized for characterization of quaternary ammonium modified crop straw adsorbents.

X-ray Photoelectron Spectroscopy study of CaV1-xMoxO3-δ

NASA Astrophysics Data System (ADS)

Belyakov, S. A.; Kuznetsov, M. V.; Shkerin, S. N.

2018-06-01

An investigation was carried out on perovskite-based derivatives of CaV1-xMoxO3-δ using X-ray Photoelectron Spectroscopy (XPS). According to the XRD pattern, the area of homogeneity covers the region from x = 0 to x = 0.6. Wide XPS-peaks of Ca, V, Mo and O are observed, signalling that elements are presented in multiple states. A model for explaining the large chemical shifts of XPS peaks due to different charging effects on different parts of the sample surface is proposed.

Analysis of XPS spectra of Fe 2+ and Fe 3+ ions in oxide materials

NASA Astrophysics Data System (ADS)

Yamashita, Toru; Hayes, Peter

2008-02-01

Samples of the iron oxides Fe 0.94O, Fe 3O 4, Fe 2O 3, and Fe 2SiO 4 were prepared by high temperature equilibration in controlled gas atmospheres. The samples were fractured in vacuum and high resolution XPS spectra of the fractured surfaces were measured. The peak positions and peak shape parameters of Fe 3p for Fe 2+ and Fe 3+ were derived from the Fe 3p XPS spectra of the standard samples of 2FeO·SiO 2 and Fe 2O 3, respectively. Using these parameters, the Fe 3p peaks of Fe 3O 4 and Fe 1- yO are analysed. The results indicate that high resolution XPS techniques can be used to determine the Fe 2+/Fe 3+ ratios in metal oxides. The technique has the potential for application to other transition metal oxide systems.

Study of fission-product segregation in used CANDU fuel by X-ray photoelectron spectroscopy (XPS) II

NASA Astrophysics Data System (ADS)

Hocking, William H.; Duclos, A. Michael; Johnson, Lawrence H.

1994-03-01

A thorough investigation of the grain-boundary chemistry of used CANDU fuel from one intact element has been conducted by X-ray photoelectron spectroscopy (XPS). Selected findings from more extensive XPS measurements on other used CANDU fuels exposed to storage conditions are included for comparison. Cesium, rubidium, tellurium and barium have been commonly observed, often reaching high degrees of surface enrichment, although their relative abundances can vary widely with a complex dependence on the fuel irradiation history. Lower concentrations of cadmium, molybdenum, strontium and iodine have also been occasionally detected. Except for iodine, chemical-shift data are indicative of oxidized species, possibly uranates. Segregation at monolayer-level coverages has been demonstrated by sequential XPS analysis and argon-ion sputtering. Calculations based on an idealized thin-film model are consistent with the depth profiles. The interpretation of these results is discussed in the context of previous studies, especially on LWR fuels.

Characterization of fossil remains using XRF, XPS and XAFS spectroscopies

NASA Astrophysics Data System (ADS)

Zougrou, I. M.; Katsikini, M.; Pinakidou, F.; Brzhezinskaya, M.; Papadopoulou, L.; Vlachos, E.; Tsoukala, E.; Paloura, E. C.

2016-05-01

Synchrotron radiation micro-X-Ray Fluorescence (μ-XRF), X-ray photoelectron (XPS) and X-ray Absorption Fine Structure (XAFS) spectroscopies are applied for the study of paleontological findings. More specifically the costal plate of a gigantic terrestrial turtle Titanochelon bacharidisi and a fossilized coprolite of the cave spotted hyena Crocuta crocuta spelaea are studied. Ca L 2,3-edge NEXAFS and Ca 2p XPS are applied for the identification and quantification of apatite and Ca containing minerals. XRF mapping and XAFS are employed for the study of the spatial distribution and speciation of the minerals related to the deposition environment.

Quantitative depth profiling of Ce(3+) in Pt/CeO2 by in situ high-energy XPS in a hydrogen atmosphere.

PubMed

Kato, Shunsuke; Ammann, Markus; Huthwelker, Thomas; Paun, Cristina; Lampimäki, Markus; Lee, Ming-Tao; Rothensteiner, Matthäus; van Bokhoven, Jeroen A

2015-02-21

The redox property of ceria is a key factor in the catalytic activity of ceria-based catalysts. The oxidation state of well-defined ceria nanocubes in gas environments was analysed in situ by a novel combination of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) and high-energy XPS at a synchrotron X-ray source. In situ high-energy XPS is a promising new tool to determine the electronic structure of matter under defined conditions. The aim was to quantitatively determine the degree of cerium reduction in a nano-structured ceria-supported platinum catalyst as a function of the gas environment. To obtain a non-destructive depth profile at near-ambient pressure, in situ high-energy XPS analysis was performed by varying the kinetic energy of photoelectrons from 1 to 5 keV, and, thus, the probing depth. In ceria nanocubes doped with platinum, oxygen vacancies formed only in the uppermost layers of ceria in an atmosphere of 1 mbar hydrogen and 403 K. For pristine ceria nanocubes, no change in the cerium oxidation state in various hydrogen or oxygen atmospheres was observed as a function of probing depth. In the absence of platinum, hydrogen does not dissociate and, thus, does not lead to reduction of ceria.

An in situ XPS study of L-cysteine co-adsorbed with water on polycrystalline copper and gold

NASA Astrophysics Data System (ADS)

Jürgensen, Astrid; Raschke, Hannes; Esser, Norbert; Hergenröder, Roland

2018-03-01

The interactions of biomolecules with metal surfaces are important because an adsorbed layer of such molecules introduces complex reactive functionality to the substrate. However, studying these interactions is challenging: they usually take place in an aqueous environment, and the structure of the first few monolayers on the surface is of particular interest, as these layers determine most interfacial properties. Ideally, this requires surface sensitive analysis methods that are operated under ambient conditions, for example ambient pressure x-ray photoelectron spectroscopy (AP-XPS). This paper focuses on an AP-XPS study of the interaction of water vapour and l-Cysteine on polycrystalline copper and gold surfaces. Thin films of l-Cysteine were characterized with XPS in UHV and in a water vapour atmosphere (P ≤ 1 mbar): the structure of the adsorbed l-Cysteine layer depended on substrate material and deposition method, and exposure of the surface to water vapour led to the formation of hydrogen bonds between H2O molecules and the COO- and NH2 groups of adsorbed l-Cysteine zwitterions and neutral molecules, respectively. This study also proved that it is possible to investigate monolayers of biomolecules in a gas atmosphere with AP-XPS using a conventional laboratory Al-Kα x-ray source.

Dynamic XPS measurements of ultrathin polyelectrolyte films containing antibacterial Ag–Cu nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taner-Camcı, Merve; Suzer, Sefik, E-mail: suzer@fen.bilkent.edu.tr

Ultrathin films consisting of polyelectrolyte layers prepared by layer-by-layer deposition technique and containing also Ag and Cu nanoparticles exhibit superior antibacterial activity toward Escherichia coli. These films have been investigated with XPS measurements under square wave excitation at two different frequencies, in order to further our understanding about the chemical/physical nature of the nanoparticles. Dubbed as dynamical XPS, such measurements bring out similarities and differences among the surface structures by correlating the binding energy shifts of the corresponding XPS peaks. Accordingly, it is observed that the Cu2p, Ag3d of the metal nanoparticles, and S2p of cysteine, the stabilizer and themore » capping agent, exhibit similar shifts. On the other hand, the C1s, N1s, and S2p peaks of the polyelectrolyte layers shift differently. This finding leads us the claim that the Ag and Cu atoms are in a nanoalloy structure, capped with cystein, as opposed to phase separated entities.« less

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

NASA Astrophysics Data System (ADS)

Arble, Chris; Jia, Meng; Newberg, John T.

2018-05-01

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.

Applications of XPS in the characterization of Battery materials

DOE PAGES

Shutthanandan, Vaithiyalingam; Nandasiri, Manjula; Zheng, Jianming; ...

2018-05-26

In this study, technological development requires reliable power sources where energy storage devices are emerging as a critical component. Wide range of energy storage devices, Redox-flow batteries (RFB), Lithium ion based batteries (LIB), and Lithium-sulfur (LSB) batteries are being developed for various applications ranging from grid-scale level storage to mobile electronics. Material complexities associated with these energy storage devices with unique electrochemistry are formidable challenge which needs to be address for transformative progress in this field. X-ray photoelectron spectroscopy (XPS) - a powerful surface analysis tool - has been widely used to study these energy storage materials because of itsmore » ability to identify, quantify and image the chemical distribution of redox active species. However, accessing the deeply buried solid-electrolyte interfaces (which dictates the performance of energy storage devices) has been a challenge in XPS usage. Herein we report our recent efforts to utilize the XPS to gain deep insight about these interfaces under realistic conditions with varying electrochemistry involving RFB, LIB and LSB.« less

Structural, XPS and magnetic studies of pulsed laser deposited Fe doped Eu{sub 2}O{sub 3} thin film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Sandeep; Prakash, Ram, E-mail: rpgiuc@gmail.com; Choudhary, R.J.

2015-10-15

Highlights: • Growth of Fe doped Eu{sub 2}O{sub 3} thin films by PLD. • XRD and Raman’s spectroscopy used for structure confirmation. • The electronic states of Eu and Fe are confirmed by XPS. • Magnetic properties reveals room temperature magnetic ordering in deposited film. - Abstract: Fe (4 at.%) doped europium (III) oxide thin film was deposited on silicon (1 0 0) substrate by pulsed laser deposition technique. Structural, spectral and magnetic properties were studied by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and magnetization measurements. XRD and Raman spectroscopy reveal that the grown film is singlemore » phased and belongs to the cubic structure of Eu{sub 2}O{sub 3}. XPS study of the Eu{sub 1.92}Fe{sub 0.08}O{sub 3} film shows that Fe exists in Fe{sup 3+} ionic state in the film. The film exhibits magnetic ordering at room temperature.« less

Hydrolysis condensation reactions of titanium alkoxides in thin films: A study of the steric hindrance effect by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Barlier, Vincent; Bounor-Legaré, Véronique; Boiteux, Gisèle; Davenas, Joël; Léonard, Didier

2008-06-01

An original approach based on X-ray photoelectron spectroscopy (XPS) is proposed to study the influence of the surrounding humidity on the hydrolysis-condensation reactions of five titanium alkoxides in thin films. More precisely, the influence of the nature of the ligands (propoxide, butoxide, isopropoxide, phenoxide, and 9H-carbazole-9-yl-ethyl-oxy) on the reaction rate was evidenced. The reaction advancement was evaluated by comparing XPS chemical compositions to theoretical compositions calculated for all the possible rates. XPS chemical environment information allowed validating the reliability of this approach through the evaluation of the condensation state. In both approaches, the influence of the steric hindrance on the reactivity of titanium alkoxides was highlighted to be similar to what has been previously observed in solution. Theses results corroborate the validity of our XPS approach to determine titanium alkoxide hydrolysis-condensation reactions in the specific application of thin films.

Applications of XPS in the characterization of Battery materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shutthanandan, Vaithiyalingam; Nandasiri, Manjula; Zheng, Jianming

In this study, technological development requires reliable power sources where energy storage devices are emerging as a critical component. Wide range of energy storage devices, Redox-flow batteries (RFB), Lithium ion based batteries (LIB), and Lithium-sulfur (LSB) batteries are being developed for various applications ranging from grid-scale level storage to mobile electronics. Material complexities associated with these energy storage devices with unique electrochemistry are formidable challenge which needs to be address for transformative progress in this field. X-ray photoelectron spectroscopy (XPS) - a powerful surface analysis tool - has been widely used to study these energy storage materials because of itsmore » ability to identify, quantify and image the chemical distribution of redox active species. However, accessing the deeply buried solid-electrolyte interfaces (which dictates the performance of energy storage devices) has been a challenge in XPS usage. Herein we report our recent efforts to utilize the XPS to gain deep insight about these interfaces under realistic conditions with varying electrochemistry involving RFB, LIB and LSB.« less

Schottky Barrier Height of Pd/MoS2 Contact by Large Area Photoemission Spectroscopy.

PubMed

Dong, Hong; Gong, Cheng; Addou, Rafik; McDonnell, Stephen; Azcatl, Angelica; Qin, Xiaoye; Wang, Weichao; Wang, Weihua; Hinkle, Christopher L; Wallace, Robert M

2017-11-08

MoS 2 , as a model transition metal dichalcogenide, is viewed as a potential channel material in future nanoelectronic and optoelectronic devices. Minimizing the contact resistance of the metal/MoS 2 junction is critical to realizing the potential of MoS 2 -based devices. In this work, the Schottky barrier height (SBH) and the band structure of high work function Pd metal on MoS 2 have been studied by in situ X-ray photoelectron spectroscopy (XPS). The analytical spot diameter of the XPS spectrometer is about 400 μm, and the XPS signal is proportional to the detection area, so the influence of defect-mediated parallel conduction paths on the SBH does not affect the measurement. The charge redistribution by Pd on MoS 2 is detected by XPS characterization, which gives insight into metal contact physics to MoS 2 and suggests that interface engineering is necessary to lower the contact resistance for the future generation electronic applications.

Quantitative analysis of Si1-xGex alloy films by SIMS and XPS depth profiling using a reference material

NASA Astrophysics Data System (ADS)

Oh, Won Jin; Jang, Jong Shik; Lee, Youn Seoung; Kim, Ansoon; Kim, Kyung Joong

2018-02-01

Quantitative analysis methods of multi-element alloy films were compared. The atomic fractions of Si1-xGex alloy films were measured by depth profiling analysis with secondary ion mass spectrometry (SIMS) and X-ray Photoelectron Spectroscopy (XPS). Intensity-to-composition conversion factor (ICF) was used as a mean to convert the intensities to compositions instead of the relative sensitivity factors. The ICFs were determined from a reference Si1-xGex alloy film by the conventional method, average intensity (AI) method and total number counting (TNC) method. In the case of SIMS, although the atomic fractions measured by oxygen ion beams were not quantitative due to severe matrix effect, the results by cesium ion beam were very quantitative. The quantitative analysis results by SIMS using MCs2+ ions are comparable to the results by XPS. In the case of XPS, the measurement uncertainty was highly improved by the AI method and TNC method.

The adsorption of methyl iodide on uranium and uranium dioxide: Surface characterization using X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES)

NASA Astrophysics Data System (ADS)

Dillard, J. G.; Moers, H.; Klewe-Nebenius, H.; Kirch, G.; Pfennig, G.; Ache, H. J.

1984-09-01

The adsorption of methyl iodide on uranium and on uranium dioxide has been studied at 25 °C. Surfaces of the substrates were characterized before and after adsorption by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The XPS binding energy results indicate that CH 3I adsorption on uranium yields a carbide-type carbon, UC, and uranium iodide, UI 3. On uranium dioxide the carbon electron binding energy measurements are consistent with the formation of a hydrocarbon, —CH 3-type moiety. The interpretation of XPS and AES spectral features for CH 3I adsorption on uranium suggest that a complex dissociative adsorption reaction takes place. Adsorption of CH 3I on UO 2 occurs via a dissociative process. Saturation coverage occurs on uranium at approximately two langmuir (1 L = 10 -6 Torr s) exposure whereas saturation coverage on uranium dioxide is found at about five langmuir.

Chemisorbed monolayers of corannulene penta-thioethers on gold.

PubMed

Angelova, Polina; Solel, Ephrath; Parvari, Galit; Turchanin, Andrey; Botoshansky, Mark; Gölzhäuser, Armin; Keinan, Ehud

2013-02-19

Penta(tert-butylthio)corannulene and penta(4-dimethylaminophenylthio)corannulene form highly stable monolayers on gold surfaces, as indicated by X-ray photoelectron spectroscopy (XPS). Formation of these homogeneous monolayers involves multivalent coordination of the five sulfur atoms to gold with the peripheral alkyl or aryl substituents pointing away from the surface. No dissociation of C-S bonds upon binding could be observed at room temperature. Yet, the XPS experiments reveal strong chemical bonding between the thioether groups and gold. Temperature-dependent XPS study shows that the thermal stability of the monolayers is higher than the typical stability of self-assembled monolayers (SAMs) of thiolates on gold.

XPS studies of Mg doped GDC (Ce0.8Gd0.2O2-δ) for IT-SOFC

NASA Astrophysics Data System (ADS)

Tyagi, Deepak; Rao, P. Koteswara; Wani, B. N.

2018-04-01

Fuel Cells have gained much attention as efficient and environment friendly device for both stationary as well as mobile applications. For intermediate temperature SOFC (IT-SOFC), ceria based electrolytes are the most promising one, due to their higher ionic conductivity at relatively lower temperatures. Gd doped ceria is reported to be having the highest ionic conductivity. In the present work, Mg is codoped along with Gd and the electronic structure of the constituents is studied by XPS. XPS confirm that the Cerium is present in +4 oxidation state only which indicates that electronic conduction can be completely avoided.

Surface Characterization of Polymer Blends by XPS and ToF-SIMS

PubMed Central

Chan, Chi Ming; Weng, Lu-Tao

2016-01-01

The surface properties of polymer blends are important for many industrial applications. The physical and chemical properties at the surface of polymer blends can be drastically different from those in the bulk due to the surface segregation of the low surface energy component. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary mass spectrometry (ToF-SIMS) have been widely used to characterize surface and bulk properties. This review provides a brief introduction to the principles of XPS and ToF-SIMS and their application to the study of the surface physical and chemical properties of polymer blends. PMID:28773777

Thickness and composition of ultrathin SiO2 layers on Si

NASA Astrophysics Data System (ADS)

van der Marel, C.; Verheijen, M. A.; Tamminga, Y.; Pijnenburg, R. H. W.; Tombros, N.; Cubaynes, F.

2004-07-01

Ultrathin SiO2 layers are of importance for the semiconductor industry. One of the techniques that can be used to determine the chemical composition and thickness of this type of layers is x-ray photoelectron spectroscopy (XPS). As shown by Seah and Spencer [Surf. Interface Anal. 33, 640 (2002)], it is not trivial to characterize this type of layer by means of XPS in a reliable way. We have investigated a series of ultrathin layers of SiO2 on Si (in the range from 0.3 to 3 nm) using XPS. The samples were also analyzed by means of transmission electron microscopy (TEM), Rutherford backscattering (RBS), and ellipsometry. The thickness of the SiO2 layers (d) was determined from the XPS results using three different approaches: the ``standard'' equation (Seah and Spencer) for d, an overlayer-substrate model calculation, and the QUASES-Tougaard [Surf. Interface Anal. 26, 249 (1998), QUASES-Tougaard: Software package for Quantitative Analysis of Surfaces by Electron Spectroscopy, version 4.4 (2000); http://www.quases.com] method. Good agreement was obtained between the results of XPS analyses using the ``standard'' equation, the overlayer-substrate model calculation, and RBS results. The QUASES-Tougaard results were approximately 62% above the other XPS results. The optical values for the thickness were always slightly higher than the thickness according to XPS or RBS. Using the model calculation, these (relatively small) deviations from the optical results could be explained as being a consequence of surface contaminations with hydrocarbons. For a thickness above 2.5 nm, the TEM results were in good agreement with the results obtained from the other techniques (apart from QUASES-Tougaard). Below 2.5 nm, significant deviations were found between RBS, XPS, and optical data on the one hand and TEM results on the other hand; the deviations became larger as the thickness of the SiO2 decreased. This effect may be related to interface states of oxygen, which have been investigated [D. A. Muller, T. Sorsch, S. Moccio, F. H. Baumann, K. Evans-Lutterodt, and G. Timp, Nature (London) 399, 758 (1999); D. A. Muller and J. B. Neaton, Structure and Energetics of the Interface Between Si and Amorphous SiO2 in Fundamental Aspects of Silicon Oxidation, edited by Y. J. Chabal (Springer, Berlin, 2001), pp. 219-246.] by means of high-resolution electron energy loss spectroscopy measurements of the O K edge in ultrathin gate oxides of SiO2. .

An Electrochemical, Microtopographical and Ambient Pressure X-Ray Photoelectron Spectroscopic Investigation of Si/TiO 2/Ni/Electrolyte Interfaces

DOE PAGES

Lichterman, Michael F.; Richter, Matthias H.; Hu, Shu; ...

2015-12-05

The electrical and spectroscopic properties of the TiO 2/Ni protection layer system, which enables stabilization of otherwise corroding photoanodes, have been investigated in contact with electrolyte solutions by scanning-probe microscopy, electrochemistry and in-situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS). Specifically, the energy-band relations of the p +-Si/ALD-TiO 2/Ni interface have been determined for a selected range of Ni thicknesses. AP-XPS measurements using tender X-rays were performed in a three-electrode electrochemical arrangement under potentiostatic control to obtain information from the semiconductor near-surface region, the electrochemical double layer (ECDL) and the electrolyte beyond the ECDL. The degree of conductivity depended on themore » chemical state of the Ni on the TiO 2 surface. At low loadings of Ni, the Ni was present primarily as an oxide layer and the samples were not conductive, although the TiO 2 XPS core levels nonetheless displayed behavior indicative of a metal-electrolyte junction. In contrast, as the Ni thickness increased, the Ni phase was primarily metallic and the electrochemical behavior became highly conductive, with the AP-XPS data indicative of a metal-electrolyte junction. Electrochemical and microtopographical methods have been employed to better define the nature of the TiO 2/Ni electrodes and to contextualize the AP-XPS results.« less

Insights into electrochemical reactions from ambient pressure photoelectron spectroscopy.

PubMed

Stoerzinger, Kelsey A; Hong, Wesley T; Crumlin, Ethan J; Bluhm, Hendrik; Shao-Horn, Yang

2015-11-17

The understanding of fundamental processes in the bulk and at the interfaces of electrochemical devices is a prerequisite for the development of new technologies with higher efficiency and improved performance. One energy storage scheme of great interest is splitting water to form hydrogen and oxygen gas and converting back to electrical energy by their subsequent recombination with only water as a byproduct. However, kinetic limitations to the rate of oxygen-based electrochemical reactions hamper the efficiency in technologies such as solar fuels, fuel cells, and electrolyzers. For these reactions, the use of metal oxides as electrocatalysts is prevalent due to their stability, low cost, and ability to store oxygen within the lattice. However, due to the inherently convoluted nature of electrochemical and chemical processes in electrochemical systems, it is difficult to isolate and study individual electrochemical processes in a complex system. Therefore, in situ characterization tools are required for observing related physical and chemical processes directly at the places where and while they occur and can help elucidate the mechanisms of charge separation and charge transfer at electrochemical interfaces. X-ray photoelectron spectroscopy (XPS), also known as ESCA (electron spectroscopy for chemical analysis), has been used as a quantitative spectroscopic technique that measures the elemental composition, as well as chemical and electronic state of a material. Building from extensive ex situ characterization of electrochemical systems, initial in situ studies were conducted at or near ultrahigh vacuum (UHV) conditions (≤10(-6) Torr) to probe solid-state electrochemical systems. However, through the integration of differential-pumping stages, XPS can now operate at pressures in the torr range, comprising a technique called ambient pressure XPS (AP-XPS). In this Account, we briefly review the working principles and current status of AP-XPS. We use several recent in situ studies on model electrochemical components as well as operando studies performed by our groups at the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory to illustrate that AP-XPS is both a chemically and an electrically specific tool since photoelectrons carry information on both the local chemistry and electrical potentials. The applications of AP-XPS to oxygen electrocatalysis shown in this Account span well-defined studies of (1) the oxide/oxygen gas interface, (2) the oxide/water vapor interface, and (3) operando measurements of half and full electrochemical cells. Using specially designed model devices, we can expose and isolate the electrode or interface of interest to the incident X-ray beam and AP-XPS analyzer to relate the electrical potentials to the composition/chemical state of the key components and interfaces. We conclude with an outlook on new developments of AP-XPS end stations, which may provide significant improvement in the observation of dynamics over a wide range of time scales, higher spatial resolution, and improved characterization of boundary or interface layers (solid/solid and liquid/solid).

X-ray Photoelectron Spectroscopy (XPS), Rutherford Back Scattering (RBS) studies

NASA Technical Reports Server (NTRS)

Neely, W. C.; Bozak, M. J.; Williams, J. R.

1993-01-01

X-ray photoelectron spectroscopy (XPS), Rutherford Back Scattering (RBS) studies of each of sample received were completed. Since low angle X-ray could not be performed because of instrumentation problems, Auger spectrometry was employed instead. The results of these measurements for each of the samples is discussed in turn.

1300929

NASA Image and Video Library

2013-08-15

ARTHUR BROWN (AST, AEROSPACE METALLIC MATERIALS) LOADS A CERAMIC COATED SILICON WAFER INTO A KRATOS (ELECTRON SPECTROSCOPY FOR CHEMICAL ANALYSIS) TO PERFORM X-RAY PHOTOELECTRON SPECTROSCOPY (XPS). XPS IS A TECHNIQUE THAT ANALYZES THE SURFACE CHEMISTRY OF A SAMPLE BY IRRADIATING IT WITH X-RAYS AND MEASURING THE NUMBER AND KINETIC ENERGY OF ELECTRON THAT ESCAPE.

Investigating early stages of biocorrosion with XPS: AISI 304 stainless steel exposed to Burkholderia species

NASA Astrophysics Data System (ADS)

Johansson, Leena-Sisko; Saastamoinen, Tuomas

1999-04-01

We have investigated the interactions of an exopolymer-producing bacteria, Burkholderia sp. with polished AISI 304 stainless steel substrates using X-ray photoelectron spectroscopy (XPS). Steel coupons were exposed to the pure bacteria culture in a specially designed flowcell for 6 h during which the experiment was monitored in situ with an optical microscope. XPS results verified the formation of biofilm containing extracellular polymer on all the samples exposed to bacteria. Sputter results indicated that some ions needed for metabolic processes were trapped within the biofilm. Changes in the relative Fe concentration and Fe 2p peak shape indicated that also iron had accumulated into the biofilm.

Samarium electrodeposited acetate and oxide thin films on stainless steel substrate characterized by XPS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Myhre, Kristian; Burns, Jonathan; Meyer, Harry

Characterization of a samarium thin film deposited on a stainless steel substrate using molecular electrodeposition was carried out using a Thermo Scientific K-Alpha X-ray photoelectron spectrometer. We studied two types of samarium electrodeposition samples, one as-deposited and one heated to 700 °C in an air flow. Survey scans include peaks coming from the stainless steel substrate, such as Fe and Cr. An X-ray photoelectron spectroscopy (XPS) survey spectrum, Sm 3d, C 1s, and O 1s narrow scans are shown. It was determined that the heating process decomposed the deposited Sm acetate to Sm 2O 3 using XPS.

Samarium electrodeposited acetate and oxide thin films on stainless steel substrate characterized by XPS

DOE PAGES

Myhre, Kristian; Burns, Jonathan; Meyer, Harry; ...

2016-06-01

Characterization of a samarium thin film deposited on a stainless steel substrate using molecular electrodeposition was carried out using a Thermo Scientific K-Alpha X-ray photoelectron spectrometer. We studied two types of samarium electrodeposition samples, one as-deposited and one heated to 700 °C in an air flow. Survey scans include peaks coming from the stainless steel substrate, such as Fe and Cr. An X-ray photoelectron spectroscopy (XPS) survey spectrum, Sm 3d, C 1s, and O 1s narrow scans are shown. It was determined that the heating process decomposed the deposited Sm acetate to Sm 2O 3 using XPS.

XPS Study of Oxide/GaAs and SiO2/Si Interfaces

NASA Technical Reports Server (NTRS)

Grunthaner, F. J.; Grunthaner, P. J.; Vasquez, R. P.; Lewis, B. F.; Maserjian, J.; Madhukar, A.

1982-01-01

Concepts developed in study of SiO2/Si interface applied to analysis of native oxide/GaAs interface. High-resolution X-ray photoelectron spectroscopy (XPS) has been combined with precise chemical-profiling technique and resolution-enhancement methods to study stoichiometry of transitional layer. Results are presented in report now available.

Use of XPS to clarify the Hall coefficient sign variation in thin niobium layers buried in silicon

NASA Astrophysics Data System (ADS)

Demchenko, Iraida N.; Lisowski, Wojciech; Syryanyy, Yevgen; Melikhov, Yevgen; Zaytseva, Iryna; Konstantynov, Pavlo; Chernyshova, Maryna; Cieplak, Marta Z.

2017-03-01

Si/Nb/Si trilayers formed with 9.5 and 1.3 nm thick niobium layer buried in amorphous silicon were prepared by magnetron sputtering and studied using XPS depth-profile techniques in order to investigate the change of Hall coefficient sign with thickness. The analysis of high-resolution (HR) XPS spectra revealed that the thicker layer sample has sharp top interface and metallic phase of niobium, thus holes dominate the transport. In contrast, the analysis indicates that the thinner layer sample has a Nb-rich mixed alloy formation at the top interface. The authors suggest that the main effect leading to a change of sign of the Hall coefficient for the thinner layer sample (which is negative contrary to the positive sign for the thicker layer sample) may be related to strong boundary scattering enhanced by the presence of silicon ions in the layer close to the interface/s. The depth-profile reconstruction was performed by SESSA software tool confirming that it can be reliably used for quantitative analysis/interpretation of experimental XPS data.

Surface chemical reactions induced on pyrite by ion bombardment

NASA Astrophysics Data System (ADS)

Ruano, Gustavo; Pomiro, Fernando; Ferrón, Julio

2018-01-01

Through X-ray photoemission spectroscopy (XPS), we studied the chemical changes induced in a natural crystal of pyrite (FeS2) upon exposure to 4.5 keV He+ beam. We found an important reducing effect induced by ion bombardment leading to the production of iron embedded in the pyrite matrix. Through a combination of the usual Doniach-Sunjic treatment and Factor Analysis of XPS yields, we were able of analyzing the full Fe 2p XPS signal. We could in this way distinguish Fe compounds with the same binding energy for the Fe 2p3/2 yield. Our results show that He+ bombardment disrupts the ionic environment producing S2-2 and S0, Fe2+ and Fe3+ ions, and the reduction to metallic iron. The remaining pyrite matrix does not passivate the embedded iron structures, which are readily oxidized under air exposure. The oxide formed resembled that of magnetite from the XPS point of view. Further He+ bombardment proved to be efficient to reduce the iron oxide back to iron again.

Preparation of gallium nitride surfaces for atomic layer deposition of aluminum oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerr, A. J.; Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093; Chagarov, E.

2014-09-14

A combined wet and dry cleaning process for GaN(0001) has been investigated with XPS and DFT-MD modeling to determine the molecular-level mechanisms for cleaning and the subsequent nucleation of gate oxide atomic layer deposition (ALD). In situ XPS studies show that for the wet sulfur treatment on GaN(0001), sulfur desorbs at room temperature in vacuum prior to gate oxide deposition. Angle resolved depth profiling XPS post-ALD deposition shows that the a-Al{sub 2}O{sub 3} gate oxide bonds directly to the GaN substrate leaving both the gallium surface atoms and the oxide interfacial atoms with XPS chemical shifts consistent with bulk-like charge.more » These results are in agreement with DFT calculations that predict the oxide/GaN(0001) interface will have bulk-like charges and a low density of band gap states. This passivation is consistent with the oxide restoring the surface gallium atoms to tetrahedral bonding by eliminating the gallium empty dangling bonds on bulk terminated GaN(0001)« less

XPS and 31P NMR inquiry of Eu3+-induced structural modification in SnO-containing phosphate glass

NASA Astrophysics Data System (ADS)

Jiménez, José A.; Fachini, Esteban Rosim; Zhao, Chunqing

2018-07-01

The influence of Eu3+ doping on the structural properties of SnO-containing phosphate glass has been investigated by X-ray photoelectron spectroscopy (XPS) and 31P nuclear magnetic resonance (NMR) spectroscopy. Oxygen 1s XPS data indicates that the Eu3+ doping results in a higher concentration of non-bridging oxygens in the glass matrix, whereas 31P NMR shows an increase in the terminal phosphate chain tetrahedral units, i.e. the amount of Q1 sites with only one bridging oxygen. Accordingly, both techniques agree with a depolymerization effect induced by the Eu3+ ions. Further, XPS reveals that together with the Eu3+ doping, the presence of Sn4+ is supported while the presence of Eu2+ is also indicated. The structural changes are then indicated to be a consequence of redox chemistry between Sn2+ and Eu3+ promoting a transition of tin from Sn2+ with a role as network former to Sn4+ acting as network modifier in the glass system.

X-ray photoelectron spectroscopy on 1-peso and 2-pesos of the Argentine Republic

NASA Astrophysics Data System (ADS)

Gard, Faramarz S.; Duffo, Gustavo; Bergamasco, Pablo; Forlerer, Elena

2018-04-01

Relative concentrations of nickel and copper at the surface of the ring and centre parts of 1-peso and 2-pesos Argentine coins have been studied by means of X-ray photoemission spectroscopy (XPS). It has been observed Ni-enrichment at the surface of the ring (silvery) part of a 1-peso, minted in 1994, whereas the XPS data reveals lack of nickel at the surface of the centre (silvery) part of a 2-pesos, minted in 2016. This discrepancy is explained by analyzing the XPS peaks of oxygen and carbon, and is suggested to be related to the contamination layer on the surface of the coins. The XPS analysis of the golden parts of the coins, namely the centre part of the 1-peso and the ring part of the 2-pesos coins were inconclusive, due to the small amount of the Ni (nominally %2) used in those parts. The possible oxidations states of the metals at the surface of the untreated and treated coins with the artificial human sweat were also identified.

Surfactant Mediated Growth of Co on MgO(111)

NASA Astrophysics Data System (ADS)

Johnson-Steigelman, H. Trevor; Parihar, Somendra S.; Lyman, Paul F.

2010-03-01

Monolayer films of Co were deposited using an electrostatic electron-beam evaporator on single-crystal MgO(111)- √3 x√3 R 30^o substrates held at room temperature, with subsequent annealing of temperatures 400 C to 800 C. These films were characterized using low-energy electron diffraction (LEED), x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and x-ray diffraction (XRD). After short anneals of 400 C, AFM, LEED, and XPS suggest that islanding has occurred at the surface. XPS and XRD indicate the presence of elemental Co. 1-2 ML films of Ag were examined as a potential surfactant to aid in the growth of smooth Co films. Despite the fact that Ag itself formed islands, it was found that the presence of Ag did have a surfactant effect upon the thin-film growth of Co on Ag/MgO(111)- √3 x√3 R 30^o. Co islands were still present, but much more smooth than islands formed without Ag. XPS and AFM suggest strongly that Ag floated to the top of these samples at temperatures above 400 ^oC.

Comparative study of the native oxide on 316L stainless steel by XPS and ToF-SIMS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tardio, Sabrina, E-mail: s.tardio@surrey.ac.uk; Abel, Marie-Laure; Castle, James E.

2015-09-15

The very thin native oxide film on stainless steel, of the order of 2 nm, is known to be readily modified by immersion in aqueous media. In this paper, X-ray photoelectron spectroscopy (XPS) and time of flight secondary ions mass spectrometry are employed to investigate the nature of the air-formed film and modification after water emersion. The film is described in terms of oxide, hydroxide, and water content. The preferential dissolution of iron is shown to occur on immersion. It is shown that a water absorbed layer and a hydroxide layer are present above the oxide-like passive film. The concentrations ofmore » water and hydroxide appear to be higher in the case of exposure to water. A secure method for the peak fitting of Fe2p and Cr2p XPS spectra of such films on their metallic substrates is described. The importance of XPS survey spectra is underlined and the feasibility of C{sub 60}{sup +} SIMS depth profiling of a thin oxide layer is shown.« less

Surface functionalization of thin-film diamond for highly stable and selective biological interfaces

PubMed Central

Stavis, Courtney; Clare, Tami Lasseter; Butler, James E.; Radadia, Adarsh D.; Carr, Rogan; Zeng, Hongjun; King, William P.; Carlisle, John A.; Aksimentiev, Aleksei; Bashir, Rashid; Hamers, Robert J.

2011-01-01

Carbon is an extremely versatile family of materials with a wide range of mechanical, optical, and mechanical properties, but many similarities in surface chemistry. As one of the most chemically stable materials known, carbon provides an outstanding platform for the development of highly tunable molecular and biomolecular interfaces. Photochemical grafting of alkenes has emerged as an attractive method for functionalizing surfaces of diamond, but many aspects of the surface chemistry and impact on biological recognition processes remain unexplored. Here we report investigations of the interaction of functionalized diamond surfaces with proteins and biological cells using X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and fluorescence methods. XPS data show that functionalization of diamond with short ethylene glycol oligomers reduces the nonspecific binding of fibrinogen below the detection limit of XPS, estimated as > 97% reduction over H-terminated diamond. Measurements of different forms of diamond with different roughness are used to explore the influence of roughness on nonspecific binding onto H-terminated and ethylene glycol (EG)-terminated surfaces. Finally, we use XPS to characterize the chemical stability of Escherichia coli K12 antibodies on the surfaces of diamond and amine-functionalized glass. Our results show that antibody-modified diamond surfaces exhibit increased stability in XPS and that this is accompanied by retention of biological activity in cell-capture measurements. Our results demonstrate that surface chemistry on diamond and other carbon-based materials provides an excellent platform for biomolecular interfaces with high stability and high selectivity. PMID:20884854

Versailles Project on Advanced Materials and Standards Interlaboratory Study on Measuring the Thickness and Chemistry of Nanoparticle Coatings Using XPS and LEIS.

PubMed

Belsey, Natalie A; Cant, David J H; Minelli, Caterina; Araujo, Joyce R; Bock, Bernd; Brüner, Philipp; Castner, David G; Ceccone, Giacomo; Counsell, Jonathan D P; Dietrich, Paul M; Engelhard, Mark H; Fearn, Sarah; Galhardo, Carlos E; Kalbe, Henryk; Won Kim, Jeong; Lartundo-Rojas, Luis; Luftman, Henry S; Nunney, Tim S; Pseiner, Johannes; Smith, Emily F; Spampinato, Valentina; Sturm, Jacobus M; Thomas, Andrew G; Treacy, Jon P W; Veith, Lothar; Wagstaffe, Michael; Wang, Hai; Wang, Meiling; Wang, Yung-Chen; Werner, Wolfgang; Yang, Li; Shard, Alexander G

2016-10-27

We report the results of a VAMAS (Versailles Project on Advanced Materials and Standards) inter-laboratory study on the measurement of the shell thickness and chemistry of nanoparticle coatings. Peptide-coated gold particles were supplied to laboratories in two forms: a colloidal suspension in pure water and; particles dried onto a silicon wafer. Participants prepared and analyzed these samples using either X-ray photoelectron spectroscopy (XPS) or low energy ion scattering (LEIS). Careful data analysis revealed some significant sources of discrepancy, particularly for XPS. Degradation during transportation, storage or sample preparation resulted in a variability in thickness of 53 %. The calculation method chosen by XPS participants contributed a variability of 67 %. However, variability of 12 % was achieved for the samples deposited using a single method and by choosing photoelectron peaks that were not adversely affected by instrumental transmission effects. The study identified a need for more consistency in instrumental transmission functions and relative sensitivity factors, since this contributed a variability of 33 %. The results from the LEIS participants were more consistent, with variability of less than 10 % in thickness and this is mostly due to a common method of data analysis. The calculation was performed using a model developed for uniform, flat films and some participants employed a correction factor to account for the sample geometry, which appears warranted based upon a simulation of LEIS data from one of the participants and comparison to the XPS results.

AFM AND XPS Characterization of Zinc-Aluminum Alloy Coatings with Attention to Surface Dross and Flow Lines

NASA Astrophysics Data System (ADS)

Harding, Felipe A.; Alarcon, Nelson A.; Toledo, Pedro G.

Surfaces of various zinc-aluminum alloy (Zn-Al) coated steel samples are studied with attention to foreign surface dross by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS/ESCA). AFM topographic maps of zinc-aluminum alloy surfaces free of dross reveal the perfect nanoscale details of two kinds of dendrites: branched and globular. In all magnifications the dendrites appear smooth and, in general, very clean. XPS analysis of the extreme surface of a Zn-Al sample reveals Al, Zn, Si and O as the main components. The XPS results show no segregation or separation of phases other than those indicated by the ternary Al-Zn-Si diagram. For surfaces of Zn-Al plagued with impurities, high resolution AFM topographic maps reveal three situations: (1) areas with well-defined dendrites, relatively free of dross; (2) areas with small, millimeter-sized black spots known as dross; and (3) areas with large black stains, known as flow lines. Dendrite deformation and dross accumulation increase notably in the neighborhood, apparently clean to the naked eye, of dross or flow lines. XPS results of areas with dross and flow lines indicate unacceptable high concentration of Si and important Si phase separation. These results, in the light of AFM work, reveal that dross and flow lines are a consequence of a high local concentration of Si from high melting point silica and silicate impurities in the Zn-Al alloy source.

Comparing XPS on bare and capped ZrN films grown by plasma enhanced ALD: Effect of ambient oxidation

NASA Astrophysics Data System (ADS)

Muneshwar, Triratna; Cadien, Ken

2018-03-01

In this article we compare x-ray photoelectron spectroscopy (XPS) measurements on bare- and capped- zirconium nitride (ZrN) films to investigate the effect of ambient sample oxidation on the detected bound O in the form of oxide ZrO2 and/or oxynitride ZrOxNy. ZrN films in both bare- and Al2O3/AlN capped- XPS samples were grown by plasma-enhanced atomic layer deposition (PEALD) technique using tetrakis dimethylamino zirconium (TDMAZr) precursor, forming gas (5% H2, rest N2) inductively coupled plasma (ICP), and as received research grade process gases under identical process conditions. Capped samples were prepared by depositing 1 nm thick PEALD AlN on ZrN, followed by additional deposition of 1 nm thick ALD Al2O3, without venting of ALD reactor. On bare ZrN sample at room temperature, spectroscopic ellipsometry (SE) measurements with increasing ambient exposure times (texp) showed a self-limiting surface oxidation with the oxide thickness (dox) approaching 3.7 ± 0.02 nm for texp > 120 min. In XPS data measured prior to sample sputtering (tsput = 0), ZrO2 and ZrOxNy were detected in bare- samples, whereas only ZrN and Al2O3/AlN from capping layer were detected in capped- samples. For bare-ZrN samples, appearance of ZrO2 and ZrOxNy up to sputter depth (dsput) of 15 nm in depth-profile XPS data is in contradiction with measured dox = 3.7 nm, but explained from sputtering induced atomic inter-diffusion within analyzed sample. Appearance of artifacts in the XPS spectra from moderately sputtered (dsput = 0.2 nm and 0.4 nm) capped-ZrN sample, provides an evidence to ion-bombardment induced modifications within analyzed sample.

Cohort study comparing prostate photovaporisation with XPS 180W and HPS 120W laser.

PubMed

López, B; Capitán, C; Hernández, V; de la Peña, E; Jiménez-Valladolid, I; Guijarro, A; Pérez-Fernández, E; Llorente, C

2016-01-01

Prostate photovaporisation with Greenlight laser for the surgical treatment of benign prostate hyperplasia has rapidly evolve to the new XPS 180W. We have previously demonstrated the safety and efficacy of the HPS 120W. The aim of this study was to assess the functional and safety results, with a year of follow-up, of photovaporisation using the XPS 180W laser compared with its predecessor. A cohort study was conducted with a series of 191 consecutive patients who underwent photovaporisation between 1/2008 and 5/2013. The inclusion criteria were an international prostate symptom score (IPSS) >15 after medical failure, a prostate volume <80 cm(3) and a maximum flow <15 mL/s. We assessed preoperative and intraoperative variables (energy used, laser time and total surgical time), complications, catheter hours, length of stay and functional results (maximum flow, IPSS, prostate-specific antigen and prostate volume) at 3, 6 and 12 months. We analysed the homogeneity in preoperative characteristics of the 2 groups through univariate analysis techniques. The postoperative functional results were assessed through an analysis of variance of repeated measures with mixed models. A total of 109 (57.1%) procedures were performed using HPS 120W, and 82 (42.9%) were performed using XPS. There were no differences between the preoperative characteristics. We observed significant differences both in the surgical time and effective laser time in favour of the XPS system. This advantage was 11% (48 ± 15.7 vs. 53.8 ± 16.2, p<.05) and 9% (32.8 ± 11.7 vs. 36 ± 11.6, p<.05), respectively. There were no statistically significant differences in the rest of the analysed parameters. The technical improvements in the XPS 180W system help reduce surgical time, maintaining the safety and efficacy profile offered by the HPS 120W system, with completely superimposable results at 1 year of follow-up. Copyright © 2015 AEU. Publicado por Elsevier España, S.L.U. All rights reserved.

The presence of Ti(II) centers in doped nanoscale TiO2 and TiO2-xNx

NASA Astrophysics Data System (ADS)

Mikulas, Tanya; Fang, Zongtang; Gole, James L.; White, Mark G.; Dixon, David A.

2012-06-01

Unusual trends are observed in the Ti (2s, 2p) XPS spectra of Fe(II) doped TiO2 and TiO2-xNx. The binding energy of Ti (2s, 2p) initially decreases with increasing Fe(II) concentration, as expected, but increases at higher Fe(II) doping levels. Density functional theory is used to analyze the results. The observed VB-XPS and core level XPS spectra are consistent with the facile charge transfer sequence Ti(IV) + Fe(II) → Ti(III) + Fe(III) followed by Ti(III) + Fe(II) → Ti(II) + Fe(III). The formed Ti(II) sites may be relevant to nanoparticle catalysis on TiO2 surfaces.

X-PEEM, XPS and ToF-SIMS characterisation of xanthate induced chalcopyrite flotation: Effect of pulp potential

NASA Astrophysics Data System (ADS)

Kalegowda, Yogesh; Chan, Yuet-Loy; Wei, Der-Hsin; Harmer, Sarah L.

2015-05-01

Synchrotron-based X-ray photoemission electron microscopy (X-PEEM), X-ray photo-electron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and ultraviolet visible spectroscopy were used to characterize the flotation behaviour of chalcopyrite with xanthate at different processing conditions. The flotation recovery of chalcopyrite decreased from 97% under oxidative conditions (Eh ~ 385 mV SHE, pH 4) to 41% at a reductive potential of - 100 mV SHE (at pH 9). X-PEEM images constructed from the metal L3 absorption edges were used to produce near-edge X-ray absorption fine structure (NEXAFS) spectra from regions of interest, allowing the variability in mineral surface chemistry of each mineral particle to be analysed, and the effect of pulp potential (Eh) on the flotation of chalcopyrite to be determined. XPS, ToF-SIMS and NEXAFS analyses of chalcopyrite particles at oxidative conditions show that the surface was mildly oxidised and covered with adsorbed molecular CuEX. The Cu 2p XPS and Cu L2,3 NEXAFS spectra were dominated by CuI species attributed to bulk chalcopyrite and adsorbed CuEX. At a reductive potential of - 100 mV SHE, an increase in concentration of CuI and FeIII oxides and hydroxides was observed. X-PEEM analysis was able to show the presence of a low percentage of CuII oxides (CuO or Cu(OH)2) with predominantly CuI oxide (Cu2O) which is not evident in Cu 2p XPS spectra.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olivieri, Giorgia; Brown, Matthew A., E-mail: matthew.brown@mat.ethz.ch; Parry, Krista M.

Over the past decade, energy-dependent ambient pressure X-ray photoelectron spectroscopy (XPS) has emerged as a powerful analytical probe of the ion spatial distributions at the vapor (vacuum)-aqueous electrolyte interface. These experiments are often paired with complementary molecular dynamics (MD) simulations in an attempt to provide a complete description of the liquid interface. There is, however, no systematic protocol that permits a straightforward comparison of the two sets of results. XPS is an integrated technique that averages signals from multiple layers in a solution even at the lowest photoelectron kinetic energies routinely employed, whereas MD simulations provide a microscopic layer-by-layer descriptionmore » of the solution composition near the interface. Here, we use the National Institute of Standards and Technology database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to quantitatively interpret atom-density profiles from MD simulations for XPS signal intensities using sodium and potassium iodide solutions as examples. We show that electron inelastic mean free paths calculated from a semi-empirical formula depend strongly on solution composition, varying by up to 30% between pure water and concentrated NaI. The XPS signal thus arises from different information depths in different solutions for a fixed photoelectron kinetic energy. XPS signal intensities are calculated using SESSA as a function of photoelectron kinetic energy (probe depth) and compared with a widely employed ad hoc method. SESSA simulations illustrate the importance of accounting for elastic-scattering events at low photoelectron kinetic energies (<300 eV) where the ad hoc method systematically underestimates the preferential enhancement of anions over cations. Finally, some technical aspects of applying SESSA to liquid interfaces are discussed.« less

Versailles Project on Advanced Materials and Standards Interlaboratory Study on Measuring the Thickness and Chemistry of Nanoparticle Coatings Using XPS and LEIS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Belsey, Natalie A.; Cant, David J. H.; Minelli, Caterina

We report the results of a VAMAS (Versailles Project on Advanced Materials and Standards) inter-laboratory study on the measurement of the shell thickness and chemistry of nanoparticle coatings. Peptide-coated gold particles were supplied to laboratories in two forms: a colloidal suspension in pure water and; particles dried onto a silicon wafer. Participants prepared and analyzed these samples using either X-ray photoelectron spectroscopy (XPS) or low energy ion scattering (LEIS). Careful data analysis revealed some significant sources of discrepancy, particularly for XPS. Degradation during transportation, storage or sample preparation resulted in a variability in thickness of 53 %. The calculation methodmore » chosen by XPS participants contributed a variability of 67 %. However, variability of 12 % was achieved for the samples deposited using a single method and by choosing photoelectron peaks that were not adversely affected by instrumental transmission effects. The study identified a need for more consistency in instrumental transmission functions and relative sensitivity factors, since this contributed a variability of 33 %. The results from the LEIS participants were more consistent, with variability of less than 10 % in thickness and this is mostly due to a common method of data analysis. The calculation was performed using a model developed for uniform, flat films and some participants employed a correction factor to account for the sample geometry, which appears warranted based upon a simulation of LEIS data from one of the participants and comparison to the XPS results.« less

Reference binding energies of transition metal carbides by core-level x-ray photoelectron spectroscopy free from Ar+ etching artefacts

NASA Astrophysics Data System (ADS)

Greczynski, G.; Primetzhofer, D.; Hultman, L.

2018-04-01

We report x-ray photoelectron spectroscopy (XPS) core level binding energies (BE's) for the widely-applicable groups IVb-VIb transition metal carbides (TMCs) TiC, VC, CrC, ZrC, NbC, MoC, HfC, TaC, and WC. Thin film samples are grown in the same deposition system, by dc magnetron co-sputtering from graphite and respective elemental metal targets in Ar atmosphere. To remove surface contaminations resulting from exposure to air during sample transfer from the growth chamber into the XPS system, layers are either (i) Ar+ ion-etched or (ii) UHV-annealed in situ prior to XPS analyses. High resolution XPS spectra reveal that even gentle etching affects the shape of core level signals, as well as BE values, which are systematically offset by 0.2-0.5 eV towards lower BE. These destructive effects of Ar+ ion etch become more pronounced with increasing the metal atom mass due to an increasing carbon-to-metal sputter yield ratio. Systematic analysis reveals that for each row in the periodic table (3d, 4d, and 5d) C 1s BE increases from left to right indicative of a decreased charge transfer from TM to C atoms, hence bond weakening. Moreover, C 1s BE decreases linearly with increasing carbide/metal melting point ratio. Spectra reported here, acquired from a consistent set of samples in the same instrument, should serve as a reference for true deconvolution of complex XPS cases, including multinary carbides, nitrides, and carbonitrides.

Colour changes by laser irradiation of reddish building limestones

NASA Astrophysics Data System (ADS)

Grossi, C. M.; Benavente, D.

2016-10-01

We have used X-ray photoelectron spectroscopy (XPS) as a novel method to investigate the causes of colour changes in a reddish limestone under irradiation by a Q-switched Nd:YAG 1064 nm laser. We irradiated clean dry and wet surfaces of Pidramuelle Roja, a building stone frequently used in the Asturian heritage, at fluences ranging from 0.12 to 1.47 J cm-2. We measured the colour coordinates and undertook XPS analysis of the state of oxidation of iron both before and after irradiation. Visible colour changes and potential aesthetic damage occurred on dry surfaces from a fluence of 0.31 J cm-2, with the stone showing a greening effect and very intense darkening. The colour change on dry surfaces was considerably higher than on wet surfaces, which at the highest fluence (1.47 J cm-2) was also above the human visual detection threshold. The use of XPS demonstrated that the change in colour (chroma and hue) is associated with a reduction in the iron oxidation state on dry surfaces during laser irradiation. This points out to a potential routinary use of XPS to analyse causes of colour changes during laser cleaning in other types of coloured building stones.

Effects of the low Earth orbit space environment on the surface chemistry of Kapton polyimide film: An XPS study

NASA Technical Reports Server (NTRS)

Lee, Myung; Rooney, William; Whiteside, James

1992-01-01

Kapton H (DuPont Trademark) polyimide specimens exposed to the low earth (LEO) space environment suffered significant weathering with surface erosions of approximately 8.0 microns. Despite these effects, no significant changes in bulk chemistry were observed. X-ray photoelectron spectroscopy (XPS) was used to determine local changes induced from approximately 25 percent in 1980 vintage ground control specimens to nearly 53 percent in space exposed specimens. The greatest increase was observed for the divalent oxygen moieties, although a slight increase in carbonyl oxygen was also measured. Furthermore, the chemical shifts of all XPS peaks of space-exposed Kapton are shifted to higher energy. This is consistent with a higher oxidation state of the space exposed surface. Finally, space exposed specimens had distinct silicon peaks (2p 100 eV and 2s 149 eV) in their XPS spectra in agreement with widespread reports of silicon contamination throughout the LDEF satellite. These results are discussed in terms of surface reactivity of the polyimide exposed to the LEO environment and the chemical nature of contaminants deposited on flight surfaces due to satellite outgassing.

Study of mesoporous CdS-quantum-dot-sensitized TiO2 films by using X-ray photoelectron spectroscopy and AFM

PubMed Central

Wojcieszak, Robert; Raj, Gijo

2014-01-01

Summary CdS quantum dots were grown on mesoporous TiO2 films by successive ionic layer adsorption and reaction processes in order to obtain CdS particles of various sizes. AFM analysis shows that the growth of the CdS particles is a two-step process. The first step is the formation of new crystallites at each deposition cycle. In the next step the pre-deposited crystallites grow to form larger aggregates. Special attention is paid to the estimation of the CdS particle size by X-ray photoelectron spectroscopy (XPS). Among the classical methods of characterization the XPS model is described in detail. In order to make an attempt to validate the XPS model, the results are compared to those obtained from AFM analysis and to the evolution of the band gap energy of the CdS nanoparticles as obtained by UV–vis spectroscopy. The results showed that XPS technique is a powerful tool in the estimation of the CdS particle size. In conjunction with these results, a very good correlation has been found between the number of deposition cycles and the particle size. PMID:24605274

Confirmation of Incorporation of Cu and Se Ions in Applied p- and n-Type-Doped Sb2S3 by Photoemission Spectroscopy

NASA Astrophysics Data System (ADS)

Validžić, Ivana Lj; Popović, Maja; Lojpur, Vesna; Bundaleski, Nenad; Rakočević, Zlatko

2018-04-01

The effect of incorporating copper (Cu) and selenium (Se) ions into stibnite (Sb2S3) lattice was investigated using x-ray photoelectron spectroscopy (XPS). The incorporation of Cu and Se ions was verified by comparing the XPS spectra of the undoped (amorphous Sb2S3), doped ( p and n-doped) and pure Se and Cu-acetate powders. The main photoelectron Cu 2p1/2 (951.8 eV) and Cu 2p3/2 (932.1 eV) lines derived from the Cu-doped and Cu-acetate powder samples were clearly observed, whereas in the undoped sample, none of the characteristic lines of Cu were detected. The Se Auger line (138.6 eV), the only line of Se which does not coincide with the lines of Sb and S, was successfully detected in an Se-doped XPS sample and the spectrum of pure Se, while Se in the undoped sample was not found. Further, the XPS measurements revealed the relative amounts of Cu and Se in antimony sulfide, as well as the oxidation state of copper incorporated into the matrix.

NEXAFS and XPS characterization of molecular oxygen adsorbed on Ni(100) at 80 K

NASA Astrophysics Data System (ADS)

Kim, C. M.; Jeong, H. S.; Kim, E. H.

2000-07-01

X-ray photoelectron spectroscopy (XPS), thermal desorption spectroscopy (TDS) and near edge extended X-ray absorption fine structure (NEXAFS) have been combined to investigate the adsorption of oxygen on Ni(100) at 80 K. Three O(1s) XPS features were observed at 530.0, 531.1 and 534.7 eV when the Ni(100) surface was exposed to 600 L of oxygen at 80 K. They are assigned as O 2-, O 1- and molecular oxygen species, respectively. The presence of molecular oxygen has been confirmed by TDS and NEXAFS. Molecular O 2 on Ni(100) is oriented perpendicular to the surface, and the OO bond length is estimated to be 1.24 Å, based on the NEXAFS σ ∗ resonance energy.

New Pt/Alumina model catalysts for STM and in situ XPS studies

NASA Astrophysics Data System (ADS)

Nartova, Anna V.; Gharachorlou, Amir; Bukhtiyarov, Andrey V.; Kvon, Ren I.; Bukhtiyarov, Valerii I.

2017-04-01

The new Pt/alumina model catalysts for STM and in situ XPS studies based on thin alumina film formed over the conductive substrate are proposed. Procedure of platinum deposition developed for porous alumina was adapted for the model alumina support. The set of Pt/AlOx-film samples with the different mean platinum particle size was prepared. Capabilities of in situ XPS investigations of the proposed catalysts were demonstrated in study of NO decomposition on platinum nanoparticles. It is shown that proposed model catalysts behave similarly to Pt/γ-Al2O3 and provide the new opportunities for the instrumental studies of platinum catalysts due to resolving several issues (charging, heating, screening) that are typical for the investigation of the porous oxide supported catalysts.

Core-level spectra and binding energies of transition metal nitrides by non-destructive x-ray photoelectron spectroscopy through capping layers

NASA Astrophysics Data System (ADS)

Greczynski, G.; Primetzhofer, D.; Lu, J.; Hultman, L.

2017-02-01

We present the first measurements of x-ray photoelectron spectroscopy (XPS) core level binding energies (BE:s) for the widely-applicable group IVb-VIb polycrystalline transition metal nitrides (TMN's) TiN, VN, CrN, ZrN, NbN, MoN, HfN, TaN, and WN as well as AlN and SiN, which are common components in the TMN-based alloy systems. Nitride thin film samples were grown at 400 °C by reactive dc magnetron sputtering from elemental targets in Ar/N2 atmosphere. For XPS measurements, layers are either (i) Ar+ ion-etched to remove surface oxides resulting from the air exposure during sample transfer from the growth chamber into the XPS system, or (ii) in situ capped with a few nm thick Cr or W overlayers in the deposition system prior to air-exposure and loading into the XPS instrument. Film elemental composition and phase content is thoroughly characterized with time-of-flight elastic recoil detection analysis (ToF-E ERDA), Rutherford backscattering spectrometry (RBS), and x-ray diffraction. High energy resolution core level XPS spectra acquired with monochromatic Al Kα radiation on the ISO-calibrated instrument reveal that even mild etching conditions result in the formation of a nitrogen-deficient surface layer that substantially affects the extracted binding energy values. These spectra-modifying effects of Ar+ ion bombardment increase with increasing the metal atom mass due to an increasing nitrogen-to-metal sputter yield ratio. The superior quality of the XPS spectra obtained in a non-destructive way from capped TMN films is evident from that numerous metal peaks, including Ti 2p, V 2p, Zr 3d, and Hf 4f, exhibit pronounced satellite features, in agreement with previously published spectra from layers grown and analyzed in situ. In addition, the N/metal concentration ratios are found to be 25-90% higher than those obtained from the corresponding ion-etched surfaces, and in most cases agree very well with the RBS and ToF-E ERDA values. The N 1 s BE:s extracted from capped TMN films, thus characteristic of a native surface, show a systematic trend, which contrasts with the large BE spread of literature "reference" values. Hence, non-destructive core level XPS employing capping layers provides an opportunity to obtain high-quality spectra, characteristic of virgin in situ grown and analyzed TMN films, although with larger versatility, and allows for extracting core level BE values that are more reliable than those obtained from sputter-cleaned N-deficient surfaces. Results presented here, recorded from a consistent set of binary TMN's grown under the same conditions and analyzed in the same instrument, provide a useful reference for future XPS studies of multinary materials systems allowing for true deconvolution of complex core level spectra.

Band alignments of different buffer layers (CdS, Zn(O,S), and In{sub 2}S{sub 3}) on Cu{sub 2}ZnSnS{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Chang; Liu, Fangyang; Song, Ning

2014-04-28

The heterojunctions of different n-type buffers, i.e., CdS, Zn(O,S), and In{sub 2}S{sub 3} on p-type Cu{sub 2}ZnSnS{sub 4} (CZTS) were investigated using X-ray Photoelectron Spectroscopy (XPS) and Near Edge X-ray Absorption Fine Structure (NEXAFS) Measurements. The band alignment of the heterojunctions formed between CZTS and the buffer materials was carefully measured. The XPS data were used to determine the Valence Band Offsets (VBO) of different buffer/CZTS heterojunctions. The Conduction Band Offset (CBO) was calculated indirectly by XPS data and directly measured by NEXAFS characterization. The CBO of the CdS/CZTS heterojunction was found to be cliff-like with CBO{sub XPS} = −0.24 ± 0.10 eV and CBO{submore » NEXAFS} = −0.18 ± 0.10 eV, whereas those of Zn(O,S) and In{sub 2}S{sub 3} were found to be spike-like with CBO{sub XPS} = 0.92 ± 0.10 eV and CBO{sub NEXAFS} = 0.87 ± 0.10 eV for Zn(O,S)/CZTS and CBO{sub XPS} = 0.41 ± 0.10 eV for In{sub 2}S{sub 3}/CZTS, respectively. The CZTS photovoltaic device using the spike-like In{sub 2}S{sub 3} buffer was found to yield a higher open circuit voltage (Voc) than that using the cliff-like CdS buffer. However, the CBO of In{sub 2}S{sub 3}/CZTS is slightly higher than the optimum level and thus acts to block the flow of light-generated electrons, significantly reducing the short circuit current (Jsc) and Fill Factor (FF) and thereby limiting the efficiency. Instead, the use of a hybrid buffer for optimization of band alignment is proposed.« less

A poly-epoxy surface explored by Hartree-Fock ΔSCF simulations of C1s XPS spectra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gavrielides, A.; Duguet, T., E-mail: thomas.duguet@ensiacet.fr, E-mail: Paul.Bagus@unt.edu; Esvan, J.

Whereas poly-epoxy polymers represent a class of materials with a wide range of applications, the structural disorder makes them difficult to model. In the present work, we use good experimental model samples in the sense that they are pure, fully polymerized, flat and smooth, defect-free, and suitable for ultrahigh vacuum x-ray photoelectron spectroscopy, XPS, experiments. In parallel, we perform Hartree-Fock, HF, calculations of the binding energies, BEs, of the C1s electrons in a model molecule composed of the two constituents of the poly-epoxy sample. These C1s BEs were determined using the HF ΔSCF method, which is known to yield accuratemore » values, especially for the shifts of the BEs, ΔBEs. We demonstrate the benefits of combining rigorous theory with careful XPS measurements in order to obtain correct assignments of the C1s XPS spectra of the polymer sample. Both the relative binding energies—by the ΔSCF method—and relative intensities—in the sudden approximation, SA, are calculated. It results in an excellent match with the experimental spectra. We are able to identify 9 different chemical environments under the C1s peak, where an exclusively experimental work would have found only 3 contributions. In addition, we observe that some contributions are localized at discrete binding energies, whereas others allow a much wider range because of the variation of their second neighbor bound polarization. Therefore, HF-ΔSCF simulations significantly increase the spectral resolution of XPS and thus offer a new avenue for the exploration of the surface of polymers.« less

Core Level Shifts of Hydrogenated Pyridinic and Pyrrolic Nitrogen in the Nitrogen-Containing Graphene-Based Electrocatalysts: In-Plane vs Edge Defects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matanovic, Ivana; Artyushkova, Kateryna; Strand, Matthew B.

A combination of N 1s X-ray photoelectron spectroscopy (XPS) and first principles calculations of nitrogen-containing model electrocatalysts was used to elucidate the nature of the nitrogen defects that contribute to the binding energy (BE) range of the N 1s XPS spectra of these materials above ~400 eV. Experimental core level shifts were obtained for a set of model materials, namely N-doped carbon nanospheres, Fe–N–carbon nanospheres, polypyrrole, polypyridine, and pyridinium chloride, and were compared to the shifts calculated using density functional theory. The results confirm that the broad peak positioned at ~400.7 eV in the N 1s XPS spectra of N-containingmore » catalysts, which is typically assigned to pyrrolic nitrogen, contains contributions from other hydrogenated nitrogen species such as hydrogenated pyridinic functionalities. Namely, N 1s BEs of hydrogenated pyridinic-N and pyrrolic-N were calculated as 400.6 and 400.7 eV, respectively, using the Perdew–Burke–Ernzerhof exchange-correlation functional. A special emphasis was placed on the study of the differences in the XPS imprint of N-containing defects that are situated in the plane and on the edges of the graphene sheet. Density functional theory calculations for BEs of the N 1s of in-plane and edge defects show that hydrogenated N defects are more sensitive to the change in the chemical environment in the carbon matrix than the non-hydrogenated N defects. In conclusion, calculations also show that edge-hydrogenated pyridinic-N and pyrrolic-N defects only contribute to the N 1s XPS peak located at ~400.7 eV if the graphene edges are oxygenated or terminated with bare carbon atoms.« less

Core Level Shifts of Hydrogenated Pyridinic and Pyrrolic Nitrogen in the Nitrogen-Containing Graphene-Based Electrocatalysts: In-Plane vs Edge Defects

DOE PAGES

Matanovic, Ivana; Artyushkova, Kateryna; Strand, Matthew B.; ...

2016-12-07

A combination of N 1s X-ray photoelectron spectroscopy (XPS) and first principles calculations of nitrogen-containing model electrocatalysts was used to elucidate the nature of the nitrogen defects that contribute to the binding energy (BE) range of the N 1s XPS spectra of these materials above ~400 eV. Experimental core level shifts were obtained for a set of model materials, namely N-doped carbon nanospheres, Fe–N–carbon nanospheres, polypyrrole, polypyridine, and pyridinium chloride, and were compared to the shifts calculated using density functional theory. The results confirm that the broad peak positioned at ~400.7 eV in the N 1s XPS spectra of N-containingmore » catalysts, which is typically assigned to pyrrolic nitrogen, contains contributions from other hydrogenated nitrogen species such as hydrogenated pyridinic functionalities. Namely, N 1s BEs of hydrogenated pyridinic-N and pyrrolic-N were calculated as 400.6 and 400.7 eV, respectively, using the Perdew–Burke–Ernzerhof exchange-correlation functional. A special emphasis was placed on the study of the differences in the XPS imprint of N-containing defects that are situated in the plane and on the edges of the graphene sheet. Density functional theory calculations for BEs of the N 1s of in-plane and edge defects show that hydrogenated N defects are more sensitive to the change in the chemical environment in the carbon matrix than the non-hydrogenated N defects. In conclusion, calculations also show that edge-hydrogenated pyridinic-N and pyrrolic-N defects only contribute to the N 1s XPS peak located at ~400.7 eV if the graphene edges are oxygenated or terminated with bare carbon atoms.« less

Acetate- and thiol-capped monodisperse ruthenium nanoparticles: XPS, XAS, and HRTEM studies.

PubMed

Chakroune, Nassira; Viau, Guillaume; Ammar, Souad; Poul, Laurence; Veautier, Delphine; Chehimi, Mohamed M; Mangeney, Claire; Villain, Françoise; Fiévet, Fernand

2005-07-19

Monodisperse ruthenium nanoparticles were prepared by reduction of RuCl3 in 1,2-propanediol. The mean particle size was controlled by appropriate choice of the reduction temperature and the acetate ion concentration. Colloidal solutions in toluene were obtained by coating the metal particles with dodecanethiol. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XANES and EXAFS for the Ru K-absorption edge) were performed on particles of two different diameters, 2 and 4 nm, and in different environments, polyol/acetate or thiol. For particles stored in polyol/acetate XPS studies revealed superficial oxidation limited to one monolayer and a surface coating containing mostly acetate ions. Analysis of the EXAFS spectra showed both oxygen and ruthenium atoms around the ruthenium atoms with a Ru-Ru coordination number N smaller than the bulk value, as expected for fine particles. In the case of 2 nm acetate-capped particles N is consistent with particles made up of a metallic core and an oxidized monolayer. For 2 nm thiol-coated particles, a Ru-S bond was evidenced by XPS and XAS. For the 4 nm particles XANES and XPS studies showed that most of the ruthenium atoms are in the zerovalent state. Nevertheless, in both cases, when capped with thiol, the Ru-Ru coordination number inferred from EXAFS is much smaller than for particles of the same size stored in polyol. This is attributed to a structural disorganization of the particles by thiol chemisorption. HRTEM studies confirm the marked dependence of the structural properties of the ruthenium particles on their chemical environment; they show the acetate-coated particles to be single crystals, whereas the thiol-coated particles appear to be polycrystalline.

Morphology and Chemical Composition of soot particles emitted by Wood-burning Cook-Stoves: a HRTEM, XPS and Elastic backscattering Studies.

NASA Astrophysics Data System (ADS)

Carabali-Sandoval, G. A., Sr.; Castro, T.; Peralta, O.; De la Cruz, W.; Días, J.; Amelines, O.; Rivera-Hernández, M.; Varela, A.; Muñoz-Muñoz, F.; Policroniades, R.; Murillo, G.; Moreno, E.

2014-12-01

The morphology, microstructure and the chemical composition on surface of soot particles were studied by using high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and elastic backscattering spectrometry. In order to obtain freshly soot particles emitted by home-made wood-burning cook stoves, copper grids for Transmission Electron Microscope (TEM) were placed on the last two of an 8-stages MOUDI cascade impactor. The analysis of HRTEM micrographs revealed the nanostructure and the particle size of soot particles. The XPS survey spectra show a large carbon peak around 285 eV and the oxygen signal at 533 eV. Some differences observed in the carbon/oxygen (C/O) ratio of the particles probably depend on the combustion process efficiency of each cook-stove analyzed. The C-1s XPS spectra show an asymmetric broad peak and other with low intensity that corresponds to sp2 and sp3hybridization, which were fitted with a convolution using Gaussian functions. Elastic backscattering technique allows a chemical elemental analysis of samples and confirms the presence of C, O and Si observed by XPS. Additionally, the morphological properties of soot aggregates were analyzed calculating the border-based fractal dimension (Df). Particles exhibit complex shapes with high values of Df. Also, real-time absorption (σabs) and scattering (σsct) coefficients of fine (with aerodynamic diameter < 2.5 µm) soot particles were measured. The trend in σabs and σsct indicate that the cooking process has two important combustion stages which varied in its flaming strength, being vigorous in the first stage and soft in the second one.

Quantitative interpretation of molecular dynamics simulations for X-ray photoelectron spectroscopy of aqueous solutions

NASA Astrophysics Data System (ADS)

Olivieri, Giorgia; Parry, Krista M.; Powell, Cedric J.; Tobias, Douglas J.; Brown, Matthew A.

2016-04-01

Over the past decade, energy-dependent ambient pressure X-ray photoelectron spectroscopy (XPS) has emerged as a powerful analytical probe of the ion spatial distributions at the vapor (vacuum)-aqueous electrolyte interface. These experiments are often paired with complementary molecular dynamics (MD) simulations in an attempt to provide a complete description of the liquid interface. There is, however, no systematic protocol that permits a straightforward comparison of the two sets of results. XPS is an integrated technique that averages signals from multiple layers in a solution even at the lowest photoelectron kinetic energies routinely employed, whereas MD simulations provide a microscopic layer-by-layer description of the solution composition near the interface. Here, we use the National Institute of Standards and Technology database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to quantitatively interpret atom-density profiles from MD simulations for XPS signal intensities using sodium and potassium iodide solutions as examples. We show that electron inelastic mean free paths calculated from a semi-empirical formula depend strongly on solution composition, varying by up to 30% between pure water and concentrated NaI. The XPS signal thus arises from different information depths in different solutions for a fixed photoelectron kinetic energy. XPS signal intensities are calculated using SESSA as a function of photoelectron kinetic energy (probe depth) and compared with a widely employed ad hoc method. SESSA simulations illustrate the importance of accounting for elastic-scattering events at low photoelectron kinetic energies (<300 eV) where the ad hoc method systematically underestimates the preferential enhancement of anions over cations. Finally, some technical aspects of applying SESSA to liquid interfaces are discussed.

Demonstration of an ultrasensitive refractive-index plasmonic sensor by enabling its quadrupole resonance in phase interrogation.

PubMed

Lee, Hsin-Cheng; Li, Chung-Tien; Chen, How-Foo; Yen, Ta-Jen

2015-11-15

We present an ultrasensitive plasmonic sensing system by introducing a nanostructured X-shaped plasmonic sensor (XPS) and measuring its localized optical properties in phase interrogation. Our tailored XPS exhibits two major resonant modes of a low-order dipole and a high-order quadrupole, between which the quadrupole resonance allows an ultrahigh sensitivity, due to its higher quality factor. Furthermore, we design an in-house common-path phase-interrogation system, in contrast to conventional wavelength-interrogation methods, to achieve greater sensing capability. The experimental measurement shows that the sensing resolution of the XPS reaches 1.15×10(-6) RIU, not only two orders of magnitude greater than the result of the controlled extinction measurement (i.e., 9.90×10(-5) RIU), but also superior than current reported plasmonic sensors.

RECENT XPS STUDIES OF THE EFFECT OF PROCESSING ON NB SRF SURFACES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hui Tian; Binping Xiao; Michael Kelley

XPS studies have consistently shown that Nb surfaces for SRF chiefly comprise of a few nm of Nb2O5 on top of Nb metal, with minor amounts of Nb sub-oxides. Nb samples after BCP/EP treatment with post-baking at the various conditions have been examined by using synchrotron based XPS. Despite the confounding influence of surface roughness, certain outcomes are clear. Lower-valence Nb species are always and only associated with the metal/oxide interface, but evidence for an explicit layer structure or discrete phases is lacking. Post-baking without air exposure shows decreased oxide layer thickness and increased contribution from lower valence species, butmore » spectra obtained after subsequent air exposure cannot be distinguished from those obtained prior to baking, though the SRF performance improvement remains.« less

Multicharged Ion Promoted Desorption (MIPD) of Reaction Co-Products

DTIC Science & Technology

2015-02-13

measurements of surface modifications using mass spectrometry, Raman spectroscopy and XPS were made to 1. REPORT DATE (DD-MM-YYYY) 4. TITLE AND...desorption and ex-situ measurements of surface modifications using mass spectrometry, Raman spectroscopy and XPS were made to determine ion-induced...irradiations were made with the samples at normal incidence to the incoming beams and post-analysis of these samples was achieved using Raman spectroscopy. It

Surface modification of EPDM rubber by plasma treatment.

PubMed

Grythe, Kai Frode; Hansen, Finn Knut

2006-07-04

The effect of argon, oxygen, and nitrogen plasma treatment of solvent cast EPDM rubber films has been investigated by means of atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and surface energy measurements. Plasma treatment leads to changes in the surface energy from 25 to 70 mN/m. Treatment conditions influenced both the changes in surface energy and the stability, and it became more difficult to obtain good contact angle measurements after longer (> ca. 4 min) treatment times, probably because of an increasingly uneven surface structure. XPS analyses revealed that up to 20 at. % oxygen can be easily incorporated and that variations of approximately 5% can be controlled by the plasma conditions. Oxygen was mainly found in hydroxyl groups, but also as carbonyl and carboxyl. XPS analyses showed more stable surfaces than expected from contact angles, probably because XPS analysis is less surface sensitive than contact angle measurements. AFM measurements revealed different surface structures with the three gases. The surface roughness increased generally with treatment time, and dramatic changes could be observed at longer times. At short times, surface energy changes were much faster than the changes in surface structure, showing that plasma treatment conditions can be utilized to tailor both surface energies and surface structure of EPDM rubber.

Surface analysis of 316 stainless steel treated with cold atmospheric plasma

NASA Astrophysics Data System (ADS)

Williams, David F.; Kellar, Ewen J. C.; Jesson, David A.; Watts, John F.

2017-05-01

The surface of 316 stainless steel has been modified using cold atmospheric plasma (CAP) to increase the surface free energy (by cleaning the and chemically activating the surface)IN preparation for subsequent processes such as painting, coating or adhesive bonding. The analyses carried out, on CAP treated 316 stainless steel surfaces, includes X-ray photoelectron spectroscopy (XPS), imaging XPS (iXPS), and surface free energy (SFE) analysis using contact angle measurements. The CAP treatment is shown to increase the SFE of as-received 316 stainless steel from ∼39 mJ m-1 to >72 mJ m-1 after a short exposure to the plasma torch. This was found to correlate to a reduction in adventitious carbon, as determined by XPS analysis of the surface. The reduction from ∼90 at% to ∼30% and ∼39 at%, after being plasma treated for 5 min and 15 s respectively, shows that the process is relatively quick at changing the surface. It is suggested that the mechanism that causes the increase in surface free energy is chain scission of the hydrocarbon contamination triggered by free electrons in the plasma plume followed by chemical functionalisation of the metal oxide surface and some of the remaining carbon contamination layer.

Morphological, chemical and structural characterisation of deciduous enamel: SEM, EDS, XRD, FTIR and XPS analysis.

PubMed

Zamudio-Ortega, C M; Contreras-Bulnes, R; Scougall-Vilchis, R J; Morales-Luckie, R A; Olea-Mejía, O F; Rodríguez-Vilchis, L E

2014-09-01

The purpose of this study was to characterise the enamel surface of sound deciduous teeth in terms of morphology, chemical composition, structure and crystalline phases. The enamel of 30 human deciduous teeth was examined by: Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDS), X-ray Powder Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and X-ray Photoelectron Spectroscopy (XPS). Chemical differences between incisors and canines were statistically evaluated using the Mann-Whitney U test (p ≤ 0.05). Three enamel patterns were observed by SEM: 'mostly smooth with some groves', 'abundant microporosities' and 'exposed prisms'. The average Ca/P molar ratios were 1.37 and 1.03 by EDS and XPS, respectively. The crystallite size determined by XRD was 210.82 ± 16.78 Å. The mean ratio between Ca bonded to phosphate and Ca bonded to hydroxyl was approximately 10:1. The enamel of sound deciduous teeth showed two main patterns: 'mostly smooth with some groves' and 'abundant microporosities'. 'Exposed prisms' was a secondary pattern. There were slight variations among the Ca/P molar ratios found by EDS and XPS, suggesting differences in the mineral content from the enamel surface to the interior. The crystalline phases found in enamel were hydroxyapatite and carbonate apatite, with major type B than type A carbonate incorporation.

Combined soft and hard X-ray ambient pressure photoelectron spectroscopy studies of semiconductor/electrolyte interfaces

DOE PAGES

Starr, David E.; Favaro, Marco; Abdi, Fatwa F.; ...

2017-05-18

The development of solar fuel generating materials would greatly benefit from a molecular level understanding of the semiconductor/electrolyte interface and changes in the interface induced by an applied potential and illumination by solar light. Ambient pressure photoelectron spectroscopy techniques with both soft and hard X-rays, AP-XPS and AP-HAXPES respectively, have the potential to markedly contribute to this understanding. In this paper we initially provide two examples of current challenges in solar fuels material development that AP-XPS and AP-HAXPES can directly a ddress. This will be followed by a brief description of the distinguishing and complementary characteristics of soft and hardmore » X-ray AP-XPS and AP-HAXPES and best approaches to achieving monolayer sensitivity in solid/aqueous electrolyte studies. In particular we focus on the detection of surface adsorbed hydroxyl groups in the presence of aqueous hydroxide anions in the electrolyte, a common situation when investigating photoanodes for solar fuel generating applications. Finally, the article concludes by providing an example of a combined AP-XPS and AP-HAXPES study of a semiconductor/aqueous electrolyte interface currently used in water splitting devices specifically the BiVO 4/aqueous potassium phosphate electrolyte interface.« less

Oxidation of palladium on Au(111) and ZnO(0001) supports

DOE PAGES

Lallo, J.; Tenney, S. A.; Kramer, A.; ...

2014-10-21

The oxidation of supported Pd-deposits on Au(111) and ZnO(0001) single crystals has been studied by x- ray photoemission spectroscopy (XPS). Oxidation has been carried out ex-situ in a high-pressure cell with subsequent vacuum-transfer and characterization by XPS in ultrahigh vacuum (UHV), as well as using in-situ characterization by synchrotron based near-ambient pressure XPS. On Au(111) alloying of Pd with the substrate competes with oxidation and only sufficiently thick Pd films have been found to oxidize. For Pd on ZnO the oxidation conditions depend on the amount of deposited Pd. Thicker Pd deposits behave similar to bulk Pd, while thinner filmsmore » oxidize already at lower temperatures. Interestingly, for very small amounts of Pd, in-situ XPS shows full oxidation at room temperature and at less than 0.6 mbar O₂ pressure. This indicates a lowering of the kinetic barriers for oxidation of very small supported Pd-clusters. The formed oxide is, however, not stable in UHV and a slow reduction is observed. The instability of this oxide indicates that the Pd-oxide formed at the interface to ZnO may have different chemical properties compared to bulk PdO or surface oxides on Pd.« less

Composite targets in HiPIMS plasmas: Correlation of in-vacuum XPS characterization and optical plasma diagnostics

NASA Astrophysics Data System (ADS)

Layes, Vincent; Monje, Sascha; Corbella, Carles; Schulz-von der Gathen, Volker; von Keudell, Achim; de los Arcos, Teresa

2017-05-01

In-vacuum characterization of magnetron targets after High Power Impulse Magnetron Sputtering (HiPIMS) has been performed by X-ray photoelectron spectroscopy (XPS). Al-Cr composite targets (circular, 50 mm diameter) mounted in two different geometries were investigated: an Al target with a small Cr disk embedded at the racetrack position and a Cr target with a small Al disk embedded at the racetrack position. The HiPIMS discharge and the target surface composition were characterized in parallel for low, intermediate, and high power conditions, thus covering both the Ar-dominated and the metal-dominated HiPIMS regimes. The HiPIMS plasma was investigated using optical emission spectroscopy and fast imaging using a CCD camera; the spatially resolved XPS surface characterization was performed after in-vacuum transfer of the magnetron target to the XPS chamber. This parallel evaluation showed that (i) target redeposition of sputtered species was markedly more effective for Cr atoms than for Al atoms; (ii) oxidation at the target racetrack was observed even though the discharge ran in pure Ar gas without O2 admixture, the oxidation depended on the discharge power and target composition; and (iii) a bright emission spot fixed on top of the inserted Cr disk appeared for high power conditions.

A quantitative model and the experimental evaluation of the liquid fuel layer for the downward flame spread of XPS foam.

PubMed

Luo, Shengfeng; Xie, Qiyuan; Tang, Xinyi; Qiu, Rong; Yang, Yun

2017-05-05

The objective of this work is to investigate the distinctive mechanisms of downward flame spread for XPS foam. It was physically considered as a moving down of narrow pool fire instead of downward surface flame spread for normal solids. A method was developed to quantitatively analyze the accumulated liquid fuel based on the experimental measurement of locations of flame tips and burning rates. The results surprisingly showed that about 80% of the generated hot liquid fuel remained in the pool fire during a certain period. Most of the consumed solid XPS foam didn't really burn away but transformed as the liquid fuel in the downward moving pool fire, which might be an important promotion for the fast fire development. The results also indicated that the dripping propensity of the hot liquid fuel depends on the total amount of the hot liquid accumulated in the pool fire. The leading point of the flame front curve might be the breach of the accumulated hot liquid fuel if it is enough for dripping. Finally, it is suggested that horizontal noncombustible barriers for preventing the accumulation and dripping of liquid fuel are helpful for vertical confining of XPS fire. Copyright © 2017 Elsevier B.V. All rights reserved.

Surface analysis of glass fibres using XPS and AFM: case study of glass fibres recovered from the glass fibre reinforced polymer using chemical recycling

NASA Astrophysics Data System (ADS)

Nzioka, A. M.; Kim, Y. J.

2018-01-01

In this study, we present the results of an experimental study of the use of the X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) to characterise the coatings of the recovered E - glass fibres. The recovered E - glass fibres were obtained using chemical recycling process coupled with ultrasound cavitation. The objective of this study was to analyse the impact of chemical recycling and the ultrasound cavitation process on the sizing properties of the recovered fibres. We obtained the recovered fibres and sized using 1 wt% 3 - aminopropyltriethoxysilane (APS). Part of the sized fibres was washed with acetone and analysed all the sample fibres using AFM and XPS. Results showed the different composition of sizing after extraction using acetone. We compared the results of this study with that of virgin clean glass fibres.

Surface and electronic structure of Bi-Ca-Sr-Cu-O superconductors studied by LEED, UPS and XPS

NASA Astrophysics Data System (ADS)

Shen, Z.-X.; Lindberg, P. A. P.; Wells, B. O.; Lindau, I.; Spicer, W. E.; Mitzi, D. B.; Eom, C. B.; Kapitulnik, A.; Geballe, T. H.; Soukiassian, P.

1989-02-01

Single crystal and polycrystalline samples of Bi2CaSr2Cu2O8 have been studied by various surface sensitive techniques, including low energy electron diffraction (LEED), ultraviolet photoemission spectroscopy (UPS) and x-ray photoemission spectroscopy (XPS). The surface structure of the single crystals was characterized by LEED to be consistent with that of the bulk structure. Our data suggest that Bi2CaSr2Cu2O8 single crystals are very stable in the ultrahigh vacuu. No change of XPS spectra with temperature was observed. We have also studied the electronic structure of Bi2Sr2CuO6, which has a lower superconducting transition temperature Tc. Comparing the electronic structure of the two Bi-Ca-Sr-Cu-O superconductors, an important difference in the density of states near EF was observed which seems to be related to the difference in Tc.

Platinized tin oxide catalysts for CO2 lasers: Effects of pretreatment

NASA Technical Reports Server (NTRS)

Gardner, Steven D.; Hoflund, Gar B.; Schryer, David R.; Upchurch, Billy T.

1990-01-01

Platinized tin oxide surfaces used for low-temperature CO oxidation in CO2 lasers have been characterized before and after reduction in CO at 125 and 250 C using ion scattering spectroscopy (ISS) and X ray photoelectron spectroscopy (XPS). XPS indicates that the Pt is present initially as PtO2. Reduction at 125 C converts the PtO2 to Pt(OH)2 while reduction at 250 C converts the PtO2 to metallic Pt. ISS shows that the Pt in the outermost atomic layer of the catalyst is mostly covered by substrate species during the 250 C reduction. Both the ISS and XPS results are consistent with Pt/Sn alloy formation. The surface dehydration and migration of substrate species over surface Pt and Sn appear to explain why a CO pretreatment at 250 C produces inferior CO oxidation activities compared to a 125 C pretreatment.

Platinized tin oxide catalysts for CO2 lasers - Effects of pretreatment

NASA Technical Reports Server (NTRS)

Gardner, Steven D.; Hoflund, Gar B.; Schryer, David R.; Upchurch, Billy T.

1989-01-01

Platinized tin oxide surfaces used for low-temperature CO oxidation in CO2 lasers have been characterized before and after reduction in CO at 125 and 250 C using ion scattering spectroscopy (ISS) and X-ray photoelectron spectroscopy (XPS). XPS indicates that the Pt is present initially as Pto2. Reduction at 125 C converts the PtO2 to Pt(OH)2 while reduction at 250 C converts the PtO2 to metallic Pt. ISS shows that the Pt in the outermost atomic layer of the catalyst is mostly covered by substrate species during the 250 C reduction. Both the ISS and XPS results are consistent with Pt/Sn alloy formation. The surface dehydration and migration of substrate species over surface Pt and Sn appear to explain why a CO pretreatment at 250 C produces inferior CO oxidation activities compared to a 125 C pretreatment.

Morphological and XPS study of ball milled Fe1-xAlx (0.3≤x≤0.6) alloys

NASA Astrophysics Data System (ADS)

Rajan, Sandeep; Kumar, Anil; Vyas, Anupam; Brajpuriya, Ranjeet

2018-05-01

The paper presents mechanical and XPS study of ball milled Fe1-xAlx (0.3≤x≤0.6) alloys. The author prepared the solid solution of Fe(Al) with different composition of Al by using mechanical alloying (MA) technique. The MA process induces a progressive dissolution of Al into Fe, resulted in the formation of an extended Fe(Al) solid solution with the bcc structure after 5 hr of milling. The SEM Images shows that the initial shape of particles disappeared completely, and their structure became a mixture of small and large angular-shaped crystallites with different sizes. The TEM micrograph also confirms the reduction in crystallite size and alloy formation. XPS study shows the shift in the binding energy position of both Fe and Al Peaks provide strong evidence of Fe(Al) phase formation after milling.

XPS studies of nitrogen doping niobium used for accelerator applications

NASA Astrophysics Data System (ADS)

Yang, Ziqin; Lu, Xiangyang; Tan, Weiwei; Zhao, Jifei; Yang, Deyu; Yang, Yujia; He, Yuan; Zhou, Kui

2018-05-01

Nitrogen doping study on niobium (Nb) samples used for the fabrication of superconducting radio frequency (SRF) cavities was carried out. The samples' surface treatment was attempted to replicate that of the Nb SRF cavities, which includes heavy electropolishing (EP), nitrogen doping and the subsequent EP with different amounts of material removal. The surface chemical composition of Nb samples with different post treatments has been studied by XPS. The chemical composition of Nb, O, C and N was presented before and after Gas Cluster Ion Beam (GCIB) etching. No signals of poorly superconducting nitrides NbNx was found on the surface of any doped Nb sample with the 2/6 recipe before GCIB etching. However, in the depth range greater than 30 nm, the content of N element is below the XPS detection precision scope even for the Nb sample directly after nitrogen doping treatment with the 2/6 recipe.

Conduction band offset at GeO{sub 2}/Ge interface determined by internal photoemission and charge-corrected x-ray photoelectron spectroscopies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, W. F.; Nishimula, T.; Nagashio, K.

2013-03-11

We report a consistent conduction band offset (CBO) at a GeO{sub 2}/Ge interface determined by internal photoemission spectroscopy (IPE) and charge-corrected X-ray photoelectron spectroscopy (XPS). IPE results showed that the CBO value was larger than 1.5 eV irrespective of metal electrode and substrate type variance, while an accurate determination of valence band offset (VBO) by XPS requires a careful correction of differential charging phenomena. The VBO value was determined to be 3.60 {+-} 0.2 eV by XPS after charge correction, thus yielding a CBO (1.60 {+-} 0.2 eV) in excellent agreement with the IPE results. Such a large CBO (>1.5more » eV) confirmed here is promising in terms of using GeO{sub 2} as a potential passivation layer for future Ge-based scaled CMOS devices.« less

Identification of the silver state in the framework of Ag-containing zeolite by XRD, FTIR, photoluminescence, 109Ag NMR, EPR, DR UV-vis, TEM and XPS investigations.

PubMed

Popovych, Nataliia; Kyriienko, Pavlo; Soloviev, Sergiy; Baran, Rafal; Millot, Yannick; Dzwigaj, Stanislaw

2016-10-26

Silver has been identified in the framework of Ag x SiBEA zeolites (where x = 3-6 Ag wt%) by the combined use of XRD, 109 Ag MAS NMR, FTIR, diffuse reflectance UV-visible, EPR and XPS spectroscopy. The incorporation of Ag ions into the framework of SiBEA zeolite has been evidenced by XRD. The consumption of OH groups as a result of their reaction with the silver precursor has been monitored by FTIR and photoluminescence spectroscopy. The changes in the silver state as a function of Ag content and thermal and hydrogen treatment at 573 K have been identified by 109 Ag MAS NMR, EPR, DR UV-visible, TEM and XPS investigations. The acidity of AgSiBEA has been investigated by FTIR spectroscopy of adsorbed CO and pyridine used as probe molecules.

XPS and ToF-SIMS analysis of natural rubies and sapphires heat-treated in a reducing (5 mol% H 2/Ar) atmosphere

NASA Astrophysics Data System (ADS)

Achiwawanich, S.; James, B. D.; Liesegang, J.

2008-12-01

Surface effects on Mong Hsu rubies and Kanchanaburi sapphires after heat treatment in a controlled reducing atmosphere (5 mol% H 2/Ar) have been investigated using advanced surface science techniques including X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Visual appearance of the gemstones is clearly affected by the heat treatment in a reducing atmosphere. Kanchanaburi sapphires, in particular, exhibit Fe-containing precipitates after the heat treatment which have not been observed in previous studies under an inert atmosphere. Significant correlation between changes in visual appearance of the gemstones and variations in surface concentration of trace elements, especially Ti and Fe are observed. The XPS and ToF-SIMS results suggest that; (1) a reducing atmosphere affects the oxidation state of Fe; (2) dissociation of Fe-Ti interaction may occur during heat treatment.

XPS and UPS studies on electronic structure of Li 2O

NASA Astrophysics Data System (ADS)

Tanaka, Satoru; Taniguchi, Masaki; Tanigawa, Hisashi

2000-12-01

The adsorption behavior of H 2O on Li 2O was studied by X-ray photo electron spectroscopy (XPS) and ultraviolet photo electron spectroscopy (UPS). XPS and UPS spectra of Li 2O single crystals which were exposed to different pressure of H 2O vapor were observed. In O(1s) region, two peaks were observed and they were assigned to O(1s) in precipitated LiOH on the surface and O(1s) in Li 2O. After H 2O exposure, a peak broadening and an appearance of a new peak were observed at the higher binding energy region than O(1s) in Li 2O. They were attributed to surface -OH and H 2O molecule adsorbed on the surface. The adsorption behavior of H 2O was discussed from the observation of electronic structure in Li 2O surface.

Toward a better determination of dairy powders surface composition through XPS matrices development.

PubMed

Nikolova, Y; Petit, J; Sanders, C; Gianfrancesco, A; Scher, J; Gaiani, C

2015-01-01

The surface composition of dairy powders prepared by mixing various amounts of micellar casein (MC), whey proteins isolate (WPI), lactose, and anhydrous milk fat (AMF) was investigated by XPS measurements. The use of matrices are generally accepted to transform surface atomic composition (i.e., C, O, N contents) into surface component composition (i.e., lactose, proteins, lipids). These atomic-based matrices were revisited and two new matrices based on the surface bond composition were developed. Surface compositions obtained from atomic and bond-based matrices were compared. A successful matrix allowing good correlations between XPS predicted and theoretical surface composition for powders free from fat was identified. Nevertheless, samples containing milk fat were found to present a possible segregation of components owing to the AMF overrepresentation on the surface. Supplementary analyses (FTIR, SEM) were carried out in order to investigate the homogeneity of the mixtures. Copyright © 2014 Elsevier B.V. All rights reserved.

Quantifying the Impact of Nanoparticle Coatings and Non-uniformities on XPS Analysis: Gold/silver Core-shell Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yung-Chen Andrew; Engelhard, Mark H.; Baer, Donald R.

2016-03-07

Abstract or short description: Spectral modeling of photoelectrons can serve as a valuable tool when combined with X-ray photoelectron spectroscopy (XPS) analysis. Herein, a new version of the NIST Simulation of Electron Spectra for Surface Analysis (SESSA 2.0) software, capable of directly simulating spherical multilayer NPs, was applied to model citrate stabilized Au/Ag-core/shell nanoparticles (NPs). The NPs were characterized using XPS and scanning transmission electron microscopy (STEM) to determine the composition and morphology of the NPs. The Au/Ag-core/shell NPs were observed to be polydispersed in size, non-circular, and contain off-centered Au-cores. Using the average NP dimensions determined from STEM analysis,more » SESSA spectral modeling indicated that washed Au/Ag-core shell NPs were stabilized with a 0.8 nm l« less

Application of surface analytical methods in thin film analysis

NASA Astrophysics Data System (ADS)

Wen, Xingu

Self-assembly and the sol-gel process are two promising methods for the preparation of novel materials and thin films. In this research, these two methods were utilized to prepare two types of thin films: self-assembled monolayers of peptides on gold and SiO2 sol-gel thin films modified with Ru(II) complexes. The properties of the resulting thin films were investigated by several analytical techniques in order to explore their potential applications in biomaterials, chemical sensors, nonlinear optics and catalysis. Among the analytical techniques employed in the study, surface analytical techniques, such as X-ray photoelectron spectroscopy (XPS) and grazing angle reflection absorption Fourier transform infrared spectroscopy (RA-FTIR), are particularly useful in providing information regarding the compositions and structures of the thin films. In the preparation of peptide thin films, monodisperse peptides were self-assembled on gold substrate via the N-terminus-coupled lipoic acid. The film compositions were investigated by XPS and agreed well with the theoretical values. XPS results also revealed that the surface coverage of the self-assembled films was significantly larger than that of the physisorbed films and that the chemisorption between the peptides and gold surface was stable in solvent. Studies by angle dependent XPS (ADXPS) and grazing angle RA-FTIR indicated that the peptides were on average oriented at a small angle from the surface normal. By using a model of orientation distribution function, both the peptide tilt angle and film thickness can be well calculated. Ru(II) complex doped SiO2 sol-gel thin films were prepared by low temperature sol-gel process. The ability of XPS coupled with Ar + ion sputtering to provide both chemical and compositional depth profile information of these sol-gel films was evaluated. This technique, together with UV-VIS and electrochemical measurements, was used to investigate the stability of Ru complexes in the composite films. The stability of Ru complexes with respect to dopant leaching was dependent on the film microstructures. Three methods aiming to improve the dopant stability were also explored. In addition, the ion exchange properties of the composite films, upon exposure to various ions in aqueous solutions, were investigated by XPS, and the ion exchange mechanism was elucidated.

Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

DOE PAGES

Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua; ...

2015-05-07

We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquidmore » and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.« less

Gold/silver core-shell 20 nm nanoparticles extracted from citrate solution examined by XPS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Engelhard, Mark H.; Smith, Jordan N.; Baer, Donald R.

Silver nanoparticles of many types are widely used in consumer and medical products. The surface chemistry of particles and the coatings that form during synthesis or use in many types of media can significantly impact the behaviors of particles including dissolution, transformation and biological or environmental impact. Consequently it is useful to be able to extract information about the thickness of surface coatings and other attributes of nanoparticles produced in a variety of ways. It has been demonstrated that X-ray Photoelectron Spectroscopy (XPS) can be reliably used to determine the thickness of organic and other nanoparticles coatings and shells. However,more » care is required to produce reliable and consistent information. Here we report the XPS spectra from gold/silver core-shell nanoparticles of nominal size 20 nm removed from a citrate saturated solution after one and two washing cycles. The Simulation of Electron Spectra for Surface Analysis (SESSA) program had been used to model peak amplitudes to obtain information on citrate coatings that remain after washing and demonstrate the presence of the gold core. This data is provided so that others can compare use of SESSA or other modeling approaches to quantify the nature of coatings to those already published and to explore the impacts particle non-uniformities on XPS signals from core-shell nanoparticles.« less

Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua

We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquidmore » and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.« less

The Effect of Thermal and Mechanical Treatments on Kaolinite: Characterization by XPS and IEP Measurements.

PubMed

Torres Sánchez RM; Basaldella; Marco

1999-07-15

The surface transformations induced on kaolinite by different thermal and mechanical treatments have been investigated by means of X-ray photoelectron spectroscopy (XPS), Bremsstrahlung induced Auger spectroscopy, and isoelectric point (IEP) measurements. Heating the kaolinite at temperatures between 500 and 750 degrees C results in the change of a substantial fraction of surface Al from octahedral to tetrahedral coordination, which we associate with the dehydroxylation of kaolinite. Heating at 900 and 980 degrees C brings about the development of an octahedral Al fraction which is associated with the formation of gamma-Al(2)O(3). The development of an Al tetrahedral component in the Al KLL spectra of the mechanically treated (ground) samples has been also observed. The Si/Al atomic ratio obtained by XPS in the thermally treated samples is the same as that shown by the original kaolinite. However, the XPS data show a clear reduction of the Si/Al atomic ratio in the mechanically treated samples, which suggests that the mechanical treatment has induced an Al enrichment of the kaolinite surface. The IEP values indicated a thermal transformation to metakaolinite and mullite with the increase of temperature (750 to 980 degrees C). The IEP change for the milled samples can be only explained by assuming a 30% kaolinite coating by the Al oxide neoformed by grinding. Copyright 1999 Academic Press.

Metal-passivated PbS nanoparticles: fabrication and characterization.

PubMed

Tchaplyguine, M; Mikkelä, M-H; Mårsell, E; Polley, C; Mikkelsen, A; Zhang, W; Yartsev, A; Hetherington, C J D; Wallenberg, L R; Björneholm, O

2017-03-08

Organic-shell-free PbS nanoparticles have been produced in the size range relevant for quantum-dot solar cells (QDSCs) by a vapor aggregation method involving magnetron reactive sputtering. This method creates a beam of free 5-10 nm particles in a vacuum. The dimensions of the particles were estimated after their deposition on a substrate by imaging them using ex situ SEM and HRTEM electron microscopy. The particle structure and chemical composition could be deduced "on the fly", prior to deposition, using X-ray photoelectron spectroscopy (XPS) with tunable synchrotron radiation. Our XPS results suggest that under certain conditions it is possible to fabricate particles with a semiconductor core and 1 to 2 monolayer shells of metallic lead. For this case the absolute energy of the highest occupied molecular orbital (HOMO) in PbS has been determined to be (5.0 ± 0.5) eV below the vacuum level. For such particles deposited on a substrate HRTEM has confirmed the XPS-based conclusions on the crystalline PbS structure of the semiconductor core. Absorption spectroscopy on the deposited film has given a value of ∼1 eV for the lowest exciton. Together with the valence XPS results this has allowed us to reconstruct the energy level scheme of the particles. The results obtained are discussed in the context of the properties of PbS QDSCs.

A Chemical View on X-ray Photoelectron Spectroscopy: the ESCA Molecule and Surface-to-Bulk XPS Shifts.

PubMed

Delesma, Francisco A; Van den Bossche, Maxime; Grönbeck, Henrik; Calaminici, Patrizia; Köster, Andreas M; Pettersson, Lars G M

2018-01-19

In this paper we remind the reader of a simple, intuitive picture of chemical shifts in X-ray photoelectron spectroscopy (XPS) as the difference in chemical bonding between the probed atom and its neighbor to the right in the periodic table, the so called Z+1 approximation. We use the classical ESCA molecule, ethyl trifluoroacetate, and 4d-transition metals to explicitly demonstrate agreement between core-level shifts computed as differences between final core-hole states and the approach where each core-ionized atom is replaced by a Z+1 atom. In this final state, or total energy picture, the XPS shift arises due to the more or less unfavorable chemical bonding of the effective nitrogen in the carbon geometry for the ESCA molecule. Surface core level shifts in metals are determined by whether the Z+1 atom as an alloy segregates to the surface or is more soluble in the bulk. As further illustration of this more chemical picture, we compare the geometry of C 1s and O 1s core-ionized CO with that of, respectively, NO + and CF + . The scope is not to propose a new method to compute XPS shifts but rather to stress the validity of this simple interpretation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal ion interaction with phosphorylated tyrosine analogue monolayers on gold.

PubMed

Petoral, Rodrigo M; Björefors, Fredrik; Uvdal, Kajsa

2006-11-23

Phosphorylated tyrosine analogue molecules (pTyr-PT) were assembled onto gold substrates, and the resulting monolayers were used for metal ion interaction studies. The monolayers were characterized by X-ray photoelectron spectroscopy (XPS), infrared reflection-absorption spectroscopy (IRAS), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), both prior to and after exposure to metal ions. XPS verified the elemental composition of the molecular adsorbate and the presence of metal ions coordinated to the phosphate groups. Both the angle-dependent XPS and IRAS results were consistent with the change in the structural orientation of the pTyr-PT monolayer upon exposure to metal ions. The differential capacitance of the monolayers upon coordination of the metal ions was evaluated using EIS. These metal ions were found to significantly change the capacitance of the pTyr-PT monolayers in contrast to the nonphosphorylated tyrosine analogue (TPT). CV results showed reduced electrochemical blocking capabilities of the phosphorylated analogue monolayer when exposed to metal ions, supporting the change in the structure of the monolayer observed by XPS and IRAS. The largest change in the structure and interfacial capacitance was observed for aluminum ions, compared to calcium, magnesium, and chromium ions. This type of monolayer shows an excellent capability to coordinate metal ions and has a high potential for use as sensing layers in biochip applications to monitor the presence of metal ions.

A perspective on two chemometrics tools: PCA and MCR, and introduction of a new one: Pattern recognition entropy (PRE), as applied to XPS and ToF-SIMS depth profiles of organic and inorganic materials

NASA Astrophysics Data System (ADS)

Chatterjee, Shiladitya; Singh, Bhupinder; Diwan, Anubhav; Lee, Zheng Rong; Engelhard, Mark H.; Terry, Jeff; Tolley, H. Dennis; Gallagher, Neal B.; Linford, Matthew R.

2018-03-01

X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) are much used analytical techniques that provide information about the outermost atomic and molecular layers of materials. In this work, we discuss the application of multivariate spectral techniques, including principal component analysis (PCA) and multivariate curve resolution (MCR), to the analysis of XPS and ToF-SIMS depth profiles. Multivariate analyses often provide insight into data sets that is not easily obtained in a univariate fashion. Pattern recognition entropy (PRE), which has its roots in Shannon's information theory, is also introduced. This approach is not the same as the mutual information/entropy approaches sometimes used in data processing. A discussion of the theory of each technique is presented. PCA, MCR, and PRE are applied to four different data sets obtained from: a ToF-SIMS depth profile through ca. 100 nm of plasma polymerized C3F6 on Si, a ToF-SIMS depth profile through ca. 100 nm of plasma polymerized PNIPAM (poly (N-isopropylacrylamide)) on Si, an XPS depth profile through a film of SiO2 on Si, and an XPS depth profile through a film of Ta2O5 on Ta. PCA, MCR, and PRE reveal the presence of interfaces in the films, and often indicate that the first few scans in the depth profiles are different from those that follow. PRE and backward difference PRE provide this information in a straightforward fashion. Rises in the PRE signals at interfaces suggest greater complexity to the corresponding spectra. Results from PCA, especially for the higher principal components, were sometimes difficult to understand. MCR analyses were generally more interpretable.

Surfactant-mediated growth of cobalt on magnesium oxide(111)

NASA Astrophysics Data System (ADS)

Johnson-Steigelman, Harry Trevor

Monolayer films of Co have been deposited using an electrostatic electron-beam evaporator on single-crystal MgO(111)-( 3x3 ) R 30° and MgO(111)-(1x1) substrates held at room temperature (RT), with subsequent annealing of temperatures 400°C to 800°C. These films have been characterized using low-energy electron diffraction (LEED), x-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Upon RT deposition of Co, the LEED pattern of the substrate disappears and the XPS signal of MgO features reduce in intensity. After short anneals of 400°C, the LEED pattern returns and the MgO features increase in intensity. AFM images suggest that islanding has occurred at the surface. This conclusion is supported by the behavior of thicker films of Co on MgO(111), which showed pronounced changes in the MgO related XPS features. The behavior of the Mg 2p and O 1s features were analyzed and compared to previously reported reconstructions of the MgO(111)-(1x1) and MgO(111)-( 3x3 ) R 30° surfaces. Ag was examined as a potential surfactant to aid in the growth of smooth Co films. Ag was deposited onto MgO(111)-( 3x3 ) R 30° substrates and investigated using XPS, LEED, and AFM. It was found that Ag formed islands upon annealing. Despite the fact that Ag formed islands, it was found that the presence of Ag did have a surfactant effect upon the thin-film growth of Co on Ag/MgO(111)-( 3x3 ) R 30° substrates with 1-2 ML of Ag. Co islands were still present, but much more smooth than islands formed without the Ag surfactant. XPS peak intensity changes and AFM suggest strongly that Ag floated to the top of these samples at temperatures above 400°C. The Co growth mode appears to be Volmer-Weber island growth, as seen in AFM.

DOE ZERH Case Study: BrightLeaf Homes, McCormick Avenue, Brookfield, IL

DOE Office of Scientific and Technical Information (OSTI.GOV)

none,

2015-09-01

Case study of a DOE 2015 Housing Innovation Award winning production home in the cold climate that got a HERS 38 without PV, with staggered 2x4 studs every 8”on a 2x6 plate with dense-packed R-25 cellulose, basement with 3” XPS exterior and 2: XPS under slab; a vented attic with spray foam top plates and R-60 blown cellulose; 96% AFUE furnace, 14 SEER AC, plus fresh air intake.

Growth and Electronic Structure of Heusler Compounds for Use in Electron Spin Based Devices

DTIC Science & Technology

2015-06-01

either Co– or MnSi– initiated films on c(4x4) GaAs. Studies using x - ray photoemission spectroscopy (XPS), STM/STS, and transmission electron microscopy...Co– or MnSi– initiated films on c(4x4) GaAs. Studies using x - ray photoemission spectroscopy (XPS), STM/STS, and transmission electron microscopy (TEM...diagram of the Palmstrøm lab in-situ growth and char- acterization setup, with 6 MBE growth chambers, 3 scanning probe microscopes, an x - ray

XPS study of ruthenium tris-bipyridine electrografted from diazonium salt derivative on microcrystalline boron doped diamond.

PubMed

Agnès, Charles; Arnault, Jean-Charles; Omnès, Franck; Jousselme, Bruno; Billon, Martial; Bidan, Gérard; Mailley, Pascal

2009-12-28

Boron doped diamond (BDD) functionalization has received an increasing interest during the last few years. Such an infatuation comes from the original properties of BDD, including chemical stability or an electrochemical window, that opens the way for the design of (bio)sensors or smart interfaces. In such a context, diazonium salts appear to be well suited for BDD functionalization as they enable covalent immobilization of functional entities such as enzymes or DNA. In this study we report microcrystalline BDD functionalization with a metallic complex, ruthenium tris(bipyridine), using the p-(tris(bipyridine)Ru(2+))phenyl diazonium salt. Electrografting using cyclic voltammetry (CV) allowed the formation of a ruthenium complex film that was finely characterized using electrochemistry and X-ray photoelectron spectroscopy (XPS). Moreover, we showed that chronopotentiometry (CP) is a convenient tool to monitor Ru complex film deposition through the control of the electrochemical pulse parameters (i.e. current density and pulse duration). Finally, such a control was demonstrated through the correlation between electrochemical and XPS characterizations.

Structural and magnetic characterization of copper sulfonated phthalocyanine grafted onto treated polyethylene

NASA Astrophysics Data System (ADS)

Reznickova, A.; Kolska, Z.; Orendac, M.; Cizmar, E.; Sajdl, P.; Svorcik, V.

2016-08-01

This study focuses on high density polyethylene (HDPE) activated by Ar plasma treatment, subsequently grafted with copper sulfonated phthalocyanine (CuPc) especially pointing out to the surface and magnetic properties of those composites. Properties of pristine PE and their plasma treated counterparts were studied by different experimental techniques: X-ray photoelectron spectroscopy (XPS), UV-vis spectroscopy, zeta potential and by electron spin resonance (ESR). XPS analysis confirmed the successful grafting of phthalocyanine. The highest absorption was found for the sample grafted with bCuPc for 1 h. Electrokinetic analysis also confirmed the plasma treatment and also subsequent CuPc grafting influence significantly the surface chemistry and charge. These results correspond well with XPS determination. ESR studies confirmed the presence of CuPc grafted on HDPE. It was found, that grafting is mediated by magnetically inactive functional groups, rather than radicals. Magnetic properties of CuPc do not seem to change significantly after grafting CuPc on polyethylene surface.

The (001) 3C SiC surface termination and band structure after common wet chemical etching procedures, stated by XPS, LEED, and HREELS

NASA Astrophysics Data System (ADS)

Tengeler, Sven; Kaiser, Bernhard; Ferro, Gabriel; Chaussende, Didier; Jaegermann, Wolfram

2018-01-01

The (001) surface of cubic silicon carbide (3C SiC) after cleaning, Ar sputtering and three different wet chemical etching procedures was thoroughly investigated via (angle resolved) XPS, HREELS, and LEED. While Ar sputtering was found to be unsuitable for surface preparation, all three employed wet chemical etching procedures (piranha/NH4F, piranha/HF, and RCA) provide a clean surface. HF as oxide removal agent tends to result in fluorine traces on the sample surface, despite thorough rinsing. All procedures yield a 1 × 1 Si-OH/C-H terminated surface. However, the XPS spectra reveal some differences in the resulting surface states. NH4F for oxide removal produces a flat band situation, whereas the other two procedures result in a slight downward (HF) or upward (RCA) band bending. Because the band bending is small, it can be concluded that the number of unsaturated surface defects is low.

In situ formation of the active sites in Pd-Au bimetallic nanocatalysts for CO oxidation: NAP (near ambient pressure) XPS and MS study.

PubMed

Bukhtiyarov, A V; Prosvirin, I P; Saraev, A A; Klyushin, A Yu; Knop-Gericke, A; Bukhtiyarov, V I

2018-06-07

Model bimetallic Pd-Au/HOPG catalysts have been investigated in the CO oxidation reaction using a combination of NAP XPS and MS techniques. The samples have shown catalytic activity at temperatures above 150 °C. The redistribution of Au and Pd on the surface depending on the reaction conditions has been demonstrated using NAP XPS. The Pd enrichment of the bimetallic particles' surface under reaction gas mixture has been shown. Apparently, CO adsorption induces Pd segregation on the surface. Heating the sample under reaction conditions above 150 °C decomposes the Pd-CO state due to CO desorption and reaction and simultaneous Pd-Au alloy formation on the surface takes place. Cooling back down to RT results in reversible Pd segregation due to Pd-CO formation and the sample becomes inactive. It has been shown that in situ studies are necessary for investigation of the active sites in Pd-Au bimetallic systems.

X-ray photoelectron and mass spectroscopic study of electron irradiation and thermal stability of polytetrafluoroethylene

NASA Technical Reports Server (NTRS)

Wheeler, Donald R.; Pepper, Stephen V.

1990-01-01

Polytetrafluoroethylene (PTFE) was subjected to 3 keV electron bombardment and then heated in vacuum to 300 C. The behavior of the material as a function of radiation dose and temperature was studied by X-ray photoelectron spectroscopy (XPS) of the surface and mass spectroscopy of the species evolved. A quantitative comparison of the radiation dose rate with that in other reported studies showed that, for a given total dose, the damage observed by XPS is greater for higher dose rates. Lightly damaged material heated to 300 C evolved saturated fluorocarbon species, whereas unsaturated fluorocarbon species evolved from heavily damaged material. After heating the heavily damaged material, those features in the XPS that were associated with damage diminished, giving the appearance that the radiation damage annealed. The apparent annealing of the radiation damage was found to be due to the covering of the network by saturated fragments that easily diffused through the decomposed material to the surface region upon heating.

Adsorption differences between low coverage enantiomers of alanine on the chiral Cu{421}R surface.

PubMed

Gladys, Michael J; Han, Jeong Woo; Pedersen, Therese S; Tadich, Anton; O'Donnell, Kane M; Thomsen, Lars

2017-05-31

Chiral separation using heterogeneous methods has long been sought after. Chiral metal surfaces have the potential to make it possible to model these systems using small amino acids, the building blocks for proteins. A comparison of submonolayer concentrations of alanine enantiomers adsorbed onto Cu{421} R has revealed a large geometrical differences between the two molecules as compared to the saturated coverage. Large differences were observed in HR-XPS and NEXAFS and complemented by theoretical DFT calculations. At approximately one third of a monolayer a comparison of the C1s XPS signal showed a shift in the methyl group of more than 300 meV indicating that the two enantiomers are in different chemical environments. NEXAFS spectroscopy confirmed the XPS variations and showed large differences in the orientation of the adsorbed molecules. Our DFT results show that the l-enantiomer is energetically the most stable in the {311} microfacet configuration. In contrast to the full monolayer coverage, these lower coverages showed enhanced selectivity.

Structural model of homogeneous As–S glasses derived from Raman spectroscopy and high-resolution XPS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Golovchak, R.; Shpotyuk, O.; Mccloy, J. S.

2010-11-28

The structure of homogeneous bulk As x S 100- x (25 ≤ x ≤ 42) glasses, prepared by the conventional rocking–melting–quenching method, was investigated using high-resolution X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. It is shown that the main building blocks of their glass networks are regular AsS 3/2 pyramids and sulfur chains. In the S-rich domain, the existence of quasi-tetrahedral (QT) S = As(S 1/2) 3 units is deduced from XPS data, but with a concentration not exceeding ~3–5% of total atomic sites. Therefore, QT units do not appear as primary building blocks of the glass backbone in thesemore » materials, and an optimally-constrained network may not be an appropriate description for glasses when x < 40. Finally, it is shown that, in contrast to Se-based glasses, the ‘chain-crossing’ model is only partially applicable to sulfide glasses.« less

Initial stages of oxide formation on the Zr surface at low oxygen pressure: An in situ FIM and XPS study

PubMed Central

Bespalov, I.; Datler, M.; Buhr, S.; Drachsel, W.; Rupprechter, G.; Suchorski, Y.

2015-01-01

An improved methodology of the Zr specimen preparation was developed which allows fabrication of stable Zr nanotips suitable for FIM and AP applications. Initial oxidation of the Zr surface was studied on a Zr nanotip by FIM and on a polycrystalline Zr foil by XPS, both at low oxygen pressure (10−8–10−7 mbar). The XPS data reveal that in a first, fast stage of oxidation, a Zr suboxide interlayer is formed which contains three suboxide components (Zr+1, Zr+2 and Zr+3) and is located between the Zr surface and a stoichiometric ZrO2 overlayer that grows in a second, slow oxidation stage. The sole suboxide layer has been observed for the first time at very early states of the oxidation (oxygen exposure ≤4 L). The Ne+ FIM observations are in accord with a two stage process of Zr oxide formation. PMID:25766998

Antioxidation performance of poly(vinyl alcohol) modified poly(vinylidene fluoride) membranes

NASA Astrophysics Data System (ADS)

Wang, Daohui; Li, Xianfeng; Li, Qing; Liu, Zhen; Li, Nana; Huang, Qinglin; Zhang, Yufeng; Xiao, Changfa

2018-03-01

Commercial poly(vinylidene fluoride) (PVDF) membranes were modified by dip-coating and crosslinking hydrophilic poly(vinyl alcohol) (PVA) on the membrane surface. The antioxidation performance of the modified PVDF membranes was evaluated via exposing the modified membranes to sodium hypochlorite and potassium permanganate solutions for 5-30 days, respectively. The evaluation was based on the influences of the two oxidants on the permeability, rejection, and hydrophility of the modified membranes, which were characterized by water flux, ink rejection, water contact angle, x-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy, and x-ray diffraction (XRD) measurements. The XPS and water contact angle results show that the hydrophilicity of PVDF membranes was significantly improved when PVA was crosslinked on the surface of PVDF membranes. When the modified membranes had been treated with sodium hypochlorite or potassium permanganate for 30 days, the permeability and hydrophilicity were basically maintained and the rejection was slightly decreased. XPS and XRD indicated that some of PVAs coated on the membrane surface could be oxidized and peeled.

Production of sp3 hybridization by swift heavy ion irradiation of HOPG

NASA Astrophysics Data System (ADS)

Zeng, J.; Zhai, P. F.; Liu, J.; Yao, H. J.; Duan, J. L.; Hou, M. D.; Sun, Y. M.; Li, G. P.

2013-07-01

Highly oriented pyrolytic graphite (HOPG) samples were irradiated by swift heavy ions (86Kr, 209Bi and 238U) with the fluence of 1011-1013 ions/cm2 at room temperature. The production of sp3 hybridization by the irradiation process has been confirmed directly by X-ray photoelectron spectroscopy (XPS). In this work, both irradiated and pristine HOPG samples were investigated by XPS and Raman spectroscopy. The existence of sp3 component is confirmed on the surface of the irradiated HOPG samples. XPS result shows that the acreage ratio Isp3/Isp2 increases with the ion fluence and saturates at a higher value of irradiation. It is found that the amount of hybridization (Isp3/Isp2) strongly depends on the electronic energy loss in the sample. Raman spectra of the irradiated samples show the increasing of acreage ratio ID/IG with the ion fluence, which indicates the change of the atomic structure and the phase transition from sp2 to sp3.

Overview of xeroderma pigmentosum proteins architecture, mutations and post-translational modifications.

PubMed

Feltes, Bruno César; Bonatto, Diego

2015-01-01

The xeroderma pigmentosum complementation group proteins (XPs), which include XPA through XPG, play a critical role in coordinating and promoting global genome and transcription-coupled nucleotide excision repair (GG-NER and TC-NER, respectively) pathways in eukaryotic cells. GG-NER and TC-NER are both required for the repair of bulky DNA lesions, such as those induced by UV radiation. Mutations in genes that encode XPs lead to the clinical condition xeroderma pigmentosum (XP). Although the roles of XPs in the GG-NER/TC-NER subpathways have been extensively studied, complete knowledge of their three-dimensional structure is only beginning to emerge. Hence, this review aims to summarize the current knowledge of mapped mutations and other structural information on XP proteins that influence their function and protein-protein interactions. We also review the possible post-translational modifications for each protein and the impact of these modifications on XP protein functions. Copyright © 2014 Elsevier B.V. All rights reserved.

Graphene Membranes for Atmospheric Pressure Photoelectron Spectroscopy.

PubMed

Weatherup, Robert S; Eren, Baran; Hao, Yibo; Bluhm, Hendrik; Salmeron, Miquel B

2016-05-05

Atmospheric pressure X-ray photoelectron spectroscopy (XPS) is demonstrated using single-layer graphene membranes as photoelectron-transparent barriers that sustain pressure differences in excess of 6 orders of magnitude. The graphene serves as a support for catalyst nanoparticles under atmospheric pressure reaction conditions (up to 1.5 bar), where XPS allows the oxidation state of Cu nanoparticles and gas phase species to be simultaneously probed. We thereby observe that the Cu(2+) oxidation state is stable in O2 (1 bar) but is spontaneously reduced under vacuum. We further demonstrate the detection of various gas-phase species (Ar, CO, CO2, N2, O2) in the pressure range 10-1500 mbar including species with low photoionization cross sections (He, H2). Pressure-dependent changes in the apparent binding energies of gas-phase species are observed, attributable to changes in work function of the metal-coated grids supporting the graphene. We expect atmospheric pressure XPS based on this graphene membrane approach to be a valuable tool for studying nanoparticle catalysis.

Depth resolved compositional analysis of aluminium oxide thin film using non-destructive soft x-ray reflectivity technique

NASA Astrophysics Data System (ADS)

Sinha, Mangalika; Modi, Mohammed H.

2017-10-01

In-depth compositional analysis of 240 Å thick aluminium oxide thin film has been carried out using soft x-ray reflectivity (SXR) and x-ray photoelectron spectroscopy technique (XPS). The compositional details of the film is estimated by modelling the optical index profile obtained from the SXR measurements over 60-200 Å wavelength region. The SXR measurements are carried out at Indus-1 reflectivity beamline. The method suggests that the principal film region is comprised of Al2O3 and AlOx (x = 1.6) phases whereas the interface region comprised of SiO2 and AlOx (x = 1.6) mixture. The soft x-ray reflectivity technique combined with XPS measurements explains the compositional details of principal layer. Since the interface region cannot be analyzed with the XPS technique in a non-destructive manner in such a case the SXR technique is a powerful tool for nondestructive compositional analysis of interface region.

Elemental content of enamel and dentin after bleaching of teeth (a comparative study between laser-induced breakdown spectroscopy and x-ray photoelectron spectroscopy)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Imam, H.; Ahmed, Doaa; Eldakrouri, Ashraf

2013-06-21

The elemental content of the superficial and inner enamel as well as that of dentin was analyzed using laser-induced breakdown spectroscopy (LIBS) and x-ray photoelectron spectroscopy (XPS) of bleached and unbleached tooth specimens. It is thus clear from the spectral analysis using both the LIBS and XPS technique that elemental changes (though insignificant within the scopes of this study) of variable intensities do occur on the surface of the enamel and extend deeper to reach dentin. The results of the LIBS revealed a slight reduction in the calcium levels in the bleached compared to the control specimens in all themore » different bleaching groups and in both enamel and dentin. The good correlation found between the LIBS and XPS results demonstrates the possibility of LIBS technique for detection of minor loss in calcium and phosphorus in enamel and dentin.« less

Discrimination between biologically relevant calcium phosphate phases by surface-analytical techniques

NASA Astrophysics Data System (ADS)

Kleine-Boymann, Matthias; Rohnke, Marcus; Henss, Anja; Peppler, Klaus; Sann, Joachim; Janek, Juergen

2014-08-01

The spatially resolved phase identification of biologically relevant calcium phosphate phases (CPPs) in bone tissue is essential for the elucidation of bone remodeling mechanisms and for the diagnosis of bone diseases. Analytical methods with high spatial resolution for the discrimination between chemically quite close phases are rare. Therefore the applicability of state-of-the-art ToF-SIMS, XPS and EDX as chemically specific techniques was investigated. The eight CPPs hydroxyapatite (HAP), β-tricalcium phosphate (β-TCP), α-tricalcium phosphate (α-TCP), octacalcium phosphate (OCP), dicalcium phosphate dihydrate (DCPD), dicalcium phosphate (DCP), monocalcium phosphate (MCP) and amorphous calcium phosphate (ACP) were either commercial materials in high purity or synthesized by ourselves. The phase purity was proven by XRD analysis. All of the eight CPPs show different mass spectra and the phases can be discriminated by applying the principal component analysis method to the mass spectrometric data. The Ca/P ratios of all phosphates were determined by XPS and EDX. With both methods some CPPs can be distinguished, but the obtained Ca/P ratios deviate systematically from their theoretical values. It is necessary in any case to determine a calibration curve, respectively the ZAF values, from appropriate standards. In XPS also the O(1s)-satellite signals are correlated to the CPPs composition. Angle resolved and long-term XPS measurements of HAP clearly prove that there is no phosphate excess at the surface. Decomposition due to X-ray irradiation has not been observed.

Cyclic fatigue resistance of XP-endo Shaper compared with different nickel-titanium alloy instruments.

PubMed

Elnaghy, Amr; Elsaka, Shaymaa

2018-04-01

The aims of this study were to assess and compare the resistance to cyclic fatigue of XP-endo Shaper (XPS; FKG Dentaire, La Chaux-de-Fonds, Switzerland) instruments with TRUShape (TRS; Dentsply Tulsa Dental Specialties, Tulsa, OK, USA), HyFlex CM (HCM; Coltene, Cuyahoga Falls, OH, USA), Vortex Blue (VB; Dentsply Tulsa Dental Specialties), and iRace (iR; FKG Dentaire) nickel-titanium rotary instruments at body temperature. Size 30, 0.01 taper of XPS, size 30, 0.04 taper of HCM, VB, iR, and size 30, 0.06 taper of TRS instruments were immersed in saline at 37 ± 1 °C during cyclic fatigue testing. The instruments were tested with 60° angle of curvature and a 3-mm radius of curvature. The number of cycles to failure (NCF) was calculated and the length of the fractured segment was measured. Fractographic examination of the fractured surface was performed using a scanning electron microscope. The data were analyzed statistically using Kruskal-Wallis H test and Mann-Whitney U tests. Statistical significance was set at P < 0.05. XPS had a significantly greater NCF compared with the other instruments (P < 0.001). The topographic appearance of the fracture surfaces of tested instruments revealed ductile fracture of cyclic fatigue failure. XPS instruments exhibited greater cyclic fatigue resistance compared with the other tested instruments. XP-endo Shaper instruments could be used more safely in curved canals due to their higher fatigue resistance.

Valence-band offsets of CoTiSb/In0.53Ga0.47As and CoTiSb/In0.52Al0.48As heterojunctions

NASA Astrophysics Data System (ADS)

Harrington, S. D.; Sharan, A.; Rice, A. D.; Logan, J. A.; McFadden, A. P.; Pendharkar, M.; Pennachio, D. J.; Wilson, N. S.; Gui, Z.; Janotti, A.; Palmstrøm, C. J.

2017-08-01

The valence-band offsets, ΔEv, between semiconducting half-Heusler compound CoTiSb and lattice-matched III-V In0.53Ga0.47As and In0.52Al0.48As heterojunction interfaces have been measured using X-ray photoemission spectroscopy (XPS). These interfaces were formed using molecular beam epitaxy and transferred in situ for XPS measurements. Valence-band offsets of 0.30 eV and 0.58 eV were measured for CoTiSb/In0.53Ga0.47As and CoTiSb/In0.52Al0.48As, respectively. By combining these measurements with previously reported XPS ΔEv (In0.53Ga0.47As/In0.52Al0.48As) data, the results suggest that band offset transitivity is satisfied. In addition, the film growth order of the interface between CoTiSb and In0.53Ga0.47As is explored and does not seem to affect the band offsets. Finally, the band alignments of CoTiSb with GaAs, AlAs, and InAs are calculated using the density function theory with the HSE06 hybrid functional and applied to predict the band alignment of CoTiSb with In0.53Ga0.47As and In0.52Al0.48As. Good agreement is found between the calculated valence-band offsets and those determined from XPS.

Effects of Mn Ion Implantation on XPS Spectroscopy of GaN Thin Films

NASA Astrophysics Data System (ADS)

Majid, Abdul; Ahmad, Naeem; Rizwan, Muhammad; Khan, Salah Ud-Din; Ali, Fekri Abdulraqeb Ahmed; Zhu, Jianjun

2018-02-01

Gallium nitride (GaN) thin film was deposited onto a sapphire substrate and then implanted with 250 keV Mn ions at two different doses of 2 × 1016 ions/cm2 and 5 × 1016 ions/cm2. The as-grown and post-implantation-thermally-annealed samples were studied in detail using x-ray photoelectron spectroscopy (XPS). The XPS peaks of Ga 3 d, Ga 2 p, N 1 s, Mn 2 p and C 1 s were recorded in addition to a full survey of the samples. The doublet peaks of Ga 2 p for pure GaN were observed blue-shifted when compared with elemental Ga, and appeared further shifted to higher energies for the implanted samples. These observations point to changes in the bonds and the chemical environment of the host as a result of ion implantation. The results revealed broadening of the N 1 s peak after implantation, which is interpreted in terms of the presence of N-Mn bonds in addition to N-Ga bonds. The XPS spectra of Mn 2 p recorded for ion-implanted samples indicated splitting of Mn 2 p 1/2 and Mn 2 p 3/2 peaks higher than that for metallic Mn, which helps rule out the possibility of clustering and points to substitutional doping of Mn. These observations provide a framework that sheds light on the local environment of the material for understanding the mechanism of magnetic exchange interactions in Mn:GaN based diluted magnetic semiconductors.

Empirical optimization of DFT  +  U and HSE for the band structure of ZnO.

PubMed

Bashyal, Keshab; Pyles, Christopher K; Afroosheh, Sajjad; Lamichhane, Aneer; Zayak, Alexey T

2018-02-14

ZnO is a well-known wide band gap semiconductor with promising potential for applications in optoelectronics, transparent electronics, and spintronics. Computational simulations based on the density functional theory (DFT) play an important role in the research of ZnO, but the standard functionals, like Perdew-Burke-Erzenhof, result in largely underestimated values of the band gap and the binding energies of the Zn 3d electrons. Methods like DFT  +  U and hybrid functionals are meant to remedy the weaknesses of plain DFT. However, both methods are not parameter-free. Direct comparison with experimental data is the best way to optimize the computational parameters. X-ray photoemission spectroscopy (XPS) is commonly considered as a benchmark for the computed electronic densities of states. In this work, both DFT  +  U and HSE methods were parametrized to fit almost exactly the binding energies of electrons in ZnO obtained by XPS. The optimized parameterizations of DFT  +  U and HSE lead to significantly worse results in reproducing the ion-clamped static dielectric tensor, compared to standard high-level calculations, including GW, which in turn yield a perfect match for the dielectric tensor. The failure of our XPS-based optimization reveals the fact that XPS does not report the ground state electronic structure for ZnO and should not be used for benchmarking ground state electronic structure calculations.

Empirical optimization of DFT  +  U and HSE for the band structure of ZnO

NASA Astrophysics Data System (ADS)

Bashyal, Keshab; Pyles, Christopher K.; Afroosheh, Sajjad; Lamichhane, Aneer; Zayak, Alexey T.

2018-02-01

ZnO is a well-known wide band gap semiconductor with promising potential for applications in optoelectronics, transparent electronics, and spintronics. Computational simulations based on the density functional theory (DFT) play an important role in the research of ZnO, but the standard functionals, like Perdew-Burke-Erzenhof, result in largely underestimated values of the band gap and the binding energies of the Zn3d electrons. Methods like DFT  +  U and hybrid functionals are meant to remedy the weaknesses of plain DFT. However, both methods are not parameter-free. Direct comparison with experimental data is the best way to optimize the computational parameters. X-ray photoemission spectroscopy (XPS) is commonly considered as a benchmark for the computed electronic densities of states. In this work, both DFT  +  U and HSE methods were parametrized to fit almost exactly the binding energies of electrons in ZnO obtained by XPS. The optimized parameterizations of DFT  +  U and HSE lead to significantly worse results in reproducing the ion-clamped static dielectric tensor, compared to standard high-level calculations, including GW, which in turn yield a perfect match for the dielectric tensor. The failure of our XPS-based optimization reveals the fact that XPS does not report the ground state electronic structure for ZnO and should not be used for benchmarking ground state electronic structure calculations.

Electron spectroscopy analysis

NASA Technical Reports Server (NTRS)

Gregory, John C.

1992-01-01

The Surface Science Laboratories at the University of Alabama in Huntsville (UAH) are equipped with x-ray photoelectron spectroscopy (XPS or ESCA) and Auger electron spectroscopy (AES) facilities. These techniques provide information from the uppermost atomic layers of a sample, and are thus truly surface sensitive. XPS provides both elemental and chemical state information without restriction on the type of material that can be analyzed. The sample is placed into an ultra high vacuum (UHV) chamber and irradiated with x-rays which cause the ejection of photoelectrons from the sample surface. Since x-rays do not normally cause charging problems or beam damage, XPS is applicable to a wide range of samples including metals, polymers, catalysts, and fibers. AES uses a beam of high energy electrons as a surface probe. Following electronic rearrangements within excited atoms by this probe, Auger electrons characteristic of each element present are emitted from the sample. The main advantage of electron induced AES is that the electron beam can be focused down to a small diameter and localized analysis can be carried out. On the rastering of this beam synchronously with a video display using established scanning electron microscopy techniques, physical images and chemical distribution maps of the surface can be produced. Thus very small features, such as electronic circuit elements or corrosion pits in metals, can be investigated. Facilities are available on both XPS and AES instruments for depth-profiling of materials, using a beam of argon ions to sputter away consecutive layers of material to reveal sub-surface (and even semi-bulk) analyses.

Surface characterization of LDEF carbon fiber/polymer matrix composites

NASA Technical Reports Server (NTRS)

Grammer, Holly L.; Wightman, James P.; Young, Philip R.; Slemp, Wayne S.

1995-01-01

XPS (x-ray photoelectron spectroscopy) and SEM (scanning electron microscopy) analysis of both carbon fiber/epoxy matrix and carbon fiber/polysulfone matrix composites revealed significant changes in the surface composition as a result of exposure to low-earth orbit. The carbon 1s curve fit XPS analysis in conjunction with the SEM photomicrographs revealed significant erosion of the polymer matrix resins by atomic oxygen to expose the carbon fibers of the composite samples. This erosion effect on the composites was seen after 10 months in orbit and was even more obvious after 69 months.

A comprehensive study of catalytic, morphological and electronic properties of ligand-protected gold nanoclusters using XPS, STM, XAFS, and TPD techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Qiyuan; Cen, Jiajie; Zhao, Yue

Ultra-small gold nanoclusters were synthesized via a ligand exchange method and deposited onto different TiO2 supports to study their properties. STM imaging revealed that the as-synthesized gold nanoclusters had 2-D morphology consisting of monolayers of gold atoms. In conclusion, subsequent XPS, XAFS, and CO oxidation TPD results indicated that heat treatments of gold clusters at different temperatures significantly altered their electronic and catalytic properties due to ligand deprotection and cluster agglomeration.

XPS and Raman studies of Pt catalysts supported on activated carbon

NASA Astrophysics Data System (ADS)

Tyagi, Deepak; Varma, Salil; Bharadwaj, S. R.

2018-04-01

Activated carbon is a widely used support for dispersing noble metals in addition to its many applications. We have prepared platinum catalyst supported on activated carbon for HI decomposition reaction of I-S thermochemical process of hydrogen generation. These catalysts were characterized by XPS and Raman before and after using for the reaction. It was observed that platinum is present in zero oxidation state, while carbon is present is both sp2 and sp3 hybridized forms along with some amount of it bonded to oxygen.

A critical study of the role of the surface oxide layer in titanium bonding

NASA Technical Reports Server (NTRS)

Dias, S.; Wightman, J. P.

1983-01-01

Scanning electron microscope/X-ray photoelectron spectroscopy (SEM/XPS) analysis of fractured adhesively bonded Ti 6-4 samples is discussed. The text adhesives incuded NR 056X polyimide, polypheylquinoxaline (PPQ), and LARC-13 polyimide. Differentiation between cohesive and interfacial failure was based on the absence of presence of a Ti 2p XPS photopeak. In addition, the surface oxide layer on Ti-(6A1-4V) adherends is characterized and bond strength and durability are addressed. Bond durability in various environmental conditions is discussed.

GaAs Surface Passivation for Device Applications.

DTIC Science & Technology

1981-12-01

Ga203.’" . QI. a) / b) x 2.5 •• 24 21 18 As3d a) b) x 2. / 0 II 2 46 43 40 BINDING ENERGY (eV) Fig. 3 XPS spectra from a Ga2O3 covered GaAs surface of Ga...wU 24 21 Gas 18 SAs3d As2O3 ) .. 46 43 40 BINDING ENERGY (e) Fig. 4 XPS spectra from a AsJ03- Ga2O3 covered GaAs surface of Ga 3d (upper panel) and As

A comprehensive study of catalytic, morphological and electronic properties of ligand-protected gold nanoclusters using XPS, STM, XAFS, and TPD techniques

DOE PAGES

Wu, Qiyuan; Cen, Jiajie; Zhao, Yue; ...

2017-12-08

Ultra-small gold nanoclusters were synthesized via a ligand exchange method and deposited onto different TiO2 supports to study their properties. STM imaging revealed that the as-synthesized gold nanoclusters had 2-D morphology consisting of monolayers of gold atoms. In conclusion, subsequent XPS, XAFS, and CO oxidation TPD results indicated that heat treatments of gold clusters at different temperatures significantly altered their electronic and catalytic properties due to ligand deprotection and cluster agglomeration.

New quaternary thallium indium germanium selenide TlInGe2Se6: Crystal and electronic structure

NASA Astrophysics Data System (ADS)

Khyzhun, O. Y.; Parasyuk, O. V.; Tsisar, O. V.; Piskach, L. V.; Myronchuk, G. L.; Levytskyy, V. O.; Babizhetskyy, V. S.

2017-10-01

Crystal structure of a novel quaternary thallium indium germanium selenide TlInGe2Se6 was investigated by means of powder X-ray diffraction method. It was determined that the compound crystallizes in the trigonal space group R3 with the unit cell parameters a = 10.1798(2) Å, c = 9.2872(3) Å. The relationship with similar structures was discussed. The as-synthesized TlInGe2Se6 ingot was tested with X-ray photoelectron spectroscopy (XPS) and X-ray emission spectroscopy (XES). In particular, the XPS valence-band and core-level spectra were recorded for initial and Ar+ ion-bombarded surfaces of the sample under consideration. The XPS data allow for statement that the TlInGe2Se6 surface is rigid with respect to Ar+ ion-bombardment. Particularly, Ar+ ion-bombardment (3.0 keV, 5 min duration, ion current density fixed at 14 μA/cm2) did not cause substantial modifications of stoichiometry in topmost surface layers. Furthermore, comparison on a common energy scale of the XES Se Kβ2 and Ge Kβ2 bands and the XPS valence-band spectrum reveals that the principal contributions of the Se 4p and Ge 4p states occur in the upper and central portions of the valence band of TlInGe2Se6, respectively, with also their substantial contributions in other portions of the band. The bandgap energy of TlInGe2Se6 at the level of αg=103 cm-1 is equal to 2.38 eV at room temperature.

A comparative theoretical study on core-hole excitation spectra of azafullerene and its derivatives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deng, Yunfeng; Department of Physics, Guizhou University, Guiyang 550025; Gao, Bin, E-mail: bin.gao@uit.no

2014-03-28

The core-hole excitation spectra—near-edge x-ray absorption spectroscopy (NEXAFS), x-ray emission spectroscopy (XES), and x-ray photoelectron spectroscopy (XPS) shake-up satellites have been simulated at the level of density functional theory for the azafullerene C{sub 59}N and its derivatives (C{sub 59}N){sup +}, C{sub 59}HN, (C{sub 59}N){sub 2}, and C{sub 59}N–C{sub 60}, in which the XPS shake-up satellites were simulated using our developed equivalent core hole Kohn-Sham (ECH-KS) density functional theory approach [B. Gao, Z. Wu, and Y. Luo, J. Chem. Phys. 128, 234704 (2008)] which aims for the study of XPS shake-up satellites of large-scale molecules. Our calculated spectra are generally inmore » good agreement with available experimental results that validates the use of the ECH-KS method in the present work. The nitrogen K-edge NEXAFS, XES, and XPS shake-up satellites spectra in general can be used as fingerprints to distinguish the azafullerene C{sub 59}N and its different derivatives. Meanwhile, different carbon K-edge spectra could also provide detailed information of (local) electronic structures of different molecules. In particular, a peak (at around 284.5 eV) in the carbon K-edge NEXAFS spectrum of the heterodimer C{sub 59}N–C{sub 60} is confirmed to be related to the electron transfer from the C{sub 59}N part to the C{sub 60} part in this charge-transfer complex.« less

Grafting titanium nitride surfaces with sodium styrene sulfonate thin films

PubMed Central

Zorn, Gilad; Migonney, Véronique; Castner, David G.

2014-01-01

The importance of titanium nitride lies in its high hardness and its remarkable resistance to wear and corrosion, which has led to its use as a coating for the heads of hip prostheses, dental implants and dental surgery tools. However, the usefulness of titanium nitride coatings for biomedical applications could be significantly enhanced by modifying their surface with a bioactive polymer film. The main focus of the present work was to graft a bioactive poly(sodium styrene sulfonate) (pNaSS) thin film from titanium nitride surfaces via a two-step procedure: first modifying the surface with 3-methacryloxypropyltrimethoxysilane (MPS) and then grafting the pNaSS film from the MPS modified titanium through free radical polymerization. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used after each step to characterize success and completeness of each reaction. The surface region of the titanium nitride prior to MPS functionalization and NaSS grafting contained a mixture of titanium nitride, oxy-nitride, oxide species as well as adventitious surface contaminants. After MPS functionalization, Si was detected by XPS, and characteristic MPS fragments were detected by ToF-SIMS. After NaSS grafting, Na and S were detected by XPS and characteristic NaSS fragments were detected by ToF-SIMS. The XPS determined thicknesses of the MPS and NaSS overlayers were ∼1.5 and ∼1.7 nm, respectively. The pNaSS film density was estimated by the toluidine blue colorimetric assay to be 260 ± 70 ng/cm2. PMID:25280842

[Quantitative surface analysis of Pt-Co, Cu-Au and Cu-Ag alloy films by XPS and AES].

PubMed

Li, Lian-Zhong; Zhuo, Shang-Jun; Shen, Ru-Xiang; Qian, Rong; Gao, Jie

2013-11-01

In order to improve the quantitative analysis accuracy of AES, We associated XPS with AES and studied the method to reduce the error of AES quantitative analysis, selected Pt-Co, Cu-Au and Cu-Ag binary alloy thin-films as the samples, used XPS to correct AES quantitative analysis results by changing the auger sensitivity factors to make their quantitative analysis results more similar. Then we verified the accuracy of the quantitative analysis of AES when using the revised sensitivity factors by other samples with different composition ratio, and the results showed that the corrected relative sensitivity factors can reduce the error in quantitative analysis of AES to less than 10%. Peak defining is difficult in the form of the integral spectrum of AES analysis since choosing the starting point and ending point when determining the characteristic auger peak intensity area with great uncertainty, and to make analysis easier, we also processed data in the form of the differential spectrum, made quantitative analysis on the basis of peak to peak height instead of peak area, corrected the relative sensitivity factors, and verified the accuracy of quantitative analysis by the other samples with different composition ratio. The result showed that the analytical error in quantitative analysis of AES reduced to less than 9%. It showed that the accuracy of AES quantitative analysis can be highly improved by the way of associating XPS with AES to correct the auger sensitivity factors since the matrix effects are taken into account. Good consistency was presented, proving the feasibility of this method.

Chemical state analysis of heavily phosphorus-doped epitaxial silicon films grown on Si (1 0 0) by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Minhyeong; Kim, Sungtae; Ko, Dae-Hong

2018-06-01

In this work, we investigated the chemical bonding states in highly P-doped Si thin films epitaxially grown on Si (0 0 1) substrates using high-resolution X-ray photoelectron spectroscopy (HR-XPS). HR-XPS P 2p core-level spectra clearly show spin-orbital splitting between P 2p1/2 and P 2p3/2 peaks in Si films doped with a high concentration of P. Moreover, the intensities of P 2p1/2 and P 2p3/2 peaks for P-doped Si films increase with P concentrations, while their binding energies remained almost identical. These results indicate that more P atoms are incorporated into the substitutional sites of the Si lattice with the increase of P concentrations. In order to identify the chemical states of P-doped Si films shown in XPS Si 2p spectra, the spectra of bulk Si were subtracted from those of Si:P samples, which enables us to clearly identify the new chemical state related to Sisbnd P bonds. We observed that the presence of the two well-resolved new peaks only for the Si:P samples at the binding energy higher than those of a Sisbnd Si bond, which is due to the strong electronegativity of P than that of Si. Experimental findings in this study using XPS open up new doors for evaluating the chemical states of P-doped Si materials in fundamental researches as well as in industrial applications.

Valence-band offsets of CoTiSb/In 0.53Ga 0.47As and CoTiSb/In 0.52Al 0.48As heterojunctions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harrington, S. D.; Sharan, A.; Rice, A. D.

2017-08-11

The valence-band offsets, ΔE v, between semiconducting half-Heusler compound CoTiSb and lattice-matched III-V In 0.53Ga 0.47As and In 0.52Al 0.48As heterojunction interfaces have been measured using X-ray photoemission spectroscopy (XPS). These interfaces were formed using molecular beam epitaxy and transferred in situ for XPS measurements. Valence-band offsets of 0.30 eV and 0.58 eV were measured for CoTiSb/In 0.53Ga 0.47As and CoTiSb/In 0.52Al 0.48As, respectively. By combining these measurements with previously reported XPS ΔE v (In 0.53Ga 0.47As/In 0.52Al 0.48As) data, the results suggest that band offset transitivity is satisfied. In addition, the film growth order of the interface between CoTiSbmore » and In 0.53Ga 0.47As is explored and does not seem to affect the band offsets. Finally, the band alignments of CoTiSb with GaAs, AlAs, and InAs are calculated using the density function theory with the HSE06 hybrid functional and applied to predict the band alignment of CoTiSb with In 0.53Ga 0.47As and In 0.52Al 0.48As. As a result, good agreement is found between the calculated valence-band offsets and those determined from XPS.« less

Effects of rare earth doping on multi-core iron oxide nanoparticles properties

NASA Astrophysics Data System (ADS)

Petran, Anca; Radu, Teodora; Borodi, Gheorghe; Nan, Alexandrina; Suciu, Maria; Turcu, Rodica

2018-01-01

New multi-core iron oxide magnetic nanoparticles doped with rare earth metals (Gd, Eu) were obtained by a one step synthesis procedure using a solvothermal method for potential biomedical applications. The obtained clusters were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray microanalysis (EDX), X-ray photoelectron spectroscopy (XPS) and magnetization measurements. They possess high colloidal stability, a saturation magnetization of up to 52 emu/g, and nearly spherical shape. The presence of rare earth ions in the obtained samples was confirmed by EDX and XPS. XRD analysis proved the homogeneous distribution of the trivalent rare earth ions in the inverse-spinel structure of magnetite and the increase of crystal strain upon doping the samples. XPS study reveals the valence state and the cation distribution on the octahedral and tetrahedral sites of the analysed samples. The observed shift of the XPS valence band spectra maximum in the direction of higher binding energies after rare earth doping, as well as theoretical valence band calculations prove the presence of Gd and Eu ions in octahedral sites. The blood protein adsorption ability of the obtained samples surface, the most important factor of the interaction between biomaterials and body fluids, was assessed by interaction with bovine serum albumin (BSA). The rare earth doped clusters surface show higher afinity for binding BSA. In vitro cytotoxicity test results for the studied samples showed no cytotoxicity in low and medium doses, establishing a potential perspective for rare earth doped MNC to facilitate multiple therapies in a single formulation for cancer theranostics.

Polyethylene imine modified hydrochar adsorption for chromium (VI) and nickel (II) removal from aqueous solution.

PubMed

Shi, Yuanji; Zhang, Tao; Ren, Hongqiang; Kruse, Andrea; Cui, Ruofan

2018-01-01

An adsorbent hydrochar was synthesized from corn cobs and modified with polyethylene imine (PEI). The hydrochars before and after modification were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis. FTIR and XPS revealed that the PEI was grafted onto the hydrochar via ether and imine bonds formed with glutaraldehyde. The maximum adsorption capacities for Cr(VI) (33.663mg/g) and Ni(II) (29.059mg/g) on the modified hydrochars were 365% and 43.7% higher, respectively, than those on the unmodified hydrochar. A pseudo-second-order model described the adsorption of Ni(II) and Cr(VI) on all the adsorbents. The adsorption of Cr(VI) was endothermic, spontaneous, increased disorder, and obeyed the Langmuir model. By contrast, the adsorption of Ni(II) was exothermic, spontaneous, decreased disorder, and obeyed the Freundlich model. XPS confirmed that the adsorption sites and mechanisms for Ni(II) and Cr(VI) on the modified hydrochars were different. Copyright © 2017 Elsevier Ltd. All rights reserved.

Potassium-doped n-type bilayer graphene

NASA Astrophysics Data System (ADS)

Yamada, Takatoshi; Okigawa, Yuki; Hasegawa, Masataka

2018-01-01

Potassium-doped n-type bilayer graphene was obtained. Chemical vapor deposited bilayer and single layer graphene on copper (Cu) foils were used. After etching of Cu foils, graphene was dipped in potassium hydroxide aqueous solutions to dope potassium. Graphene on silicon oxide was characterized by X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), and Raman spectroscopy. Both XPS and EDX spectra indicated potassium incorporation into the bilayer graphene via intercalation between the graphene sheets. The downward shift of the 2D peak position of bilayer graphene after the potassium hydroxide (KOH) treatment was confirmed in Raman spectra, indicating that the KOH-treated bilayer graphene was doped with electrons. Electrical properties were measured using Hall bar structures. The Dirac points of bilayer graphene were shifted from positive to negative by the KOH treatment, indicating that the KOH-treated bilayer graphene was n-type conduction. For single layer graphene after the KOH treatment, although electron doping was confirmed from Raman spectra, the peak of potassium in the X-ray photoelectron spectroscopy (XPS) spectrum was not detected. The Dirac points of single layer graphene with and without the KOH treatment showed positive.

Surface characterization in composite and titanium bonding: Carbon fiber surface treatments for improved adhesion to thermoplastic polymers

NASA Technical Reports Server (NTRS)

Devilbiss, T. A.; Wightman, J. P.

1987-01-01

The effect of anodization in NaOH, H2SO4, and amine salts on the surface chemistry of carbon fibers was examined by X-ray photoelectron spectroscopy (XPS). The surfaces of carbon fibers after anodization in NaOH and H2SO4 were examined by scanning transmission electron microscopy (STEM), angular dependent XPS, UV absorption spectroscopy of the anodization bath, secondary ion mass spectrometry, and polar/dispersive surface energy analysis. Hercules AS-4, Dexter Hysol XAS, and Union Carbide T-300 fibers were examined by STEM, angular dependent XPS, and breaking strength measurement before and after commercial surface treatment. Oxygen and nitrogen were added to the fiber surfaces by anodization in amine salts. Analysis of the plasmon peak in the carbon 1s signal indicated that H2SO4 anodization affected the morphological structure of the carbon fiber surface. The work of adhesion of carbon fibers to thermoplastic resins was calculated using the geometric mean relationship. A correlation was observed between the dispersive component of the work of adhesion and the interfacial adhesion.

Evaluation of the surface properties of PTFE foam coating filter media using XPS and contact angle measurements

NASA Astrophysics Data System (ADS)

Park, Byung Hyun; Lee, Myong-Hwa; Kim, Sang Bum; Jo, Young Min

2011-02-01

A newly developed PTFE foam coating filter was developed which can be used for hot gas cleaning at temperatures up to 250 °C. The emulsion-type PTFE was coated onto a woven glass fiber using a foam coating method. The filter surface was closely examined using X-ray photoelectron spectroscopy (XPS) and contact angle measurements. The XPS results were used to determine the binding force between the carbon and fluorine of PTFE, which imparts coating stability to the filter medium. More than 95% of the bonds of the PTFE foam coating filter were between carbon and fluorine, and this filter demonstrated excellent hydrophobic and good oleophobic properties at the same time. The contact angles of liquid droplets on the filter surface were used to predict the potential wetability of the filter against water or oil. In addition, the very low surface free energy of the filter medium, which was evaluated using the Owens-Wendt method, demonstrates a very stable surface and a high de-dusting quality.

Deposition and characterization of stoichiometric films of V2O5 on Pd(111)

NASA Astrophysics Data System (ADS)

Feng, Xu; Abdel-Rahman, Mohammed K.; Kruppe, Christopher M.; Trenary, Michael

2017-10-01

A simple and efficient method has been used to grow V2O5 thin films on Pd(111) at a substrate temperature of 300 K through physical vapor deposition by heating a fine powder of V2O5 in a non-oxidative, UHV environment. X-ray photoelectron spectroscopy (XPS), reflection absorption infrared spectroscopy (RAIRS) and low energy electron diffraction (LEED) were used to characterize the thin films. When the as-grown films exceed a minimum thickness, characteristic features of V2O5 were revealed by XPS and RAIRS, which confirms the presence of stoichiometric V2O5. LEED indicates no long range order of the as-grown films at 300 K. Annealing to temperatures between 600 and 700 K causes a reduction of V2O5 to VO2 as identified by XPS and the formation of ordered structures as determined by LEED, and VO2 is predominant after annealing to 800 K. After further annealing to 1000 K, only an ordered form of V2O3 is present on Pd(111).

Long-term lithium-ion battery performance improvement via ultraviolet light treatment of the graphite anode

DOE PAGES

An, Seong Jin; Li, Jianlin; Sheng, Yangping; ...

2016-01-01

Effects of ultraviolet (UV) light on dried graphite anodes were investigated in terms of the cycle life of lithium ion batteries. The time variations for the UV treatment were 0 (no treatment), 20, 40, and 60 minutes. UV-light-treated graphite anodes were assembled for cycle life tests in pouch cells with pristine Li 1.02Ni 0.50Mn 0.29Co 0.19O 2 (NMC 532) cathodes. UV treatment for 40 minutes resulted in the highest capacity retention and the lowest resistance after the cycle life testing. X-ray photoelectron spectroscopy (XPS) and contact angle measurements on the graphite anodes showed changes in surface chemistry and wetting aftermore » the UV treatment. XPS also showed increases in solvent products and decreases in salt products on the SEI surface when UV-treated anodes were used. In conclusion, the thickness of the surface films and their compositions on the anodes and cathodes were also estimated using survey scans and snapshots from XPS depth profiles.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoshimoto, Shinya, E-mail: yosshi@issp.u-tokyo.ac.jp; Shiozawa, Yuichiro; Koitaya, Takanori

Electronic states and electrical conductivity of the native oxide Si(111) surface adsorbed with an electron donor tetrakis(dimethylamino)ethylene (TDAE) were investigated using ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy (XPS), and independently driven four-probe conductivity measurements. The formation of positively charged TDAE species is confirmed by the downward shift of the vacuum level by 1.45 eV, the absence of HOMO level in the valence band, and observation of the positively charged state in the N 1s XPS spectra. Si 2p XPS spectra and four-probe conductivity measurements revealed that TDAE adsorption induces an increase in downward band bending and a reduction in electrical resistancemore » of the surface, respectively. The sheet conductivity and the electron density of the surface are 1.1 μS/◻ and 4.6 × 10{sup 9} cm{sup −2}, respectively, after TDAE adsorption, and they are as high as 350% of the original surface. These results demonstrate that the electron density of the semiconductor surface is successfully controlled by the electron donor molecule TDAE.« less

Epitaxial corundum-VTiO 3 thin films grown on c-cut sapphire

DOE PAGES

Kramer, Alan; Sutter, Eli; Su, Dong; ...

2017-04-12

Corundum structured VTiO 3 has been grown as epitaxial films on c-cut sapphire by laser molecular beam epitaxy. The properties of the film were characterized by reflection high energy electron diffraction, x-ray diffraction, transmission electron microscopy, and photoemission spectroscopy. All the structural probes clearly indicate the corundum structure of the film. X-ray photoemission spectroscopy (XPS) indicates that V is in a 3+ charge state implying that Ti also needs to adopt a 3+ charge state in order for the corundum structure to form. However, the Ti-2p XPS, while clearly broadened to the lower binding energy side compared to TiO 2,more » also exhibits a pronounced Ti 4+ component. This is tentatively assigned to a final state effect in XPS measurements and not as the true cation state. In conclusion, the valence band spectra show occupation of 3d metal states that resemble more closely those of Ti 2O 3 than for V 2O 3, suggesting that only the a1g molecular states are occupied.« less

Quantification of Efficiency of Beneficiation of Lunar Regolith

NASA Technical Reports Server (NTRS)

Trigwell, Steve; Lane, John; Captain, James; Weis, Kyle; Quinn, Jacqueline; Watanabe, Fumiya

2011-01-01

Electrostatic beneficiation of lunar regolith is being researched at Kennedy Space Center to enhance the ilmenite concentration of the regolith for the production of oxygen in in-situ resource utilization on the lunar surface. Ilmenite enrichment of up to 200% was achieved using lunar simulants. For the most accurate quantification of the regolith particles, standard petrographic methods are typically followed, but in order to optimize the process, many hundreds of samples were generated in this study that made the standard analysis methods time prohibitive. In the current studies, X-ray photoelectron spectroscopy (XPS) and Secondary Electron microscopy/Energy Dispersive Spectroscopy (SEM/EDS) were used that could automatically, and quickly, analyze many separated fractions of lunar simulant. In order to test the accuracy of the quantification, test mixture samples of known quantities of ilmenite (2, 5, 10, and 20 wt%) in silica (pure quartz powder), were analyzed by XPS and EDS. The results showed that quantification for low concentrations of ilmenite in silica could be accurately achieved by both XPS and EDS, knowing the limitations of the techniques. 1

Perspective: Chemical reactions in ionic liquids monitored through the gas (vacuum)/liquid interface.

PubMed

Maier, F; Niedermaier, I; Steinrück, H-P

2017-05-07

This perspective analyzes the potential of X-ray photoelectron spectroscopy under ultrahigh vacuum (UHV) conditions to follow chemical reactions in ionic liquids in situ. Traditionally, only reactions occurring on solid surfaces were investigated by X-ray photoelectron spectroscopy (XPS) in situ. This was due to the high vapor pressures of common liquids or solvents, which are not compatible with the required UHV conditions. It was only recently realized that the situation is very different when studying reactions in Ionic Liquids (ILs), which have an inherently low vapor pressure, and first studies have been performed within the last years. Compared to classical spectroscopy techniques used to monitor chemical reactions, the advantage of XPS is that through the analysis of their core levels all relevant elements can be quantified and their chemical state can be analyzed under well-defined (ultraclean) conditions. In this perspective, we cover six very different reactions which occur in the IL, with the IL, or at an IL/support interface, demonstrating the outstanding potential of in situ XPS to gain insights into liquid phase reactions in the near-surface region.

Lattice and Valence Electronic Structures of Crystalline Octahedral Molybdenum Halide Clusters-Based Compounds, Cs2[Mo6X14] (X = Cl, Br, I), Studied by Density Functional Theory Calculations.

PubMed

Saito, Norio; Cordier, Stéphane; Lemoine, Pierric; Ohsawa, Takeo; Wada, Yoshiki; Grasset, Fabien; Cross, Jeffrey S; Ohashi, Naoki

2017-06-05

The electronic and crystal structures of Cs 2 [Mo 6 X 14 ] (X = Cl, Br, I) cluster-based compounds were investigated by density functional theory (DFT) simulations and experimental methods such as powder X-ray diffraction, ultraviolet-visible spectroscopy, and X-ray photoemission spectroscopy (XPS). The experimentally determined lattice parameters were in good agreement with theoretically optimized ones, indicating the usefulness of DFT calculations for the structural investigation of these clusters. The calculated band gaps of these compounds reproduced those experimentally determined by UV-vis reflectance within an error of a few tenths of an eV. Core-level XPS and effective charge analyses indicated bonding states of the halogens changed according to their sites. The XPS valence spectra were fairly well reproduced by simulations based on the projected electron density of states weighted with cross sections of Al K α , suggesting that DFT calculations can predict the electronic properties of metal-cluster-based crystals with good accuracy.

Characterization of Colloidal Quantum Dot Ligand Exchange by X-ray Photoelectron Spectroscopy

NASA Astrophysics Data System (ADS)

Atewologun, Ayomide; Ge, Wangyao; Stiff-Roberts, Adrienne D.

2013-05-01

Colloidal quantum dots (CQDs) are chemically synthesized semiconductor nanoparticles with size-dependent wavelength tunability. Chemical synthesis of CQDs involves the attachment of long organic surface ligands to prevent aggregation; however, these ligands also impede charge transport. Therefore, it is beneficial to exchange longer surface ligands for shorter ones for optoelectronic devices. Typical characterization techniques used to analyze surface ligand exchange include Fourier-transform infrared spectroscopy, x-ray diffraction, transmission electron microscopy, and nuclear magnetic resonance spectroscopy, yet these techniques do not provide a simultaneously direct, quantitative, and sensitive method for evaluating surface ligands on CQDs. In contrast, x-ray photoelectron spectroscopy (XPS) can provide nanoscale sensitivity for quantitative analysis of CQD surface ligand exchange. A unique aspect of this work is that a fingerprint is identified for shorter surface ligands by resolving the regional XPS spectrum corresponding to different types of carbon bonds. In addition, a deposition technique known as resonant infrared matrix-assisted pulsed laser evaporation is used to improve the CQD film uniformity such that stronger XPS signals are obtained, enabling more accurate analysis of the ligand exchange process.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masuda, Takuya; PRESTO, Japan Science and Technology Agency; Yoshikawa, Hideki

In situ electrochemical X-ray photoelectron spectroscopy (XPS) apparatus, which allows XPS at solid/liquid interfaces under potential control, was constructed utilizing a microcell with an ultra-thin Si membrane, which separates vacuum and a solution. Hard X-rays from a synchrotron source penetrate into the Si membrane surface exposed to the solution. Electrons emitted at the Si/solution interface can pass through the membrane and be analyzed by an analyzer placed in vacuum. Its operation was demonstrated for potential-induced Si oxide growth in water. Effect of potential and time on the thickness of Si and Si oxide layers was quantitatively determined at sub-nanometer resolution.

Co-axial Electrospun Polyacrylonitrile-Poly(methylmethacrylate) Nanofibers: Atomic Force Microscopy and Compositional Characterization

PubMed Central

Zander, N.E.; Strawhecker, K.E.; Orlicki, J.A.; Rawlett, A.M.; Beebe, T.P.

2011-01-01

Poly(methylmethacrylate) (PMMA)- Polyacrylonitrile (PAN) fibers were prepared using a conventional single-nozzle electrospinning technique. The as-spun fibers exhibited core-shell morphology as verified by transmission electron microscopy (TEM) and atomic force microscopy (AFM). AFM-phase and modulus mapping images of the fiber cross-section and x-ray photoelectron spectroscopy (XPS) analysis indicated PAN formed the shell and PMMA the core material. XPS, thermal gravimetric analysis (TGA), and elemental analysis were used to determine fiber compositional information. Soaking the fibers in solvent demonstrated removal of the core material, generating hollow PAN fibers. PMID:21928836

Chemical Visualization of a GaN p-n junction by XPS

PubMed Central

Caliskan, Deniz; Sezen, Hikmet; Ozbay, Ekmel; Suzer, Sefik

2015-01-01

We report on an operando XPS investigation of a GaN diode, by recording the Ga2p3/2 peak position under both forward and reverse bias. Areal maps of the peak positions under reverse bias are completely decoupled with respect to doped regions and allow a novel chemical visualization of the p-n junction in a 2-D fashion. Other electrical properties of the device, such as leakage current, resistivity of the domains are also tapped via recording line-scan spectra. Application of a triangular voltage excitation enables probing photoresponse of the device. PMID:26359762

High resolution X-ray photoelectron spectroscopy of styrene oxide adsorption and reaction on Ag(1 1 1)

NASA Astrophysics Data System (ADS)

Piao, H.; Enever, M. C. N.; Adib, K.; Hrbek, J.; Barteau, M. A.

2004-11-01

Synchrotron-based X-ray photoelectron spectroscopy (XPS) has been used to investigate the adsorption and reaction of styrene oxide on Ag(1 1 1). When adsorption is carried out at 250 K or above, ring opening of styrene oxide forms a stable surface oxametallacycle intermediate which eventually reacts at 485 K to regenerate styrene oxide. High resolution XPS is capable of distinguishing the oxametallacycle from molecularly adsorbed and condensed styrene oxide on the basis of different C1s peak separations. The observed separations are well accounted for by the results of DFT calculations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Pragati, E-mail: pkumar.phy@gmail.com; Department of Physics and Astrophysics, University of Delhi, Delhi, 110 007; Saxena, Nupur

This work shows the influence of Ag concentration on structural properties of pulsed laser deposited nanocrystalline CdS thin film. X-ray photoelectron spectroscopy (XPS) studies confirm the dopant concentration in CdS films and atomic concentration of elements. XPS studies show that the samples are slightly sulfur deficient. GAXRD scan reveals the structural phase transformation from cubic to hexagonal phase of CdS without appearance of any phase of CdO, Ag{sub 2}O or Ag{sub 2}S suggesting the substitutional doping of Ag ions. Photoluminescence studies illustrate that emission intensity increases with increase in dopant concentration upto 5% and then decreases for higher dopant concentration.

Surface studies of low molecular weight photolysis products from UV-ozone oxidised polystyrene

NASA Astrophysics Data System (ADS)

Davidson, M. R.; Mitchell, S. A.; Bradley, R. H.

2005-05-01

The production of low molecular weight oxidised material during UV-ozone treatment of polystyrene has been studied by XPS, GC-MS, FTIR and UV/visible spectroscopy. XPS analysis of the oxidised polystyrene surfaces before and after washing with water or methanol indicates that the removal of oxidation products and the surface that remains after washing is strongly dependent on the choice of solvent. Methanol washing removes a greater proportion of the more highly oxidised carbonyl and carboxyl groups resulting in a surface with a lower oxygen content than that remaining after water washing. Extended exposure to UV-ozone treatment reveals a two-stage oxidation process with mono-substituted benzene rings such as benzaldehyde, acetophenone and benzoic acid being produced at exposure times less than 15 min. Compounds, more typical of those formed via dehydration reactions of existing oxidised species, are produced at longer exposure times. UV-visible spectroscopy and Fourier transform infrared spectroscopy also confirm the presence of carboxylic acid, aromatic ketones and esters. Measurements of water contact angle on a 10 min treated surface reveals that methanol washing produces a more hydrophilic surface than water washing, the resulting water contact angles being 47° and 62° respectively. Ageing of methanol washed surfaces for 24 h leads to a recovery of the water contact angle back to 62° which suggests some form of post-washing surface relaxation process. Since XPS analyses show no increase in the oxygen concentration of the methanol washed surfaces after a 24 h ageing period, the increase in contact angle found with ageing is attributed to the reorientation of very near-surface functional groups i.e. within the XPS sampling depth.

Band line-up determination at p- and n-type Al/4H-SiC Schottky interfaces using photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Kohlscheen, J.; Emirov, Y. N.; Beerbom, M. M.; Wolan, J. T.; Saddow, S. E.; Chung, G.; MacMillan, M. F.; Schlaf, R.

2003-09-01

The band lineup of p- and n-type 4H-SiC/Al interfaces was determined using x-ray photoemission spectroscopy (XPS). Al was deposited in situ on ex situ cleaned SiC substrates in several steps starting at 1.2 Å up to 238 Å nominal film thickness. Before growth and after each growth step, the sample surface was characterized in situ by XPS. The analysis of the spectral shifts indicated that during the initial deposition stages the Al films react with the ambient surface contamination layer present on the samples after insertion into vacuum. At higher coverage metallic Al clusters are formed. The band lineups were determined from the analysis of the core level peak shifts and the positions of the valence bands maxima (VBM) depending on the Al overlayer thickness. Shifts of the Si 2p and C 1s XPS core levels occurred to higher (lower) binding energy for the p-(n-)type substrates, which was attributed to the occurrence of band bending due to Fermi-level equilibration at the interface. The hole injection barrier at the p-type interface was determined to be 1.83±0.1 eV, while the n-type interface revealed an electron injection barrier of 0.98±0.1 eV. Due to the weak features in the SiC valence bands measured by XPS, the VBM positions were determined using the Si 2p peak positions. This procedure required the determination of the Si 2p-to-VBM binding energy difference (99.34 eV), which was obtained from additional measurements.

Surface characterization of LDEF materials

NASA Astrophysics Data System (ADS)

Wightman, J. P.; Grammer, Holly Little

1993-10-01

The NASA Long Duration Exposure Facility (LDEF), a passive experimental satellite, was placed into low-Earth orbit by the Shuttle Challenger in Apr. 1984. The LDEF spent an unprecedented 69 months in space. The flight and recovery of the LDEF provided a wealth of information on the longterm space environmental effects of a variety of materials exposed to the low-Earth orbit environment. Surface characterization of LDEF materials included polymers, composites, thermal control paints, and aluminum. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), scanning electron microscopy (SEM), and contact angle analysis were used to document changes in both the surface composition and surface chemistry of these materials. Detailed XPS analysis of the polymer systems, such as Kapton, polyimide polysiloxane copolymers, and fluorinated ethylene propylene thermal blankets on the backside of the LDEF revealed significant changes in both the surface composition and surface chemistry as a result of exposure to the low-Earth orbit environment. Polymer systems such as Kapton, polyimide polysiloxane copolymers, and polysulfone showed a common trend of decreasing carbon content and increasing oxygen content with respect to the control sample. Carbon 1s curve fit XPS analysis of the composite samples, in conjunction with SEM photomicrographs, revealed significant ablation of the polymer matrix resin to expose the carbon fibers of the composite during exposure to the space environment. Surface characterization of anodized aluminum tray clamps, which were located at regular intervals over the entire LDEF frame, provided the first results to evaluate the extent of contamination with respect to position on the LDEF. The XPS results clearly showed that the amount and state of both silicon and fluorine contamination were directly dependent upon the position of the tray clamp on the LDEF.

Surface characterization of LDEF materials

NASA Technical Reports Server (NTRS)

Wightman, J. P.; Grammer, Holly Little

1993-01-01

The NASA Long Duration Exposure Facility (LDEF), a passive experimental satellite, was placed into low-Earth orbit by the Shuttle Challenger in Apr. 1984. The LDEF spent an unprecedented 69 months in space. The flight and recovery of the LDEF provided a wealth of information on the longterm space environmental effects of a variety of materials exposed to the low-Earth orbit environment. Surface characterization of LDEF materials included polymers, composites, thermal control paints, and aluminum. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), scanning electron microscopy (SEM), and contact angle analysis were used to document changes in both the surface composition and surface chemistry of these materials. Detailed XPS analysis of the polymer systems, such as Kapton, polyimide polysiloxane copolymers, and fluorinated ethylene propylene thermal blankets on the backside of the LDEF revealed significant changes in both the surface composition and surface chemistry as a result of exposure to the low-Earth orbit environment. Polymer systems such as Kapton, polyimide polysiloxane copolymers, and polysulfone showed a common trend of decreasing carbon content and increasing oxygen content with respect to the control sample. Carbon 1s curve fit XPS analysis of the composite samples, in conjunction with SEM photomicrographs, revealed significant ablation of the polymer matrix resin to expose the carbon fibers of the composite during exposure to the space environment. Surface characterization of anodized aluminum tray clamps, which were located at regular intervals over the entire LDEF frame, provided the first results to evaluate the extent of contamination with respect to position on the LDEF. The XPS results clearly showed that the amount and state of both silicon and fluorine contamination were directly dependent upon the position of the tray clamp on the LDEF.

TIMED solar EUV experiment: preflight calibration results for the XUV photometer system

NASA Astrophysics Data System (ADS)

Woods, Thomas N.; Rodgers, Erica M.; Bailey, Scott M.; Eparvier, Francis G.; Ucker, Gregory J.

1999-10-01

The Solar EUV Experiment (SEE) on the NASA Thermosphere, Ionosphere, and Mesosphere Energetics and Dynamics (TIMED) mission will measure the solar vacuum ultraviolet (VUV) spectral irradiance from 0.1 to 200 nm. To cover this wide spectral range two different types of instruments are used: a grating spectrograph for spectra between 25 and 200 nm with a spectral resolution of 0.4 nm and a set of silicon soft x-ray (XUV) photodiodes with thin film filters as broadband photometers between 0.1 and 35 nm with individual bandpasses of about 5 nm. The grating spectrograph is called the EUV Grating Spectrograph (EGS), and it consists of a normal- incidence, concave diffraction grating used in a Rowland spectrograph configuration with a 64 X 1024 array CODACON detector. The primary calibrations for the EGS are done using the National Institute for Standards and Technology (NIST) Synchrotron Ultraviolet Radiation Facility (SURF-III) in Gaithersburg, Maryland. In addition, detector sensitivity and image quality, the grating scattered light, the grating higher order contributions, and the sun sensor field of view are characterized in the LASP calibration laboratory. The XUV photodiodes are called the XUV Photometer System (XPS), and the XPS includes 12 photodiodes with thin film filters deposited directly on the silicon photodiodes' top surface. The sensitivities of the XUV photodiodes are calibrated at both the NIST SURF-III and the Physikalisch-Technische Bundesanstalt (PTB) electron storage ring called BESSY. The other XPS calibrations, namely the electronics linearity and field of view maps, are performed in the LASP calibration laboratory. The XPS and solar sensor pre-flight calibration results are primarily discussed as the EGS calibrations at SURF-III have not yet been performed.

Polyphenylsilole multilayers--an insight from X-ray electron spectroscopy and density functional theory.

PubMed

Diller, Katharina; Ma, Yong; Luo, Yi; Allegretti, Francesco; Liu, Jianzhao; Tang, Ben Zhong; Lin, Nian; Barth, Johannes V; Klappenberger, Florian

2015-12-14

We present a combined investigation by means of X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy of condensed multilayers of two polyphenylsiloles, namely hexaphenylsilole (HPS) and tetraphenylsilole (TPS). Both compounds exhibit very similar spectroscopic signatures, whose interpretation is aided by density functional theory (DFT) calculations. High-resolution XPS spectra of the Si 2p and C 1s core levels of these multilayers indicate a positively charged silicon ion flanked by two negatively charged adjacent carbon atoms in the silole core of both molecules. This result is corroborated quantitatively by DFT calculations on isolated HPS (TPS) molecules, which show a natural bond orbital partial charge of +1.67 e (+1.58 e) on the silicon and -0.34 e (-0.58 e) on the two neighbouring carbon atoms in the silole ring. These charges are conserved in direct contact with a Cu(111) substrate for films of submonolayer coverage, as evidenced by the Si 2p XPS data. The C K-edge NEXAFS spectra of HPS and TPS multilayers exhibit distinct and differing features. Their main characteristics reappear in the simulated spectra and are assigned to the different inequivalent carbon species in the molecule. The angle-dependent measurements hardly reveal any dichroism, i.e., the molecular π-systems are not uniformly oriented parallel or perpendicular with respect to the surface. Changes in the growth conditions of TPS, i.e., a reduction of the substrate temperature from 240 K to 80 K during deposition, lead to a broadening of both XPS and NEXAFS signatures, as well as an upward shift of the Si 2p and C 1s binding energies, indicative of a less ordered growth mode at low temperature.

Quantification of the toxic hexavalent chromium content in an organic matrix by X-ray photoelectron spectroscopy (XPS) and ultra-low-angle microtomy (ULAM)

NASA Astrophysics Data System (ADS)

Greunz, Theresia; Duchaczek, Hubert; Sagl, Raffaela; Duchoslav, Jiri; Steinberger, Roland; Strauß, Bernhard; Stifter, David

2017-02-01

Cr(VI) is known for its corrosion inhibitive properties and is, despite legal regulations, still a potential candidate to be added to thin (1-3 μm) protective coatings applied on, e.g., electrical steel as used for transformers, etc. However, Cr(VI) is harmful to the environment and to the human health. Hence, a reliable quantification of it is of decisive interest. Commonly, an alkaline extraction with a photometric endpoint detection of Cr(VI) is used for such material systems. However, this procedure requires an accurate knowledge on sample parameters such as dry film thickness and coating density that are occasionally associated with significant experimental errors. We present a comprehensive study of a coating system with a defined Cr(VI) pigment concentration applied on electrical steel. X-ray photoelectron spectroscopy (XPS) was employed to resolve the elemental chromium concentration and the chemical state. Turning to the fact that XPS is extremely surface sensitive (<10 nm) and that the lowest commonly achievable lateral resolution is a number of times higher than the coating thickness (∼2 μm), a bulk analysis was achieved with XPS line scans on extended wedge-shaped tapers through the coating. For that purpose a special sample preparation step performed on an ultra-microtome was required prior to analysis. Since a temperature increase leads to a reduction of Cr(VI) we extend our method on samples, which were subjected to different curing temperatures. We show that our proposed approach now allows to determine the elemental and Cr(VI) concentration and distribution inside the coating.

In situ NAP-XPS spectroscopy during methane dry reforming on ZrO2/Pt(1 1 1) inverse model catalyst

NASA Astrophysics Data System (ADS)

Rameshan, C.; Li, H.; Anic, K.; Roiaz, M.; Pramhaas, V.; Rameshan, R.; Blume, R.; Hävecker, M.; Knudsen, J.; Knop-Gericke, A.; Rupprechter, G.

2018-07-01

Due to the need of sustainable energy sources, methane dry reforming is a useful reaction for conversion of the greenhouse gases CH4 and CO2 to synthesis gas (CO  +  H2). Syngas is the basis for a wide range of commodity chemicals and can be utilized for fuel production via Fischer–Tropsch synthesis. The current study focuses on spectroscopic investigations of the surface and reaction properties of a ZrO2/Pt inverse model catalyst, i.e. ZrO2 particles (islands) grown on a Pt(1 1 1) single crystal, with emphasis on in situ near ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) during MDR reaction. In comparison to technological systems, model catalysts facilitate characterization of the surface (oxidation) state, surface adsorbates, and the role of the metal-support interface. Using XPS and infrared reflection absorption spectroscopy we demonstrated that under reducing conditions (UHV or CH4) the ZrO2 particles transformed to an ultrathin ZrO2 film that started to cover (wet) the Pt surface in an SMSI-like fashion, paralleled by a decrease in surface/interface oxygen. In contrast, (more oxidizing) dry reforming conditions with a 1:1 ratio of CH4 and CO2 were stabilizing the ZrO2 particles on the model catalyst surface (or were even reversing the strong metal support interaction (SMSI) effect), as revealed by in situ XPS. Carbon deposits resulting from CH4 dissociation were easily removed by CO2 or by switching to dry reforming conditions (673–873 K). Thus, at these temperatures the active Pt surface remained free of carbon deposits, also preserving the ZrO2/Pt interface.

Simulation and Modeling of Self-Assembled Monolayers of Carboxylic Acid Thiols on Flat and Nanoparticle Gold Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Techane, Sirnegeda D.; Baer, Donald R.; Castner, David G.

2011-09-01

Quantitative analysis of the 16-mercaptohexadecanoic acid self-assembled monolayer (C16 COOH-SAM) layer thickness on gold nanoparticles (AuNPs) was performed using simulation of electron spectra for surface analysis (SESSA) and x-ray photoelectron spectroscopy (XPS). XPS measurements of C16 COOH SAMs on flat gold surfaces were made at 9 different photoelectron take-off angles (5o to 85o in 5o increments), corrected using geometric weighting factors and then summed together to approximate spherical AuNPs. The SAM thickness and relative surface roughness (RSA) in SESSA were optimized to determine the best agreement between simulated and experimental surface composition. Based on the glancing angle results, it wasmore » found that inclusion of a hydrocarbon contamination layer on top the C16 COOH-SAM was necessary to improve the agreement between the SESSA and XPS results. For the 16 COOH-SAMs on flat Au surfaces, using a SAM thickness of 1.1Å/CH2 group, an RSA of 1.05 and a 1.5Å CH2-contamination overlayer (total film thickness = 21.5Å) for the SESSA calculations provided the best agreement with the experimental XPS data. After applying the appropriate geometric corrections and summing the SESSA flat surface compositions, the best fit results for the 16 COOH-SAM thickness and surface roughness on the AuNPs were determined to be 0.9Å/CH2 group and 1.06 RSA with a 1.5Å CH2-contamination overlayer (total film thickness = 18.5Å). The three angstrom difference in SAM thickness between the flat Au and AuNP surfaces suggests the alkyl chains of the SAM are slightly more tilted or disordered on the AuNP surfaces.« less

In situ laser annealing system for real-time surface kinetic analysis

NASA Astrophysics Data System (ADS)

Wang, Q.; Sun, Y.-M.; Zhao, W.; Campagna, J.; White, J. M.

2002-11-01

For real-time analysis during thermal annealing, a continuous wave CO2 infrared laser was coupled to a surface analysis system equipped for x-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS). The laser beam was directed into the vacuum chamber through a ZnSe window to the back side of the sample. With 10 W laser output, the sample temperature reached 563 K. The chamber remained below 10-8 Torr during annealing and allowed XPS and ISS data to be gathered as a function of time at selected temperatures. As a test example, real time Cu2O reduction at 563 K was investigated.

History Detectives Visit NASA Goddard Space Flight Center

NASA Image and Video Library

2017-12-08

The name of the instrument is X-Ray Photoelecton Spectrometer (acronymed XPS); the lab is in the Materials Engineering Branch and aptly titled the X-Ray Photoelectron Spectrometry Lab. XPS is a non-destructive surface analysis technique that provides an elemental composition of the surface. It is capable of detecting any element with the exception of hydrogen and helium. In the picture, I am analyzing a piece of the film that the History Detectives believed was from the Echo II Project. I was looking for the presence of chromium, which would help confirm that the exterior of the film had a chromium conversion coating. PHOTO CREDIT: NASA/Debbie Mccallum

Modification of Wetting Properties of PMMA by Immersion Plasma Ion Implantation

NASA Astrophysics Data System (ADS)

Mireault, N.; Ross, G. G.

Advancing and receding contact angles below 5° have been obtained on PMMA surfaces with the implantation of argon and oxygen ions. The ion implantations were performed by means of the Immersion Plasma Ion Implantation (IPII) technique, a hybrid between ion beams and immersion plasmas. Characterization of treated PMMA surfaces by means of XPS and its combination with chemical derivatization (CD-XPS) have revealed the depletion of oxygen and the creation of dangling bonds, together with the formation of new chemical functions such as -OOH, -COOH and C=C. These observations provide a good explanation for the strong increase of the wetting properties of the PMMA surfaces.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hyung Kim, Do; Department of Physics, University of Dongguk, Seoul 100-715; Youn Yoo, Dong

The origin of instability under positive bias stress (PBS) in amorphous Si-In-Zn-O (SIZO) thin film transistor (TFT) with different Si concentration has been investigated by x-ray photoelectron spectroscopy (XPS) and density of states (DOSs) analysis. It is found that stability of SIZO-TFT with 3 wt. % Si under PBS became more deteriorated than that of 1 wt. % Si incorporated SIZO-TFT due to the increased oxygen related trap distributed in energy range from conduction band to {approx}0.3 eV below the conduction band. The origin of instability under PBS was discussed in terms of oxygen related trap derived from DOSs andmore » XPS analysis.« less

Electronic structure evolution in doping of fullerene (C{sub 60}) by ultra-thin layer molybdenum trioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Chenggong; Wang, Congcong; Kauppi, John

2015-08-28

Ultra-thin layer molybdenum oxide doping of fullerene has been investigated using ultraviolet photoemission spectroscopy (UPS) and X-ray photoemission spectroscopy (XPS). The highest occupied molecular orbital (HOMO) can be observed directly with UPS. It is observed that the Fermi level position in fullerene is modified by ultra-thin-layer molybdenum oxide doping, and the HOMO onset is shifted to less than 1.3 eV below the Fermi level. The XPS results indicate that charge transfer was observed from the C{sub 60} to MoO{sub x} and Mo{sup 6+} oxides is the basis as hole dopants.

Surface Functionalization of Diamond Films by Photoreaction of Elemental Sulfur and Their Surface Properties

NASA Astrophysics Data System (ADS)

Nakamura, Takako; Ohana, Tsuguyori

2012-08-01

A useful method for direct sulfurization of diamond film surfaces by photoreaction of elemental sulfur was developed. The introduction of thiol groups onto the diamond films was confirmed by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, and scanning electron microscopy (SEM) analyses. The sulfur-modified diamond films attached to gold nanoparticles by self-assembly. The degrees of thiol group introduction and gold attachment were found to depend on photoirradiation time by monitoring by XPS. The gold-modified diamond film was observed to act as a surface-enhanced Raman scattering substrate for measurement of picric acid.

Cellulose gum and copper nanoparticles based hydrogel as antimicrobial agents against urinary tract infection (UTI) pathogens.

PubMed

Al-Enizi, Abdullah M; Ahamad, Tansir; Al-Hajji, Abdullah Baker; Ahmed, Jahangeer; Chaudhary, Anis Ahmad; Alshehri, Saad M

2018-04-01

In the present study, stable copper nanoparticles (CuNPs) were successfully prepared in the hydrogel matrix. The prepared nanocomposite (HCuNPs) was characterized via x-ray diffraction (XRD), electron microscopy (TEM), and energy-dispersive (EDX) and x-ray photoelectron spectroscopic (XPS) studies. The wide scan XPS spectra support the presence of C, N and O in neat hydrogel; while, the XPS spectra of HCuNPs demonstrate the presence of Cu along with C, N, and O elements. TEM studies show the formation of spherical shaped CuNPs in the size range from 7 to 12nm. The rheology results reveal that the storage modulus (G') of the HCuNPs was found to be higher than the loss modulus (G"). Additionally, the antibacterial activities and cytotoxic were carried out against urinary tract infection (UTI) microbes and HeLa (cervical) cells respectively. The antibacterial results reveal that HCuNPs composites show higher zone of inhibition against these pathogens then that of corresponding hydrogel matrix. The cytotoxic effects suggest that the prepared nanocomposite could be used as promising candidates for biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

XPS/NEXAFS spectroscopic and conductance studies of glycine on AlGaN/GaN transistor devices

NASA Astrophysics Data System (ADS)

Myers, Matthew; Khir, Farah Liyana Muhammad; Home, Michael A.; Mennell, Christopher; Gillbanks, Jeremy; Tadich, Anton; Baker, Murray V.; Nener, Brett D.; Parish, Giacinta

2018-03-01

We report on a study using a combination of XPS/NEXAFS and conductivity measurements to develop a fundamental understanding of how dipolar molecules interact with the heterostructure device surface and affect the device conductivity of AlGaN/GaN heterostructure-based transistors. In such structures, which are increasingly being investigated for chemical and biological sensing, a 2-dimensional electron gas spontaneously forms at the layer interface that is sensitive to the charge characteristics of the exposed surface. Glycine, chosen for this study because it is the simplest of the amino acids and is known to form a zwitterionic configuration when stabilized through intermolecular interactions, was evaporated under ultra-high vacuum conditions onto the device surface and subsequently both XPS/NEXAFS and conductivity measurements were conducted. NEXAFS spectra show a preferential orientation for the Glycine molecules on the surface and evidence for both neutral and zwitterionic species on the surface. In situ conductivity measurements suggest that the negatively charged carboxylate group is closest to the surface. These results are a unique and pivotal contribution to the previous and at times conflicting literature on the zwitterionic nature of Glycine.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Matthew A.; Redondo, Amaia Beloqui; Duyckaerts, Nicolas

A new liquid microjet endstation designed for ultraviolet (UPS) and X-ray (XPS) photoelectron, and partial electron yield X-ray absorption (XAS) spectroscopies at the Swiss Light Source is presented. The new endstation, which is based on a Scienta HiPP-2 R4000 electron spectrometer, is the first liquid microjet endstation capable of operating in vacuum and in ambient pressures up to the equilibrium vapor pressure of liquid water at room temperature. In addition, the Scienta HiPP-2 R4000 energy analyzer of this new endstation allows for XPS measurements up to 7000 eV electron kinetic energy that will enable electronic structure measurements of bulk solutionsmore » and buried interfaces from liquid microjet samples. The endstation is designed to operate at the soft X-ray SIM beamline and at the tender X-ray Phoenix beamline. The endstation can also be operated using a Scienta 5 K ultraviolet helium lamp for dedicated UPS measurements at the vapor-liquid interface using either He I or He II α lines. The design concept, first results from UPS, soft X-ray XPS, and partial electron yield XAS measurements, and an outlook to the potential of this endstation are presented.« less

Evolution of Eu valence and superconductivity in layered Eu0.5La0.5FBiS2 -xSex system

NASA Astrophysics Data System (ADS)

Mizuguchi, Y.; Paris, E.; Wakita, T.; Jinno, G.; Puri, A.; Terashima, K.; Joseph, B.; Miura, O.; Yokoya, T.; Saini, N. L.

2017-02-01

We have studied the effect of Se substitution on Eu valence in a layered Eu0.5La0.5FBiS2 -xSex superconductor using a combined analysis of x-ray absorption near-edge structure (XANES) and x-ray photoelectron spectroscopy (XPS) measurements. Eu L3-edge XANES spectra reveal that Eu is in the mixed valence state with coexisting Eu2 + and Eu3 +. The average Eu valence decreases sharply from ˜2.3 for x =0.0 to ˜2.1 for x =0.4 . Consistently, Eu 3 d XPS shows a clear decrease in the average valence by Se substitution. Bi 4 f XPS indicates that effective charge carriers in the BiCh2 (Ch = S, Se) layers are slightly increased by Se substitution. On the basis of the present results it has been discussed that the metallic character induced by Se substitution in Eu0.5La0.5FBiS2 -xSex is likely to be due to increased in-plane orbital overlap driven by reduced in-plane disorder that affects the carrier mobility.

Oxidation of MnO(100) and NaMnO2 formation: Characterization of Mn2+ and Mn3+ surfaces via XPS and water TPD

NASA Astrophysics Data System (ADS)

Feng, Xu; Cox, David F.

2018-09-01

The oxidation of clean and Na precovered MnO(100) has been investigated by X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and temperature programmed desorption (TPD) of adsorbed water. XPS results indicate that Mn3O4-like and Mn2O3-like surfaces can be formed by various oxidation treatments of clean and nearly-stoichiometric MnO(100), while a NaMnO2-like surface can be produced by the oxidation of MnO(100) pre-covered with multilayers of metallic Na. Water TPD results indicate that water adsorption/desorption is sensitive to the available oxidation states of surface Mn cations, and can be used to distinguish between surfaces exposing Mn2+and Mn3+ cations, or a combination of these oxidation states. Carbon dioxide and water TPD results from the NaMnO2-like surface indicate that pre-adsorbed water blocks the uptake of CO2, while water displaces pre-adsorbed CO2. No indication of a strong reactive interaction is observed between CO2, water and the NaMnO2-like surface under the conditions of our study.

Composite Behavior of a Novel Insulated Concrete Sandwich Wall Panel Reinforced with GFRP Shear Grids: Effects of Insulation Types.

PubMed

Kim, JunHee; You, Young-Chan

2015-03-03

A full-scale experimental program was used in this study to investigate the structural behavior of novel insulated concrete sandwich wall panels (SWPs) reinforced with grid-type glass-fiber-reinforced polymer (GFRP) shear connectors. Two kinds of insulation-expanded polystyrene (EPS) and extruded polystyrene (XPS) with 100 mm thickness were incased between the two concrete wythes to meet the increasing demand for the insulation performance of building envelope. One to four GFRP shear grids were used to examine the degree of composite action of the two concrete wythes. Ten specimens of SWPs were tested under displacement control subjected to four-point concentrated loads. The test results showed that the SWPs reinforced with GFRP grids as shear connectors developed a high degree of composite action resulting in high flexural strength. The specimens with EPS foam exhibited an enhanced load-displacement behavior compared with the specimens with XPS because of the relatively stronger bond between insulation and concrete. In addition, the ultimate strength of the test results was compared to the analytical prediction with the mechanical properties of only GRFP grids. The specimens with EPS insulation presented higher strength-based composite action than the ones with XPS insulation.

UV irradiation study of a tripeptide isolated in an argon matrix: A tautomerism process evidenced by infrared and X-ray photoemission spectroscopies

NASA Astrophysics Data System (ADS)

Mateo-Marti, E.; Pradier, C. M.

2013-05-01

Matrix isolation is a powerful tool for studying photochemical processes occurring in isolated molecules. In this way, we characterized the chemical modifications occurring within a tri peptide molecule, IGF, when exposed to the influence of Ultraviolet (UV) irradiation. This paper first describes the successful formation of the tripeptide (IGF) argon matrix under vacuum conditions, followed by the in situ UV irradiation and characterization of the molecular matrix reactivity after UV-irradiation. These studies have been performed by combining two complementary spectroscopic techniques, Fourier-Transform Reflexion Absorption Spectroscopy (FT-IRRAS) and X-ray Photoelectron Spectroscopy (XPS). The IR spectra of the isolated peptide-matrix, before and after UV irradiation, revealed significant differences that could be associated either to a partial deprotonation of the molecule or to a tautomeric conversion of some amide bonds to imide ones on some peptide molecules. XPS analyses undoubtedly confirmed the second hypothesis; the combination of IRRAS and XPS results provide evidence that UV irradiation of peptides induces a chemical reaction, namely a shift of the double bond, meaning partial conversion from amide tautomer into an imidic acid tautomer.

John Grant and the multifaceted nature of true professionalism: Personal perspective

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baer, Donald R.; Artyushkova, Kateryna; Fulghum, Julia E.

Consideration of the elements that contribute to professional and scientific impact is relevant in a volume honoring John Grant for two reasons. First, John has contributed in many ways to both advancing the methodology and the practical application of surface-analytical tools to understanding surfaces and interfaces of technological importance. The second reason is a little more complex. In an era when there is an effort to quantify contributions in various ways (e.g., citations, H-index, number of publications) and when social media seems, at least anecdotally, to lead a younger generation of scientists to be less involved in traditional professional activities,more » it is appropriate to examine the nature of the activities that make a lasting contribution to the advancement of science and technology and the professional community that makes progress possible. The multifaceted nature of John’s professional activities provides an appropriate background for exploring the nature of professionalism. With no reservations one can say that the foundation of professionalism is rooted in a scientist’s expertise in some area of research or practice. This expertise might be measured in numerous ways depending upon the field and could include numbers of publications, citations, patents, problems solved, research support obtained, or students produced. These “products” may or may not be readily visible to the community at large. Chuck Wagner – a pioneer in XPS, developer of an empirical set of XPS sensitivity factors and the modified Auger-parameter plot, and winner of the AVS Nerken Award in 1989 – observed that he could not publish or talk about 90% of the work he had done when working for Shell Oil. However, based on XPS capability developments that he could publish, he had a major impact on the development and application of XPS. To some degree John Grant’s research fits this model as well. Much of his early work at the Air Force Materials Research Laboratory was directed at solving materials problems and this important and often ground-breaking work was not published. However, a great deal of creativity and development was required to enable surface-sensitive tools such as AES and XPS to become useful for solving critical problems, and this work could be published.« less

A combined ToF-SIMS and XPS study for the elucidation of the role of water in the performances of a Post-Plasma Process using LaMnO3+δ as catalyst in the total oxidation of trichloroethylene

NASA Astrophysics Data System (ADS)

Nuns, N.; Beaurain, A.; Dinh, M. T. Nguyen; Vandenbroucke, A.; De Geyter, N.; Morent, R.; Leys, C.; Giraudon, J.-M.; Lamonier, J.-F.

2014-11-01

LaMnO3+δ which is an environment-friendly and inexpensive material has been previously used as catalyst in Post-Plasma Catalysis (PPC) in the total oxidation of trichloroethylene (TCE) which is a solvent widely used in dry cleaning and degreasing processes. It has been shown that the process efficiency increases in moist air (RH = 18%).The issue we want to address herein is the effect of water on the location of chlorine at the surface of the catalyst as chlorine is able to alter the catalyst structure, activity and stability. Therefore, a combined Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS) study has been carried out on the fresh LaMnO3+δ catalyst (LM) and used catalysts after performing PPC with TCE diluted in dry synthetic air (LM0) or with industrial air containing water (LM18; 18 stands for the Relative Humidity) and CO2 (about 560 ppmv) at a temperature of 150 °C. XPS and ToF-SIMS results both show the presence of chlorine on the tested catalysts whose amount increases by exposure of the catalyst to the reactive mixture in dry synthetic air. XPS results reveal that chlorine is present as both chloride ion and covalent chlorine on LM0 while organic chlorinated residues are absent on LM18 catalyst. ToF-SIMS study indicates that lanthanum excess as oxide(hydroxide) partially covering the perovskite mainly transforms into LaOCl and to a minor extent into LaCl3. Extent of Mn chlorination seems to be favored over LM0 having a higher MnClx±/MnOCl± ionic ratio compared to LM18. Furthermore ToF-SIMS clearly identifies C1 chlorinated organic ions, mainly CH2Cl+ and CHCl2-, on LM0 which may contribute to the XPS Cl organic component. From the combined ToF-SIMS and XPS results it is found that water delays the surface degradation extent of the perovskite into related (oxy)(hydroxy)chlorinated inorganic phases by less molecular chlorine and related chlorine species on the catalyst surface. A reaction scheme of Cl removal over LaMnO3+δ emphasing the role of water is given taking into account the detection of ToF-SIMS ions representative of the successive Mn intermediate states. As a consequence water allows tuning the degradation pathways of the main intermediate of the reaction, dichloroacetyl chloride (DCAC), which decomposes to give phosgene, HCCl3 and CCl4 by a successive Cl incorporation over (oxy)(hydroxy)chorinated perovskite or/and Mn species while COx species are likely formed over the perovskite.

In-situ XPS analysis of oxidized and reduced plasma deposited ruthenium-based thin catalytic films

NASA Astrophysics Data System (ADS)

Balcerzak, Jacek; Redzynia, Wiktor; Tyczkowski, Jacek

2017-12-01

A novel in-situ study of the surface molecular structure of catalytically active ruthenium-based films subjected to the oxidation (in oxygen) and reduction (in hydrogen) was performed in a Cat-Cell reactor combined with a XPS spectrometer. The films were produced by the plasma deposition method (PEMOCVD). It was found that the films contained ruthenium at different oxidation states: metallic (Ru0), RuO2 (Ru+4), and other RuOx (Ru+x), of which content could be changed by the oxidation or reduction, depending on the process temperature. These results allow to predict the behavior of the Ru-based catalysts in different redox environments.

Interfacial development of electrophoretically deposited graphene oxide films on Al alloys

DOE PAGES

Jin, Sumin; Dickerson, James H.; Pham, Viet Hung; ...

2015-07-28

Adhesion between film and substrate is critical for electronic device and coating applications. Interfacial development between electrophoretically deposited graphene oxide films on Al 1100 and Al 5052 alloys were investigated using FT-IR and XPS depth profiling techniques. Obtained results suggest metal ion permeation from the substrates into deposited graphene oxide films. The interface between the films and the substrates were primarily composed of Al-O-C bonds from oxygenated defects on graphene oxide plane rather than expected Al-C formation. Films heat treated at 150 °C had change in microstructure and peak shifts in XPS spectra suggesting change in chemical structure of bondsmore » between the films and the substrates.« less

Solar Ion Processing of Major Element Surface Compositions of Mature Mare Soils: Insights from Combined XPS and Analytical TEM Observations

NASA Technical Reports Server (NTRS)

Christoffersen, R.; Dukes, C.; Keller, L. P.; Baragiola, R.

2012-01-01

Solar wind ions are capable of altering the sur-face chemistry of the lunar regolith by a number of mechanisms including preferential sputtering, radiation-enhanced diffusion and sputter erosion of space weathered surfaces containing pre-existing compositional profiles. We have previously reported in-situ ion irradiation experiments supported by X-ray photoelectron spectroscopy (XPS) and analytical TEM that show how solar ions potentially drive Fe and Ti reduction at the monolayer scale as well as the 10-100 nm depth scale in lunar soils [1]. Here we report experimental data on the effect of ion irradiation on the major element surface composition in a mature mare soil.

Calculation of density of states of transition metals: From bulk sample to nanocluster

NASA Astrophysics Data System (ADS)

Krasavin, Andrey V.; Borisyuk, Petr V.; Vasiliev, Oleg S.; Zhumagulov, Yaroslav V.; Kashurnikov, Vladimir A.; Kurelchuk, Uliana N.; Lebedinskii, Yuriy Yu.

2018-03-01

A technique is presented of restoring the electronic density of states of the valence band from data of X-ray photoelectron spectroscopy (XPS). The originality of the technique consists in using a stochastic procedure to solve an integral equation relating the density of states and the experimental X-ray photoelectron spectra via the broadening function. To obtain the broadening function, only the XPS spectra of the core levels are needed. The results are presented for bulk sample of gold and tungsten and nanoclusters of tantalum; the possibility of using the results to determine the density of states of low-dimensional structures, including ensembles of metal nanoclusters, is demonstrated.

Silicon (100)/SiO2 by XPS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jensen, David S.; Kanyal, Supriya S.; Madaan, Nitesh

2013-09-25

Silicon (100) wafers are ubiquitous in microfabrication and, accordingly, their surface characteristics are important. Herein, we report the analysis of Si (100) via X-ray photoelectron spectroscopy (XPS) using monochromatic Al K radiation. Survey scans show that the material is primarily silicon and oxygen, and the Si 2p region shows two peaks that correspond to elemental silicon and silicon dioxide. Using these peaks the thickness of the native oxide (SiO2) was estimated using the equation of Strohmeier.1 The oxygen peak is symmetric. The material shows small amounts of carbon, fluorine, and nitrogen contamination. These silicon wafers are used as the basemore » material for subsequent growth of templated carbon nanotubes.« less

In Situ X-Ray Photoelectron Spectroscopy of Model Catalysts: At the Edge of the Gap

NASA Astrophysics Data System (ADS)

Blomberg, S.; Hoffmann, M. J.; Gustafson, J.; Martin, N. M.; Fernandes, V. R.; Borg, A.; Liu, Z.; Chang, R.; Matera, S.; Reuter, K.; Lundgren, E.

2013-03-01

We present high-pressure x-ray photoelectron spectroscopy (HP-XPS) and first-principles kinetic Monte Carlo study addressing the nature of the active surface in CO oxidation over Pd(100). Simultaneously measuring the chemical composition at the surface and in the near-surface gas phase, we reveal both O-covered pristine Pd(100) and a surface oxide as stable, highly active phases in the near-ambient regime accessible to HP-XPS. Surprisingly, no adsorbed CO can be detected during high CO2 production rates, which can be explained by a combination of a remarkably short residence time of the CO molecule on the surface and mass-transfer limitations in the present setup.

Transformation of multiwall carbon nanotubes to onions with layers cross-linked by sp3 bonds under high pressure and shear deformation

NASA Astrophysics Data System (ADS)

Pankov, A. M.; Bredikhina, A. S.; Kulnitskiy, B. A.; Perezhogin, I. A.; Skryleva, E. A.; Parkhomenko, Yu. N.; Popov, M. Yu.; Blank, V. D.

2017-08-01

A pressure-induced phase transition of multiwall carbon nanotubes (MWNT) to a new structure at room temperature is studied using a shear diamond anvil cell, X-ray photoelectron spectra (XPS), transmission electron microscope (TEM) and Raman procedures. We observe a cardinal pressure-induced change in the nanoparticles shape from multi-shell tubes to multi-shell spheres. MWNT transforms to onions with layers cross-linked by sp3 bonds under the 45-65 GPa compressive stress combined with shear deformation at room temperature. TEM and XPS results show that about 40% of the carbon atoms in the new phase are sp3-bounded.

XPS Investigation on Changes in UO 2 Speciation following Exposure to Humidity

DOE PAGES

Donald, Scott B.; Davisson, M. Lee; Nelson, Art J.

2016-04-27

High purity UO 2powder samples were subjected to accelerated aging under controlled conditions with relative humidity ranging from 34% to 98%. Characterization of the chemical speciation of the products was accomplished using X-ray photoelectron spectroscopy (XPS). A shift to higher uranium oxidation states was found to be directly correlated to increased relative humidity exposure. In addition, the relative abundance of O 2-, OH -, and H 2O was found to vary with exposure time. Therefore, it is expected that uranium oxide materials exposed to high relative humidity conditions during processing and storage would display a similar increase in average uraniummore » valence.« less

Summary: Update to ASTM Guide E 1523 to Charge Control and Charge Referencing Techniques in X-ray Photoelectron Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baer, Donald R.

2005-04-22

An updated version of the ASTM guide E1523 to the methods to charge control and charge referencing techniques in x-ray photoelectron spectroscopy has been released by ASTM. The guide is meant to acquaint x-ray photoelectron spectroscopy (XPS) users with the various charge control and charge referencing techniques that are and have been used in the acquisition and interpretation of XPS data from surfaces of insulating specimens. The current guide has been expanded to include new references as well as recommendations for reporting information on charge control and charge referencing. The previous version of the document had been published in 1997.

Impact of ambient environment on the electronic structure of CuPc/Au sample

NASA Astrophysics Data System (ADS)

Sinha, Sumona; Mukherjee, M.

2018-02-01

The performances of organic devices are crucially connected with their stability in the ambient environment. The impact of 24 h. Ambient environment exposure to the electronic structures of about 12 nm thick CuPc thin film on clean Au substrate have been studied employing UV photoemission spectroscopy technique. X-ray photoemission spectroscopy (XPS) was used to find out the origin of the change of the electronic structures in the sample with the exposure. The XPS study suggests that the oxidation occurs at the CuPc thin film. Due to the adsorption of oxygen in the CuPc film from the ambient air, charge carriers are formed within the CuPc film. Moreover, the XPS results imply that the CuPc film is sufficiently thinner for diffusing oxygen molecules through it and gets physically absorbed on Au substrate during the ambient exposure. Consequently, the hole injection barrier height of pristine CuPc film, grown on Au substrate, is reduced by about 0.50 eV and work-function of the pristine CuPc sample is enhanced by around 0.25 eV in the exposure. The findings will help to understand the mechanism that governs the degradation of performance of CuPc based devices in ambient environment.

Characterization of Natural Dyes and Traditional Korean Silk Fabric by Surface Analytical Techniques.

PubMed

Lee, Jihye; Kang, Min Hwa; Lee, Kang-Bong; Lee, Yeonhee

2013-05-15

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS) are well established surface techniques that provide both elemental and organic information from several monolayers of a sample surface, while also allowing depth profiling or image mapping to be carried out. The static TOF-SIMS with improved performances has expanded the application of TOF-SIMS to the study of a variety of organic, polymeric and biological materials. In this work, TOF-SIMS, XPS and Fourier Transform Infrared (FTIR) measurements were used to characterize commercial natural dyes and traditional silk fabric dyed with plant extracts dyes avoiding the time-consuming and destructive extraction procedures necessary for the spectrophotometric and chromatographic methods previously used. Silk textiles dyed with plant extracts were then analyzed for chemical and functional group identification of their dye components and mordants. TOF-SIMS spectra for the dyed silk fabric showed element ions from metallic mordants, specific fragment ions and molecular ions from plant-extracted dyes. The results of TOF-SIMS, XPS and FTIR are very useful as a reference database for comparison with data about traditional Korean silk fabric and to provide an understanding of traditional dyeing materials. Therefore, this study shows that surface techniques are useful for micro-destructive analysis of plant-extracted dyes and Korean dyed silk fabric.

XPS Spectra Analysis of Ti2+, Ti3+ Ions and Dye Photodegradation Evaluation of Titania-Silica Mixed Oxide Nanoparticles

NASA Astrophysics Data System (ADS)

Chinh, Vu Duc; Broggi, Alessandra; Di Palma, Luca; Scarsella, Marco; Speranza, Giorgio; Vilardi, Giorgio; Thang, Pham Nam

2018-04-01

TiO2-SiO2 mixed oxides have been prepared by the sol-gel technique from tetrabutyl orthotitanate and tetraethyl orthosilicate. The prepared materials were characterized by x-ray diffraction, scanning electron microscopy, energy dispersive x-ray spectroscopy, nitrogen physisorption, Fourier-transform infrared spectroscopy (FT-IR) and x-ray photoelectron spectroscopy (XPS). The results indicate that the TiO2-SiO2 mixed oxides have a large surface area and a nanoscale size. FT-IR spectra show that Ti atoms are bonded to silica by oxygen bridging atoms in Ti-O-Si bonds. The titanium valence states in TiO2-SiO2 mixed oxides were investigated by XPS, and their spectra report the presence of Ti2+ and Ti3+ cations for high silica concentration, suggesting the formation of oxygen vacancies. The photocatalytic activity of the prepared materials has been evaluated for the photodegradation of methylene blue (MB). The mixed oxides were activated by means of a UV light source, and the concentration of MB was monitored by UV-Vis spectroscopy. The synthesized TiO2-SiO2 shows significantly higher MB removal efficiency in comparison with that of the commercial TiO2 Degussa, P25.

Spectroellipsometric, AFM and XPS probing of stainless steel surfaces subjected to biological influences

NASA Astrophysics Data System (ADS)

Vinnichenko, M.; Chevolleau, Th; Pham, M. T.; Poperenko, L.; Maitz, M. F.

2002-11-01

Surface modification of austenitic stainless steel (SS) 316L after incubation in growing cell cultures and cell-free media as control has been studied. The following treatments were applied: mouse fibrosarcoma cells L929 for 3 and 7 days, polymorphonuclear neutrophils for 3 and 7 days and human osteosarcoma cells SAOS-2 for 7 and 14 days. Cells were enzymatically removed in all cases. The modified surfaces were probed in comparison with untreated ones by means of spectroscopic ellipsometry (SE), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). XPS shows the appearance of the peak of bonded nitrogen at 400.5 eV characteristic for adsorbed proteins on the surface for each type of cells and for the cell-free medium. Migration of Ni in the adsorbed layer is observed in all cases for samples after the cell cultures. The protein layer thickness is ellipsometrically determined to be within 2.5-6.0 nm for all treated samples with parameterization of its optical constants in Cauchy approach. The study showed that for such biological treatments of the SS the protein layer adsorption is the dominating process in the first 2 weeks, which could play a role in the process of corrosion by complex forming properties with metal ions.

Surface modification of amorphous substrates by disulfide derivatives: A photo-assisted route to direct functionalization of chalcogenide glasses

NASA Astrophysics Data System (ADS)

Amalric, Julien; Marchand-Brynaert, Jacqueline

2011-12-01

A novel route for chalcogenide glass surface modification is disclosed. The formation of an organic monolayer from disulfide derivatives is studied on two different glasses of formula GexAsySez by water contact angle measurement, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy in attenuated total reflection mode (FTIR-ATR). The potential anchoring group is the disulfide functionality. Since thioctic acid derivatives absorb around 335 nm, an irradiation step is included, in order to favor S-S disruption. Three types of disulfide compounds are grafted onto small glass breaks for contact angle and XPS analyses. The results show effective changes of surface state. According to contact angle measurement, the deposited organic layer functionalized by a small polyethylene glycol chain leads to a more hydrophilic surface, long alkyl chain or a perfluorinated carbon chain leads to a more hydrophobic surface. XPS shows the presence at the surface of an organic layer with sulfur and ethylene oxide chains, or augmentation of organic carbons or fluorine and Csbnd F bonds. The photo-assisted grafting of the disulfides onto an ATR prism made of chalcogenide glass shows that this surface modification process does not affect infrared transparency, despite UV treatment, and accurate structural analysis can be performed.

Depth profile composition studies of thin film CdS:Cu2S solar cells using XPS and AES

NASA Astrophysics Data System (ADS)

Bhide, V. G.; Salkalachen, S.; Rastogi, A. C.; Rao, C. N. R.; Hegde, M. S.

1981-09-01

Studies of the surface composition and depth profiles of thin film CdS:Cu2S solar cells based on the techniques of X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) are reported. Specimens were fabricated by the thermal deposition of polycrystalline CdS films onto silver-backed electrodes predeposited on window glass substrates, followed by texturization in hot HCl and chemical plating in a hot CuCl(I) bath for a few seconds to achieve the topotaxial growth of CuS films. The XPS and AES studies indicate the junction to be fairly diffused in the as-prepared cell, with heat treatment in air at 210 C sharpening the junction, improving the stoichiometry of the Cu2S layer and thus improving cell performance. The top copper sulfide layer is found to contain impurities such as Cd, Cl, O and C, which may be removed by mild Ar(+) ion beam etching. The presence of copper deep in the junction is invariably detected, apparently in the grain boundary region in the form of CuS or Cu(2+) trapped in the lattice. It is also noted that the nominal valence state of copper changes abruptly from Cu(+) to Cu(2+) across the junction.

New insights into micro/nanoscale combined probes (nanoAuger, μXPS) to characterize Ag/Au@SiO2 core-shell assemblies.

PubMed

Ledeuil, J B; Uhart, A; Soulé, S; Allouche, J; Dupin, J C; Martinez, H

2014-10-07

This work has examined the elemental distribution and local morphology at the nanoscale of core@shell Ag/Au@SiO2 particles. The characterization of such complex metal/insulator materials becomes more efficient when using an initial cross-section method of preparation of the core@shell nanoparticles (ion milling cross polisher). The originality of this route of preparation allows one to obtain undamaged, well-defined and planar layers of cross-cut nano-objects. Once combined with high-resolution techniques of characterization (XPS, Auger and SEM), the process appears as a powerful way to minimize charging effects and enhance the outcoming electron signal (potentially affected by the topography of the material) during analysis. SEM experiments have unambiguously revealed the hollow-morphology of the metal core, while Auger spectroscopy observations showed chemical heterogeneity within the particles (as silver and gold are randomly found in the core ring). To our knowledge, this is the first time that Auger nano probe spectroscopy has been used and successfully optimized for the study of some complex metal/inorganic interfaces at such a high degree of resolution (≈12 nm). Complementarily, XPS Au 4f and Ag 3d peaks were finally detected attesting the possibility of access to the whole chemistry of such nanostructured assemblies.

Examining the temperature behavior of stainless steel surfaces exposed to hydrogen plasmas in the Lithium Tokamak eXperiment (LTX)

NASA Astrophysics Data System (ADS)

Bedoya, Felipe; Allain, Jean Paul; Kaita, Robert; Lucia, Matthew; St-Onge, Denis; Ellis, Robert; Majeski, Richard

2014-10-01

The Materials Analysis Particle Probe (MAPP) is an in-situ diagnostic designed to characterize plasma-facing components (PFCs) in tokamak devices. MAPP is installed in LTX at Princeton Plasma Physics Laboratory. MAPP's capabilities include remotely operated XPS acquisition and temperature control of four samples. The recent addition of a focused ion beam allows XPS depth profiling analysis. Recent published results show an apparent correlation between hydrogen retention and temperature of Li coated stainless steel (SS) PFCs exposed to plasmas like those of LTX. According to XPS data, the retention of hydrogen by the coated surfaces decreases at above 180 °C. In the present study MAPP will be used to study the oxidation of Li coatings as a function of time and temperature of the walls when Li coatings are applied. Experiments in the ion-surface interaction experiment (IIAX) varying the hydrogen fluence on the SS samples will be also performed. Conclusions resulting from this study will be key to explain the PFC temperature-dependent variation of plasma performance observed in LTX. This work was supported by U.S. DOE Contracts DE-AC02-09CH11466, DE-AC52-07NA27344 and DE-SC0010717.

Electron-spectroscopy and -diffraction study of the conductivity of CVD diamond ( 0 0 1 )2×1 surface

NASA Astrophysics Data System (ADS)

Kono, S.; Takano, T.; Shimomura, M.; Goto, T.; Sato, K.; Abukawa, T.; Tachiki, M.; Kawarada, H.

2003-04-01

A chemical vapor deposition as-grown diamond (0 0 1) single-domain 2 × 1 surface was studied by electron-spectroscopy and electron-diffraction in ultrahigh vacuum (UHV). In order to change the surface conductivity (SC) of the diamond in UHV, three annealing stages were used; without annealing, annealing at 300 °C and annealing at 550 °C. From low energy electron diffraction and X-ray photoelectron spectroscopic (XPS) studies, an existence of SC was suggested for the first two stages of annealing and an absence of SC was suggested for the last stage of annealing. Changes in C KVV Auger electron spectroscopic spectra, C KVV Auger electron diffraction (AED) patterns and C 1s XPS peak positions were noticed between the annealing stages at 300 and 550 °C. These changes are interpreted as such that the state of hydrogen involvement in a subsurface of diamond (0 0 1)2 × 1 changes as SC changes. In particular, the presence of local disorder in diamond configuration in SC subsurface is pointed out from C KVV AED. From C 1s XPS peak shifts, a lower bound for the Fermi-level for SC layers from the valence band top is presented to be ˜0.5 eV.

Investigation of trimethylacetic acid adsorption on stoichiometric and oxygen-deficient CeO 2 (111) surfaces

DOE PAGES

Sanghavi, Shail; Wang, Weina; Nandasiri, Manjula I.; ...

2016-05-12

We studied the interactions between the carboxylate anchoring group from trimethylacetic acid (TMAA) and CeO 2(111) surfaces as a function of oxygen stoichiometry using in situ X-ray photoelectron spectroscopy (XPS). The stoichiometric CeO 2(111) surface was obtained by annealing the thin film under 2.0 × 10 –5 Torr of oxygen at ~550 °C for 30 min. In order to reduce the CeO 2(111) surface, the thin film was annealed under ~5.0 × 10 –10 Torr vacuum conditions at 550 °C, 650 °C, 750 °C and 850 °C for 30 min to progressively increase the oxygen defect concentration on the surface.more » The saturated TMAA coverage on the CeO 2(111) surface determined from XPS elemental composition is found to increase with increasing oxygen defect concentration. This is attributed to the increase of under-coordinated cerium sites on the surface with the increase in the oxygen defect concentrations. Furthermore, XPS results were in agreement with periodic density functional theory (DFT) calculations and indicate a stronger binding between the carboxylate group from TMAA and the oxygen deficient CeO 2–δ(111) surface through dissociative adsorption.« less

Influence of surface pretreatments on the quality of trivalent chromium process coatings on aluminum alloy

NASA Astrophysics Data System (ADS)

Viroulaud, Rémi; Światowska, Jolanta; Seyeux, Antoine; Zanna, Sandrine; Tardelli, Joffrey; Marcus, Philippe

2017-11-01

The effects of surface pretreatments (degreasing and pickling) on the characteristics of the Trivalent Chromium Process (TCP) coating on pure aluminum and on AA2024-T351 aluminum alloy were investigated here by means of surface sensitive techniques: X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The XPS and ToF-SIMS results evidence that the TCP coating homogeneity is strongly dependent on the pretreatment process used. The TCP coverage factor, calculated from XPS results, is significantly lower, on both pure aluminum and AA2024-T351 alloy surface, when a pickling step is applied. One of the main effects of pickling pretreatment is strong metallic copper enrichment at the surface of the 2024 alloy, associated with chemical dissolution of Al-Cu intermetallic particles. However, it is evidenced here, that the copper enrichment is not detrimental for the quality of the TCP coating. The coating failure, observed when the pickling step is applied, can be assigned to a faster kinetics of the coating growth leading to formation of thicker conversion coating more susceptible to cracking or to the localized presence of aluminum fluoride species leading to the appearance of coating defects or detachment.

Composite Behavior of a Novel Insulated Concrete Sandwich Wall Panel Reinforced with GFRP Shear Grids: Effects of Insulation Types

PubMed Central

Kim, JunHee; You, Young-Chan

2015-01-01

A full-scale experimental program was used in this study to investigate the structural behavior of novel insulated concrete sandwich wall panels (SWPs) reinforced with grid-type glass-fiber-reinforced polymer (GFRP) shear connectors. Two kinds of insulation-expanded polystyrene (EPS) and extruded polystyrene (XPS) with 100 mm thickness were incased between the two concrete wythes to meet the increasing demand for the insulation performance of building envelope. One to four GFRP shear grids were used to examine the degree of composite action of the two concrete wythes. Ten specimens of SWPs were tested under displacement control subjected to four-point concentrated loads. The test results showed that the SWPs reinforced with GFRP grids as shear connectors developed a high degree of composite action resulting in high flexural strength. The specimens with EPS foam exhibited an enhanced load-displacement behavior compared with the specimens with XPS because of the relatively stronger bond between insulation and concrete. In addition, the ultimate strength of the test results was compared to the analytical prediction with the mechanical properties of only GRFP grids. The specimens with EPS insulation presented higher strength-based composite action than the ones with XPS insulation. PMID:28787978

A new endstation at the Swiss Light Source for ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy measurements of liquid solutions.

PubMed

Brown, Matthew A; Redondo, Amaia Beloqui; Jordan, Inga; Duyckaerts, Nicolas; Lee, Ming-Tao; Ammann, Markus; Nolting, Frithjof; Kleibert, Armin; Huthwelker, Thomas; Müächler, Jean-Pierre; Birrer, Mario; Honegger, Juri; Wetter, Reto; Wörner, Hans Jakob; van Bokhoven, Jeroen A

2013-07-01

A new liquid microjet endstation designed for ultraviolet (UPS) and X-ray (XPS) photoelectron, and partial electron yield X-ray absorption (XAS) spectroscopies at the Swiss Light Source is presented. The new endstation, which is based on a Scienta HiPP-2 R4000 electron spectrometer, is the first liquid microjet endstation capable of operating in vacuum and in ambient pressures up to the equilibrium vapor pressure of liquid water at room temperature. In addition, the Scienta HiPP-2 R4000 energy analyzer of this new endstation allows for XPS measurements up to 7000 eV electron kinetic energy that will enable electronic structure measurements of bulk solutions and buried interfaces from liquid microjet samples. The endstation is designed to operate at the soft X-ray SIM beamline and at the tender X-ray Phoenix beamline. The endstation can also be operated using a Scienta 5 K ultraviolet helium lamp for dedicated UPS measurements at the vapor-liquid interface using either He I or He II α lines. The design concept, first results from UPS, soft X-ray XPS, and partial electron yield XAS measurements, and an outlook to the potential of this endstation are presented.

Surface Chemistry of a Microcoated Energetic Material, Pentaerythritoltetranitrate (PETN)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Worley, C.M.; Vannet, M.D.; Ball, G.L.

1987-01-01

A microcoating technique was used to apply a polymer to an energetic explosive material. The explosive was pentaerythritoltetranitrate (PETN), and the coating was a copolymer consisting of vinylchloride/trifluorochloroethylene in a 1.5/1.0 molecular ratio. X-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS) were used to study the surface and interfacial chemistry of PETN powders and pellets made from compressed powders having either 0.5 or 20 wt% coating. Two simple models were used to discuss the nature of the copolymer film on the PETN. Model I shows the copolymer completely coating PETN; Model II depicts the copolymer as only partially coveringmore » PETN. Model II was applicable in explaining the 0.5 and 20 wt% microcoating of powders, as well as the 0.5 wt% coated pellets. However, the pellets with 20 wt% coating showed the copolymer to completely coat PETN (Model I), suggesting copolymer redistribution during pelletization. XPS and ISS results showed the copolymer film to be thin. An XPS expression modified to accommodate ISS data was developed for the calculation of the average copolymer thickness of PETN. The thicknesses were determined to be 10 {angstrom} and 6 {angstrom} for 0.5 wt% coated PETN powders and pellets, respectively. Bonding between the copolymer and PETN was concluded to be mechanical.« less

XPS study of the surface chemistry of UO2 (111) single crystal film

NASA Astrophysics Data System (ADS)

Maslakov, Konstantin I.; Teterin, Yury A.; Popel, Aleksej J.; Teterin, Anton Yu.; Ivanov, Kirill E.; Kalmykov, Stepan N.; Petrov, Vladimir G.; Springell, Ross; Scott, Thomas B.; Farnan, Ian

2018-03-01

A (111) air-exposed surface of UO2 thin film (150 nm) on (111) YSZ (yttria-stabilized zirconia) before and after the Ar+ etching and subsequent in situ annealing in the spectrometer analytic chamber was studied by XPS technique. The U 5f, U 4f and O 1s electron peak intensities were employed for determining the oxygen coefficient kO = 2 + x of a UO2+x oxide on the surface. It was found that initial surface (several nm) had kO = 2.20. A 20 s Ar+ etching led to formation of oxide UO2.12, whose composition does not depend significantly on the etching time (up to 180 s). Ar+ etching and subsequent annealing at temperatures 100-380 °C in vacuum was established to result in formation of stable well-organized structure UO2.12 reflected in the U 4f XPS spectra as high intensity (∼28% of the basic peak) shake-up satellites 6.9 eV away from the basic peaks, and virtually did not change the oxygen coefficient of the sample surface. This agrees with the suggestion that a stable (self-assembling) phase with the oxygen coefficient kO ≈ 2.12 forms on the UO2 surface.

Surface Reactivity of Li2MnO3: First-Principles and Experimental Study.

PubMed

Quesne-Turin, Ambroise; Flahaut, Delphine; Croguennec, Laurence; Vallverdu, Germain; Allouche, Joachim; Charles-Blin, Youn; Chotard, Jean-Noël; Ménétrier, Michel; Baraille, Isabelle

2017-12-20

This article deals with the surface reactivity of (001)-oriented Li 2 MnO 3 crystals investigated from a multitechnique approach combining material synthesis, X-ray photoemission spectroscopy (XPS), scanning electron microscopy, Auger electron spectroscopy, and first-principles calculations. Li 2 MnO 3 is considered as a model compound suitable to go further in the understanding of the role of tetravalent manganese atoms in the surface reactivity of layered lithium oxides. The knowledge of the surface properties of such materials is essential to understand the mechanisms involved in parasitic phenomena responsible for early aging or poor storage performances of lithium-ion batteries. The surface reactivity was probed through the adsorption of SO 2 gas molecules on large Li 2 MnO 3 crystals to be able to focus the XPS beam on the top of the (001) surface. A chemical mapping and XPS characterization of the material before and after SO 2 adsorption show in particular that the adsorption is homogeneous at the micro- and nanoscale and involves Mn reduction, whereas first-principles calculations on a slab model of the surface allow us to conclude that the most energetically favorable species formed is a sulfate with charge transfer implying reduction of Mn.

Epitaxial growth of cobalt oxide phases on Ru(0001) for spintronic device applications

NASA Astrophysics Data System (ADS)

Olanipekun, Opeyemi; Ladewig, Chad; Kelber, Jeffry A.; Randle, Michael D.; Nathawat, Jubin; Kwan, Chun-Pui; Bird, Jonathan P.; Chakraborti, Priyanka; Dowben, Peter A.; Cheng, Tao; Goddard, W. A., III

2017-09-01

Cobalt oxide films are of technological interest as magnetic substrates that may support the direct growth of graphene, for use in various spintronic applications. In this work, we demonstrate the controlled growth of both Co3O4(111) and CoO(111) on Ru(0001) substrates. The growth is performed by Co molecular beam epitaxy, at a temperature of 500 K and in an O2 partial pressure of 10-4 Torr for Co3O4(111), and 7.5 × 10-7 Torr for CoO(111). The films are distinguished by their dissimilar Co 2p x-ray photoemission (XPS) spectra, while XPS-derived O/Co stoichiometric ratios are 1.33 for Co3O4(111) and 1.1 for CoO(111). Electron energy loss (EELS) spectra for Co3O4(111) indicate interband transitions at ˜2.1 and 3.0 eV, while only a single interband transition near 2.0 eV is observed for CoO(111). Low energy electron diffraction (LEED) data for Co3O4(111) indicate twinning during growth, in contrast to the LEED data for CoO(111). For Co3O4(111) films of less than 20 Å average thickness, however, XPS, LEED and EELS data are similar to those of CoO(111). XPS data indicate that both Co oxide phases are hydroxylated at all thicknesses. The two phases are moreover found to be thermally stable to at least 900 K in UHV, while ex situ atomic force microscopy measurements of Co3O4(111)/Ru(0001) indicate an average surface roughness below 1 nm. Electrical measurements indicate that Co3O4(111)/Ru(0001) films exhibit dielectric breakdown at threshold voltages of ˜1 MV cm-1. Collectively, these data show that the growth procedures yield Co3O4(111) films with topographical and electrical characteristics that are suitable for a variety of advanced device applications.

Deduction of the chemical state and the electronic structure of Nd{sub 2}Fe{sub 14}B compound from X-ray photoelectron spectroscopy core-level and valence-band spectra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jing; Liang, Le; Zhang, Lanting, E-mail: lantingzh@sjtu.edu.cn, E-mail: lmsun@sjtu.edu.cn

2014-10-28

Characterization of chemical state and electronic structure of the technologically important Nd{sub 2}Fe{sub 14}B compound is attractive for understanding the physical nature of its excellent magnetic properties. X-ray photoelectron spectroscopy (XPS) study of such rare-earth compound is important and also challenging due to the easy oxidation of surface and small photoelectron cross-sections of rare-earth 4f electrons and B 2p electrons, etc. Here, we reported an investigation based on XPS spectra of Nd{sub 2}Fe{sub 14}B compound as a function of Ar ion sputtering time. The chemical state of Fe and that of B in Nd{sub 2}Fe{sub 14}B compound can be clearlymore » determined to be 0 and −3, respectively. The Nd in Nd{sub 2}Fe{sub 14}B compound is found to have the chemical state of close to +3 instead of +3 as compared with the Nd in Nd{sub 2}O{sub 3}. In addition, by comparing the valence-band spectrum of Nd{sub 2}Fe{sub 14}B compound to that of the pure Fe, the contributions from Nd, Fe, and B to the valence-band structure of Nd{sub 2}Fe{sub 14}B compound is made more clear. The B 2p states and B 2s states are identified to be at ∼11.2 eV and ∼24.6 eV, respectively, which is reported for the first time. The contribution from Nd 4f states can be identified both in XPS core-level spectrum and XPS valence-band spectrum. Although Nd 4f states partially hybridize with Fe 3d states, Nd 4f states are mainly localized in Nd{sub 2}Fe{sub 14}B compound.« less

Charge transfer and injection barrier at the metal-organic interfaces

NASA Astrophysics Data System (ADS)

Yan, Li

2002-09-01

The metal-organic interface plays a critical role in determining the functionality and performance of many innovative organic based devices. It has attracted extensive research interests in recent years. This thesis presents investigations of the electronic structures of organic materials, such as tris-(8-hydroxyquinoline) aluminum (Alq3) and copper phthalocyanine (CuPc), during their interface formation with metals. The characterization is accomplished by X-ray and ultraviolet photoelectron spectroscopes (XPS and UPS) and inverse photoelectron spectroscopy (IPES). As discussed herein, both occupied and unoccupied electronic states at the interfaces are carefully examined in different aspects. In Chapter 4, the charge transfer and chemical reaction at various metal/Alq3 interfaces are investigated using XPS and UPS to study the electron injection into the Alga film. Electron transfer from the low work function metal and Al/LiF(CsF) bilayer to the Alga has been observed. The role of the dielectric and possible chemistry at the interface are discussed in comparison of the low work function metals. Further in Chapter 5, the origin of the metal-interface dipole and the estimation of charge injection barrier is explored using several organic materials. A thermodynamic equilibrium model is extended to explain the relation between the charge transfer process ad the interface dipole. Further, in Chapter 6 the combination of XPS, UPS and IPES detailed the evolution of both occupied and unoccupied energy states during the alkali metal doping. The energy gap modification in organic due to metal doping is observed directly for the spectra. Chapter 7 provides stability study of the organic thin films under x-ray and UV light. The results verify the usability of UPS and XPS for the organic materials used in the thesis. Chapter 7 also shows the secondary ion mass spectroscopy results of metal diffusion in organic thin films.

A New NIST Database for the Simulation of Electron Spectra for Surface Analysis (SESSA): Application to Angle-Resolved X-ray Photoelectron Spectroscopy of HfO2, ZrO2, HfSiO4, and ZrSiO4 Films on Silicon

NASA Astrophysics Data System (ADS)

Powell, C. J.; Smekal, W.; Werner, W. S. M.

2005-09-01

We describe a new NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA). This database provides data for the many parameters needed in quantitative Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). In addition, AES and XPS spectra can be simulated for layered samples. The simulated spectra, for layer compositions and thicknesses specified by the user, can be compared with measured spectra. The layer compositions and thicknesses can then be adjusted to find maximum consistency between simulated and measured spectra. In this way, AES and XPS can provide more detailed characterization of multilayer thin-film materials. We report on the use of SESSA for determining the thicknesses of HfO2, ZrO2, HfSiO4, and ZrSiO4 films on Si by angle-resolved XPS. Practical effective attenuation lengths (EALs) have been computed from SESSA as a function of film thickness and photoelectron emission angle (i.e., to simulate the effects of tilting the sample). These EALs have been compared with similar values obtained from the NIST Electron Effective-Attenuation-Length Database (SRD 82). Generally good agreement was found between corresponding EAL values, but there were differences for film thicknesses less than the inelastic mean free path of the photoelectrons in the overlayer film. These differences are due to a simplifying approximation in the algorithm used to compute EALs in SRD 82. SESSA, with realistic cross sections for elastic and inelastic scattering in the film and substrate materials, is believed to provide more accurate EALs than SRD 82 for thin-film thickness measurements, particularly in applications where the film and substrate have different electron-scattering properties.

A New NIST Database for the Simulation of Electron Spectra for Surface Analysis (SESSA): Application to Angle-Resolved X-ray Photoelectron Spectroscopy of HfO2, ZrO2, HfSiO4, and ZrSiO4 Films on Silicon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Powell, C.J.; Smekal, W.; Werner, W.S.M.

2005-09-09

We describe a new NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA). This database provides data for the many parameters needed in quantitative Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). In addition, AES and XPS spectra can be simulated for layered samples. The simulated spectra, for layer compositions and thicknesses specified by the user, can be compared with measured spectra. The layer compositions and thicknesses can then be adjusted to find maximum consistency between simulated and measured spectra. In this way, AES and XPS can provide more detailed characterization of multilayer thin-film materials. Wemore » report on the use of SESSA for determining the thicknesses of HfO2, ZrO2, HfSiO4, and ZrSiO4 films on Si by angle-resolved XPS. Practical effective attenuation lengths (EALs) have been computed from SESSA as a function of film thickness and photoelectron emission angle (i.e., to simulate the effects of tilting the sample). These EALs have been compared with similar values obtained from the NIST Electron Effective-Attenuation-Length Database (SRD 82). Generally good agreement was found between corresponding EAL values, but there were differences for film thicknesses less than the inelastic mean free path of the photoelectrons in the overlayer film. These differences are due to a simplifying approximation in the algorithm used to compute EALs in SRD 82. SESSA, with realistic cross sections for elastic and inelastic scattering in the film and substrate materials, is believed to provide more accurate EALs than SRD 82 for thin-film thickness measurements, particularly in applications where the film and substrate have different electron-scattering properties.« less

Compositional and surface characterization of HULIS by UV-Vis, FTIR, NMR and XPS: Wintertime study in Northern India

NASA Astrophysics Data System (ADS)

Kumar, Varun; Goel, Anubha; Rajput, Prashant

2017-09-01

This study (first attempt) characterizes HULIS (Humic Like Substances) in wintertime aerosols (n = 12 during day and nighttime each) from Indo-Gangetic Plain (IGP, at Kanpur) by using various state-of-the art techniques such as UV-VIS, FTIR, 1H NMR and XPS. Based on UV-Vis analysis the absorption coefficient at 365 nm (babs-365) of HULIS was found to average at 13.6 and 28.8 Mm-1 during day and nighttime, respectively. Relatively high babs-365 of HULIS during the nighttime is attributed to influence of fog-processing. However, the power fit of UV-Vis spectrum provided near similar AAE (absorption Angstrom exponent) value of HULIS centering at 4.9 ± 1.4 and 5.1 ± 1.3 during daytime and nighttime, respectively. FTIR spectra and its double derivative revealed the presence of various functional groups viz. alcohols, ketones aldehydes, carboxylic acids as well as unsaturated and saturated carbon bonds. 1H NMR spectroscopy was applied to quantify relative percentage of various types of hydrogen atoms contained in HULIS, whereas XPS technique provided information on surface composition and oxidation states of various elements present. A significantly high abundance of H‒C‒O group has been observed in HULIS (based on 1H NMR); 41.4± 2.7% and 30.9± 2.4% in day and nighttime, respectively. However, aromatic protons (Ar-H) were higher in nighttime samples (19.3± 1.8%) as compared to that in daytime samples (7.5 ± 1.9). XPS studies revealed presence of various species on the surface of HULIS samples. Carbon existed in 7 different chemical states while total nitrogen and sulfur exhibited 3 and 2 different oxidation states (respectively) on the surface of HULIS. This study reports structural information and absorption properties of HULIS which has implications to their role as cloud condensation nuclei and atmospheric direct radiative forcing.

Applications Performance on NAS Intel Paragon XP/S - 15#

NASA Technical Reports Server (NTRS)

Saini, Subhash; Simon, Horst D.; Copper, D. M. (Technical Monitor)

1994-01-01

The Numerical Aerodynamic Simulation (NAS) Systems Division received an Intel Touchstone Sigma prototype model Paragon XP/S- 15 in February, 1993. The i860 XP microprocessor with an integrated floating point unit and operating in dual -instruction mode gives peak performance of 75 million floating point operations (NIFLOPS) per second for 64 bit floating point arithmetic. It is used in the Paragon XP/S-15 which has been installed at NAS, NASA Ames Research Center. The NAS Paragon has 208 nodes and its peak performance is 15.6 GFLOPS. Here, we will report on early experience using the Paragon XP/S- 15. We have tested its performance using both kernels and applications of interest to NAS. We have measured the performance of BLAS 1, 2 and 3 both assembly-coded and Fortran coded on NAS Paragon XP/S- 15. Furthermore, we have investigated the performance of a single node one-dimensional FFT, a distributed two-dimensional FFT and a distributed three-dimensional FFT Finally, we measured the performance of NAS Parallel Benchmarks (NPB) on the Paragon and compare it with the performance obtained on other highly parallel machines, such as CM-5, CRAY T3D, IBM SP I, etc. In particular, we investigated the following issues, which can strongly affect the performance of the Paragon: a. Impact of the operating system: Intel currently uses as a default an operating system OSF/1 AD from the Open Software Foundation. The paging of Open Software Foundation (OSF) server at 22 MB to make more memory available for the application degrades the performance. We found that when the limit of 26 NIB per node out of 32 MB available is reached, the application is paged out of main memory using virtual memory. When the application starts paging, the performance is considerably reduced. We found that dynamic memory allocation can help applications performance under certain circumstances. b. Impact of data cache on the i860/XP: We measured the performance of the BLAS both assembly coded and Fortran coded. We found that the measured performance of assembly-coded BLAS is much less than what memory bandwidth limitation would predict. The influence of data cache on different sizes of vectors is also investigated using one-dimensional FFTs. c. Impact of processor layout: There are several different ways processors can be laid out within the two-dimensional grid of processors on the Paragon. We have used the FFT example to investigate performance differences based on processors layout.

Functionalization to control microstructural, optical, electronic and wetting properties of metal oxide surfaces

NASA Astrophysics Data System (ADS)

Singh, Jagdeep

This thesis focuses on engineering the surface chemistry of oxide surfaces in order to control their microstructural, optical, electronic and wetting properties. Several different types of experiments have been performed to tailor the properties of silicon oxide, titanium dioxide, and zinc oxide surfaces. Applications of this work include organic electronics, sensors and nanomanufacturing. Adsorption of 3-mercaptopropyltrimethoxysilane (MPS) on hydroxylated silicon oxide substrates by immersion in MPS solution or exposure to MPS vapor has been compared using X-ray photoelectron spectroscopy (XPS). To aid the interpretation, MPS has also been cryogenically condensed in ultrahigh vacuum (UHV) onto gold surfaces. Condensation of MPS vapor on gold in the absence of water does not result in MPS polymerization, as evidenced by multilayer desorption upon warming to room temperature. The C1s XPS spectrum has been used to infer the relative abundance of methoxy groups. Vapor-deposition on hydroxylated silicon oxide leads to an unpolymerized MPS monolayer consisting of molecules with two methoxy groups. UV induced hydrophilicity of titanium dioxide surfaces could possibly be used to provide a means of registration and alignment in high-rate nanomanufacturing applications or to induce transfer of nanoelements. In order to understand the nature and magnitude of intermolecular forces, force-distance curves have been measured on TiO2. Toward the goal of possibly using light to induce nanoparticle transfer, force curves have been recorded using an SiO2 colloidal probe before and after irradiating the TiO 2 surface with UV light. In order to eliminate the effects of capillary forces, the relative humidity has been kept below 1% by flowing either N 2 or N2/O2 (1:1) into the AFM chamber. In a dry nitrogen environment, no difference is observed in adhesive forces measured with and without UV exposure. Gold-coated atomic force microscope (AFM) tips functionalized with amine-, hydroxyl, carboxylic acid, and methyl-terminated alkanethiol molecules have been used to probe the adhesive forces of polystyrene and poly(acrylic acid) films in dry air (relative humidity < 0.5%). XPS and contact angle measurements confirm the quality and uniformity of similarly treated gold surfaces and the polymer films. XPS indicates that the amine-functionalized thiol films are protonated and comprised of multilayers. Toward the goal of modifying its optical properties, ZnO nanorod surfaces have been modified using 3-mercaptopropyltriethoxysilane (MPTES) and 1-propanethiol (PPT), and XPS has been used to investigate the changes occurring on the nanorods after surface modification. XPS reveals that in the case of MPTES-modified nanorods, bonding occurs via both S-Zn and Si-O-Zn bond formation. For comparison, 3-mercaptopropyltrimethoxysilane (MPTMS), dodecanethiol and methanethiol have been adsorbed on sputter-cleaned Zn-terminated ZnO (0001) in ultrahigh vacuum (UHV). In this case, XPS indicates that bonding of thiols on ZnO surfaces occurs via S-Zn bond formation. Photoluminescence spectroscopy has been used to study the effect of surface functionalization on the optical properties of the nanorods. MPTES- and PPT-functionalized nano-ZnO show an increase in intensity of the UV emission peak relative to the unfunctionalized nanorods due to reduced probability of surface dependent non-radiative processes. A decrease in the visible peak in both cases is believed to be due to passivation of surface defects. A simple method for encapsulating zinc oxide nanoparticles within an organic matrix has been discovered that consists of dispersing them in an ethanolic solution, adding an organothiol and stirring while heating. Electron microscopy, photoemission, Raman spectroscopy and thermal gray metric analyses demonstrate that partial dissolution of the oxide occurs accompanied by encapsulation within a matrix consisting of a 1:2 zinc-thiol complex. Using this methodology, it is possible to surround ZnO within diverse matrices, including fluorescent ones. (Abstract shortened by UMI.)

XPS and biocompatibility studies of titania film on anodized NiTi shape memory alloy.

PubMed

Chu, C L; Wang, R M; Hu, T; Yin, L H; Pu, Y P; Lin, P H; Dong, Y S; Guo, C; Chung, C Y; Yeung, K W K; Chu, Paul K

2009-01-01

A dense titania film is fabricated in situ on NiTi shape memory alloy (SMA) by anodic oxidation in a Na(2)SO(4) electrolyte. The microstructure of the titania film and its influence on the biocompatibility of NiTi SMA are investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICPMS), hemolysis analysis, and platelet adhesion test. The results indicate that the titania film has a Ni-free zone near the surface and can effectively block the release of harmful Ni ions from the NiTi substrate in simulated body fluids. Moreover, the wettability, hemolysis resistance, and thromboresistance of the NiTi sample are improved by this anodic oxidation method.

A study of the UV and VUV degradation of FEP

NASA Technical Reports Server (NTRS)

George, Graeme A.; Hill, David J. T.; Odonnell, James H.; Pomery, Peter J.; Rasoul, Firas A.

1993-01-01

UV and VUV degradation of fluorinated ethylene propylene (FEP) copolymer was studied using electron spin resonance (ESR) spectroscopy, x-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The ESR study revealed the formation of a terminal polymer radical. The stability of this radical was investigated under different environments. An XPS study of FEP film exposed to VUV and atomic oxygen showed that oxidation takes place on the polymer surface. The study revealed also that the percentage of CF2 in the polymer surface decreased with exposure time and the percentage of CF, CF3, and carbon attached to oxygen increased. SEM micrographs of FEP film exposed to VUV and atomic oxygen identified a rough surface with undulations similar to sand dunes.

Electronic structure of LiGaS 2

NASA Astrophysics Data System (ADS)

Atuchin, V. V.; Isaenko, L. I.; Kesler, V. G.; Lobanov, S.; Huang, H.; Lin, Z. S.

2009-04-01

X-ray photoelectron spectroscopy (XPS) measurement has been performed to determine the valence band structure of LiGaS 2 crystals. The experimental measurement is compared with the electronic structure obtained from the density functional calculations. It is found that the Ga 3d states in the XPS spectrum are much higher than the calculated results. In order to eliminate this discrepancy, the LDA+ U method is employed and reasonable agreement is achieved. Further calculations show that the difference of the linear and nonlinear optical coefficients between LDA and LDA+ U calculations is negligibly small, indicating that the Ga 3d states are actually independent of the excited properties of LiGaS 2 crystals since they are located at a very deep position in the valence bands.

X-ray photoelectron spectroscopy and atomic force microscopy characterization of the effects of etching Zn xCd 1- xTe surfaces

NASA Astrophysics Data System (ADS)

George, M. A.; Azoulay, M.; Jayatirtha, H. N.; Burger, A.; Collins, W. E.; Silberman, E.

1993-10-01

X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) was used for the first time to characterize the chemical composition of modified surfaces of Zn xCd 1- xTe single crystals. These surface treatments were selected for their relevance to device preparation procedures. The XPS peaks indicated an increase of the tellurium and a depletion of the cadmium concentrations upon etching in bromine methanol solution. AFM revealed the formation of pronounced Te inclusions. Higher x values correlated with a decrease in residual bromine left on the surface, while cut and polished samples had higher oxide concentrations and increased bromination of the surface than cleaved samples.

X-ray photoelectron spectroscopy study of chemically-etched Nd-Ce-Cu-O surfaces

NASA Technical Reports Server (NTRS)

Vasquez, R. P.; Gupta, A.; Kussmaul, A.

1991-01-01

Acetic acid, Br2, and HCl solutions are investigated for removing insulating species from Nd(1.85)Ce(0.15)CuO(4-delta) (NCCO) thin film surfaces. X-ray photoelectron spectroscopy (XPS) shows that the HCl etch is most effective, yielding O 1s spectra comparable to those obtained from samples cleaned in vacuum and a clear Fermi edge in the valence band region. Reduction and oxidation reversibly induces and eliminates, respectively, Fermi level states for undoped samples, but has no clearly observable effect on the XPS spectra for doped samples. Reactivity to air is much less for NCCO compared to hole superconductors, which is attributed to the lack of reactive alkaline earth elements in NCCO.

Intrinsic ferromagnetism in nanocrystalline Mn-doped ZnO depending on Mn concentration.

PubMed

Subramanian, Munisamy; Tanemura, Masaki; Hihara, Takehiko; Soga, Tetsuo; Jimbo, Takashi

2011-04-01

The physical properties of Zn(1-x)Mn(x)O nanoparticles synthesized by thermal decomposition are extensively investigated by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman light scattering and Hysteresis measurements. XRD and XPS spectra reveal the absence of secondary phase in nanocrystalline ZnO doped with 5% or less Mn; and, later confirms that the valance state of Mn to be 2+ for all the samples. Raman spectra exhibit a peak at 660 cm(-1) which we attribute to the intrinsic lattice defects of ZnO with increasing Mn concentration. Overall, our results demonstrate that ferromagnetic properties can be realized while Mn-doped ZnO obtained in the nanocrystalline form.

Time-dependent investigation of sub-monolayers of Ni on Pd using Positron-annihilation induced Auger Electron Spectroscopy and XPS

NASA Astrophysics Data System (ADS)

Zimnik, Samantha; Piochacz, Christian; Vohburger, Sebastian; Hugenschmidt, Christoph

2016-01-01

The surface of a polycrystalline Pd-substrate covered with (sub-) monolayers of Ni was investigated with Positron-annihilation induced Auger Electron Spectroscopy (PAES). Comparative studies using conventional AES induced by electrons and X-rays showed the outstanding surface sensitivity of PAES. Time-dependent PAES was performed on a 0.5 ML Ni cover layer on Pd and compared with conventional X-ray induced Photoelectron Spectroscopy (XPS) in order to observe changes in the elemental composition of the surface. The PAES results appear to show a migration of Ni atoms into the Pd substrate, whereas the Ni signal shows a decrease of 12% within 13 h with respect to the initial value.

Raman enhancement by graphene-Ga2O3 2D bilayer film.

PubMed

Zhu, Yun; Yu, Qing-Kai; Ding, Gu-Qiao; Xu, Xu-Guang; Wu, Tian-Ru; Gong, Qian; Yuan, Ning-Yi; Ding, Jian-Ning; Wang, Shu-Min; Xie, Xiao-Ming; Jiang, Mian-Heng

2014-01-28

2D β-Ga2O3 flakes on a continuous 2D graphene film were prepared by a one-step chemical vapor deposition on liquid gallium surface. The composite was characterized by optical microscopy, scanning electron microscopy, Raman spectroscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy (XPS). The experimental results indicate that Ga2O3 flakes grew on the surface of graphene film during the cooling process. In particular, tenfold enhancement of graphene Raman scattering signal was detected on Ga2O3 flakes, and XPS indicates the C-O bonding between graphene and Ga2O3. The mechanism of Raman enhancement was discussed. The 2D Ga2O3-2D graphene structure may possess potential applications.

An investigation of adhesive/adherend and fiber matrix interactions. [Ti 6-4 surfaces

NASA Technical Reports Server (NTRS)

Beck, B.; Siriwardane, R.; Wightman, J. P.

1981-01-01

Research during the report period focused on continued scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) of lap shear samples and flatwise tensile specimens and on the surface characterization of TiO2, Ti 6-4, and Ti powders with particular emphasis on their interaction with primer solutions of both polyphenylquinoxaline and LaRC-13 polyimide. The use of SEM and XPS in the analysis of Ti 6-4 adherend surfaces is described as well as differences in Ti 6-4 surface composition after different chemical pretreatments. Analysis of fractured surfaces is used to established the failure mode. The surface acidity of Ti 6-4 coupons can be established by reflectance visible spectroscopy using indicator dyes.

Effect of sputtering power on structure, adhesion strength and corrosion resistance of nitrogen doped diamond-like carbon thin films.

PubMed

Khun, N W; Liu, E

2011-06-01

Nitrogen doped diamond-like carbon (DLC:N) thin films were deposited on highly conductive p-Si substrates using a DC magnetron sputtering deposition system. The DLC:N films were characterized using X-ray photoelectron spectroscopy (XPS), micro-Raman spectroscopy, atomic force microscopy (AFM), contact angle measurement and micro-scratch test. The XPS and Raman results indicated that the sputtering power significantly influenced the properties of the films in terms of bonding configuration in the films. The corrosion performance of the DLC:N films was investigated in a 0.6 M NaCl solution by means of potentiodynamic polarization testing. It was found that the corrosion performance of the films could be enhanced by higher sputtering powers.

Application of surface analysis to solve problems of wear

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1981-01-01

Results are presented for the use of surface analytical tools including field ion microscopy, Auger emission spectroscopy analysis (AES), cylindrical mirror Auger analysis and X-ray photoelectron spectroscopy (XPS). Data from the field ion microscope reveal adhesive transfer (wear) at the atomic level with the formation of surface compounds not found in the bulk, and AES reveals that this transfer will occur even in the presence of surface oxides. Both AES and XPS reveal that in abrasive wear with silicon carbide and diamond contacting the transition metals, the surface and the abrasive undergo a chemical or structural change which effects wear. With silicon carbide, silicon volatilizes leaving behind a pseudo-graphitic surface and the surface of diamond is observed to graphitize.

Atmospheric-Pressure Plasma Interaction with Soft Materials as Fundamental Processes in Plasma Medicine.

PubMed

Takenaka, Kosuke; Miyazaki, Atsushi; Uchida, Giichiro; Setsuhara, Yuichi

2015-03-01

Molecular-structure variation of organic materials irradiated with atmospheric pressure He plasma jet have been investigated. Optical emission spectrum in the atmospheric-pressure He plasma jet has been measured. The spectrum shows considerable emissions of He lines, and the emission of O and N radicals attributed to air. Variation in molecular structure of Polyethylene terephthalate (PET) film surface irradiated with the atmospheric-pressure He plasma jet has been observed via X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). These results via XPS and FT-IR indicate that the PET surface irradiated with the atmospheric-pressure He plasma jet was oxidized by chemical and/or physical effect due to irradiation of active species.

Synthesis of TiN/a-Si3N4 thin film by using a Mather type dense plasma focus system

NASA Astrophysics Data System (ADS)

Hussain, T.; R., Ahmad; Khalid, N.; A. Umar, Z.; Hussnain, A.

2013-05-01

A 2.3 kJ Mather type pulsed plasma focus device was used for the synthesis of a TiN/a-Si3N4 thin film at room temperature. The film was characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The XRD pattern confirms the growth of polycrystalline TiN thin film. The XPS results indicate that the synthesized film is non-stoichiometric and contains titanium nitride, silicon nitride, and a phase of silicon oxy-nitride. The SEM and AFM results reveal that the surface of the synthesized film is quite smooth with 0.59 nm roughness (root-mean-square).

Facile and fast synthesis of SnS2 nanoparticles by pulsed laser ablation in liquid

NASA Astrophysics Data System (ADS)

Johny, J.; Sepulveda-Guzman, S.; Krishnan, B.; Avellaneda, D.; Shaji, S.

2018-03-01

Nanoparticles (NPs) of tin disulfide (SnS2) were synthesized using pulsed laser ablation in liquid (PLAL) technique. Effects of different liquid media and ablation wavelengths on the morphology and optical properties of the nanoparticles were studied. Nd: YAG laser wavelengths of 532 nm and 1064 nm (frequency 10 Hz and pulse width 10 ns) were used to irradiate SnS2 target immersed in liquid for the synthesis of SnS2 nanoparticles. Here PLAL was a fast synthesis technique, the ablation was only for 30 s. Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, UV-vis absorption spectroscopy and photoluminescence spectroscopy were used to characterize the SnS2 NPs. TEM images showed that the liquid medium and laser wavelength influence the morphology of the NPs. SAED patterns and high resolution TEM (HRTEM) images confirmed the crystallinity of the particles. XRD and XPS analyses confirmed that SnS2 NPs were having exact crystalline structure and chemical states as that of the target. Raman analysis also supported the results obtained by XRD and XPS. Optical band gaps of the nanocolloids evaluated from their UV-vis absorption spectra were 2.4-3.05 eV. SnS2 NPs were having luminescence spectra in the blue-green region irrespective of the liquid media and ablation wavelength.

Investigation of lithium PFC surface characteristics and low recycling at LTX/LTX-Beta

NASA Astrophysics Data System (ADS)

Maan, Anurag; Kaita, Robert; Elliott, Drew; Boyle, Dennis; Majeski, Richard; Donovan, David; Buzi, Luxherta; Koel, Bruce E.; Biewer, Theodore M.

2017-10-01

Lithium coatings on high-Z PFCs at LTX have led to improved plasma performance. The initial hypothesis was that lithium retains hydrogen by forming lithium hydride and thereby enabling low recycling in LTX. However, recent in-vacuo measurements indicate the presence of lithium oxide in deposited lithium coatings. Improved plasma performance continued to be observed in the presence of lithium oxide. These observations raise questions like what is the nature of the lithium oxide surface, whether the PFC is an amorphous mixture of lithium and lithium oxide or something more ordered like a lithium oxide layer growing on top of lithium, and whether lithium oxide is responsible for any retention of hydrogen from the plasma. To investigate the mechanism by which the LTX PFC might be responsible for low recycling, we discuss the results of deuterium retention measurements using NRA/RBS and sample characterization using high resolution XPS (HR-XPS) in bulk lithium samples. Baseline HR-XPS scans indicate the presence of Lithium Oxide on sputtered lithium samples. Status of related planned experiments at LTX- β will also be discussed. This work was supported by the US. D.O.E. contract DE-AC05-00OR22725 and DE-AC02-09CH11466. BEK acknowledges support of this work by the U.S. DOE, Office of Science/FES under Award Number DE-SC0012890.

Rondorfite-type structure — XPS and UV–vis study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dulski, M., E-mail: mateusz.dulski@smcebi.edu.pl; A.Chelkowski Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice; Bilewska, K., E-mail: kbilewska@us.edu.pl

2015-10-15

Highlights: • Structural and spectroscopic characterization of chlorosilicate mineral, rondorfite. • Characterization of main photoemission lines and valence band spectra. • The study of color origin’s using UV–vis spectroscopy. • Analysis of structural changes in context of origin of natural fluorescence. • Discussion of a new application possibilities of analyzed mineral - Abstract: This paper focuses on X-ray diffraction, X-ray photoelectron and UV–vis spectroscopy of two different (green, orange) rondorfite samples. The differences in the sample color originate from various O/Cl ratios. The orange color was found to be related either to the isomorphic substitution of Fe{sup 3+}/Al{sup 3+} formore » Mg{sup 2+}, the presence of atypical [MgO{sub 4}] tetrahedrons in crystal structure or electronegativity of the sample. The tetrahedron is known to be very prone to accumulation of impurities and substitute atoms. Moreover, the XPS data showed tetrahedrally coordinated Mg{sup 2+} and isomorphic substitution of Al{sup 3+}/Fe{sup 3+} for Mg{sup 2+}, which influences local disordering and the point defects density and distribution. Non-equilibrium chlorine positions inside the crystal cages as well as Ca-Cl bonds have also been found. The XPS measurements as a function of temperature indicate occurrence of a structural transformation at about 770 K which is accompanied by a rotation of silicate tetrahedra within magnesiosilicate pentamer and luminescence disappearance.« less

Monitoring N3 dye adsorption and desorption on TiO2 surfaces: a combined QCM-D and XPS study.

PubMed

Wayment-Steele, Hannah K; Johnson, Lewis E; Tian, Fangyuan; Dixon, Matthew C; Benz, Lauren; Johal, Malkiat S

2014-06-25

Understanding the kinetics of dye adsorption and desorption on semiconductors is crucial for optimizing the performance of dye-sensitized solar cells (DSSCs). Quartz crystal microbalance with dissipation monitoring (QCM-D) measures adsorbed mass in real time, allowing determination of binding kinetics. In this work, we characterize adsorption of the common RuBipy dye N3 to the native oxide layer of a planar, sputter-coated titanium surface, simulating the TiO2 substrate of a DSSC. We report adsorption equilibrium constants consistent with prior optical measurements of N3 adsorption. Dye binding and surface integrity were also verified by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy (XPS). We further study desorption of the dye from the native oxide layer on the QCM sensors using tetrabutylammonium hydroxide (TBAOH), a commonly used industrial desorbant. We find that using TBAOH as a desorbant does not fully regenerate the surface, though little ruthenium or nitrogen is observed by XPS after desorption, suggesting that carboxyl moieties of N3 remain bound. We demonstrate the native oxide layer of a titanium sensor as a valid and readily available planar TiO2 morphology to study dye adsorption and desorption and begin to investigate the mechanism of dye desorption in DSSCs, a system that requires further study.

Recovery Act. Advanced Building Insulation by the CO 2 Foaming Process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Arthur

In this project, ISTN proposed to develop a new "3rd" generation of insulation technology. The focus was a cost-effective foaming process that could be used to manufacture XPS and other extruded polymer foams using environmentally clean blowing agents, and ultimately achieve higher R-values than existing products while maintaining the same level of cost-efficiency. In the U.S., state-of-the-art products are primarily manufactured by two companies: Dow and Owens Corning. These products (i.e., STYROFOAM and FOAMULAR) have a starting thermal resistance of R-5.0/inch, which declines over the life of the product as the HFC blowing agents essential to high R-value exchange withmore » air in the environment. In the existing technologies, the substitution of CO2 for HFCs as the primary foaming agent results in a much lower starting R-value, as evidenced in CO2-foamed varieties of XPS in Europe with R-4.2/inch insulation value. The major overarching achievement from this project was ISTN's development of a new process that uses CO2 as a clean blowing agent to achieve up to R-5.2/inch at the manufacturing scale, with a production cost on a per unit basis that is less than the cost of Dow and Owens Corning XPS products.« less

The production and verification of pristine semi-fluorinated thiol monolayers on gold.

PubMed

Ford, Kym; Battersby, Bronwyn J; Wood, Barry J; Gentle, Ian R

2012-03-15

The presence of adventitious contamination of self-assembled monolayers (SAMs) is a well-known phenomenon that is often overlooked or underestimated in the literature. Herein, we demonstrate that it is possible to produce pristine self-assembled monolayers (SAMs) on gold surfaces that are devoid of adventitious species. The chemical purity or the pristine quality of the SAM was verified by the experimental relative atomic ratios measured by X-ray photoelectron spectroscopy (XPS) of all elements including carbon and corresponded to within 5% of the stoichiometric ratios. Perfluoro-octyl-thiolate (F8) was used as a model compound in this study, where monolayers were assembled from solutions of an acetylated F8 precursor. Quantitative elemental characterization of the acetylated F8 precursor by cold-stage XPS provided valuable reference data for the analysis of the subsequent SAMs. Comprehensive analysis of high-resolution XPS C 1s spectra proved to be essential for establishing the purity of the SAMs, since the peaks of the adventitious species were easily distinguished from those of the F8. Analyses of deliberately contaminated F8 SAMs showed that the adventitious species persisted during the process of self-assembly and therefore co-existed with the SAM in the interfacial region. The work also established that even a lengthy deposition time of 18 h was incapable of displacing the adventitious species present at the interface. Copyright © 2011 Elsevier Inc. All rights reserved.

"Un-annealed and Annealed Pd Ultra-Thin Film on SiC Characterized by Scanning Probe Microscopy and X-ray Photoelectron Spectroscopy"

NASA Technical Reports Server (NTRS)

Lu, W. J.; Shi, D. T.; Elshot, K.; Bryant, E.; Lafate, K.; Chen, H.; Burger, A.; Collins, W. E.

1998-01-01

Pd/SiC has been used as a hydrogen and a hydrocarbon gas sensor operated at high temperature. UHV (Ultra High Vacuum)-Scanning Tunneling Microscopy (STM), Atomic Force Microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS) techniques were applied to study the relationship between the morphology and chemical compositions for Pd ultra-thin films on SiC (less than 30 angstroms) at different annealing temperatures. Pd ultra-thin film on 6H-SiC was prepared by the RF sputtering method. The morphology from UHV-STM and AFM shows that the Pd thin film was well deposited on SiC substrate, and the Pd was partially aggregated to round shaped participates at an annealing temperature of 300 C. At 400 C, the amount of surface participates decreases, and some strap shape participates appear. From XPS, Pd2Si was formed on the surface after annealing at 300 C, and all Pd reacted with SiC to form Pd2Si after annealing at 400 C. The intensity of the XPS Pd peak decreases enormously at 400 C. The Pd film diffused into SiC, and the Schottky barrier height has almost no changes. The work shows the Pd sicilides/SiC have the same electronic properties with Pd/SiC, and explains why the Pd/SiC sensor still responds to hydrogen at high operating temperatures.

Genetically engineered oncolytic Newcastle disease virus mediates cytolysis of prostate cancer stem like cells.

PubMed

Raghunath, Shobana; Pudupakam, Raghavendra Sumanth; Allen, Adria; Biswas, Moanaro; Sriranganathan, Nammalwar

2017-10-20

Oncolytic virotherapy is a promising novel approach that overcomes the limitations posed by radiation and chemotherapy. In this study, the oncolytic efficacy of a recombinant Newcastle disease virus (rNDV) BC-KLQL-GFP, against prostate cancer stem-like/tumor initiating cells was evaluated. Xenograft derived prostaspheres (XPS) induced tumor more efficiently than monolayer cell derived prostaspheres (MCPS) in nude mice. Primary and secondary XPS show enhanced self-renewal and clonogenic potential compared to MCPS. XPS also expressed embryonic stem cell markers, such as Nanog, CD44 and Nestin. Further, prostate specific antigen (PSA) activated recombinant Newcastle Disease Virus (rNDV) was selectively cytotoxic to tumor derived DU145 prostaspheres. An effective concentration (EC 50 ) of 0.11-0.14 multiplicity of infection was sufficient to cause prostasphere cell death in serum free culture. DU145 tumor xenograft derived prostaspheres were used as tumor surrogates as they were enriched for a putative tumor initiating cell population. PSA activated rNDV was efficient in inducing cell death of cells and prostaspheres derived from primary xenografts ex-vivo, thus signifying a potential in vivo efficacy. The EC 50 (∼0.1 MOI) for cytolysis of tumor initiating cells was slightly higher than that was required for the parental cell line, but within the therapeutic margin for safety and efficacy. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of substrate surface treatment on electrochemically assisted photocatalytic activity of N-S co-doped TiO2 films

NASA Astrophysics Data System (ADS)

Parada-Gamboa, N. J.; Pedraza-Avella, J. A.; Meléndez, A. M.

2017-01-01

To investigate whether different metal surface treatments, performed on meshes of stainless steel 304 and titanium, affect the photocatalytic activity (PCA) of supported modified anodic TiO2 films, metallic substrates were coated with titanium isopropoxide sol-gel precursor modified with thiourea. Substrates were pretreated by some of the following techniques: a) sandblasting, b) pickling, c) hydroxylation and d) passivation. The as-prepared electrode materials were characterized by X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), and voltammetry in the dark and under light UVA irradiation. PCA of modified N-S-TiO2 electrodes was evaluated by electrochemically assisted photocatalytic degradation of methyl orange. The results of XPS revealed that N and S were incorporated into the lattice of TiO2. FESEM showed that surface roughness and thickness of films varies depending on surface treatment. Voltammetric and XPS characterization of N-S co-doped TiO2 films supported on stainless steel revealed that their surface contains alpha-Fe2O3/FeOOH. Accordingly, iron contamination of the films coming from stainless steel was detrimental to the degradation of methyl orange. Prior to sol-gel coating process, sandblasting followed by nitric acid passivation for stainless steel or hydrofluoric acid pickling process in the case of titanium improved the PCA of N-S co-doped TiO2 films.

Novel durable bio-photocatalyst purifiers, a non-heterogeneous mechanism: accelerated entrapped dye degradation into structural polysiloxane-shield nano-reactors.

PubMed

Dastjerdi, Roya; Montazer, Majid; Shahsavan, Shadi; Böttcher, Horst; Moghadam, M B; Sarsour, Jamal

2013-01-01

This research has designed innovative Ag/TiO(2) polysiloxane-shield nano-reactors on the PET fabric to develop novel durable bio-photocatalyst purifiers. To create these very fine nano-reactors, oppositely surface charged multiple size nanoparticles have been applied accompanied with a crosslinkable amino-functionalized polysiloxane (XPs) emulsion. Investigation of photocatalytic dye decolorization efficiency revealed a non-heterogeneous mechanism including an accelerated degradation of entrapped dye molecules into the structural polysiloxane-shield nano-reactors. In fact, dye molecules can be adsorbed by both Ag and XPs due to their electrostatic interactions and/or even via forming a complex with them especially with silver NPs. The absorbed dye and active oxygen species generated by TiO(2) were entrapped by polysiloxane shelter and the presence of silver nanoparticles further attract the negative oxygen species closer to the adsorbed dye molecules. In this way, the dye molecules are in close contact with concentrated active oxygen species into the created nano-reactors. This provides an accelerated degradation of dye molecules. This non-heterogeneous mechanism has been detected on the sample containing all of the three components. Increasing the concentration of Ag and XPs accelerated the second step beginning with an enhanced rate. Further, the treated samples also showed an excellent antibacterial activity. Copyright © 2012 Elsevier B.V. All rights reserved.

Analysis of Ti and TiO2 nanolayers by total reflection X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Kubala-Kukuś, A.; Banaś, D.; Stabrawa, I.; Szary, K.; Sobota, D.; Majewska, U.; Wudarczyk-Moćko, J.; Braziewicz, J.; Pajek, M.

2018-07-01

Total reflection X-ray photoelectron spectroscopy (TRXPS) is applied in the analysis of Ti and TiO2 nanolayers deposited on silicon and silicon dioxide substrates. The idea of application of total-reflection phenomenon for exciting X-ray used in the XPS technique is briefly discussed. The experimental setup and measurement conditions for the studied Ti and TiO2 layers are presented. The XPS spectra were registered both for the non-total and total reflection regimes. The survey spectra and C1s, N1s, Ti2p and O1s photoelectron peaks are shown. For energy calibration, the position of C1s photoelectron peak was applied (C-C component, binding energy 284.8 eV). The peak to background ratios are discussed as regards the dependence of the excitation angle. An increase of this ratio for the glancing angle 1°, being below critical angle of the X-ray beam and sample material, results in an improvement of XPS detection limit by factor up to 2. In the case of the Ti nanolayer, additionally, the thickness of the overlayer TiO2 is determined. As an example of applying the TRXPS technique, the analysis of Ti nanolayers implanted by highly charged Xe35+ ions of 280 keV energy is discussed. The Xe3d and O1s photoelectron peaks are presented and discussed.

Synthesis and Structural Characterization of Silver Nanoparticles Stabilized with 3-Mercapto-1-Propansulfonate and 1-Thioglucose Mixed Thiols for Antibacterial Applications

PubMed Central

Porcaro, Francesco; Carlini, Laura; Ugolini, Andrea; Visaggio, Daniela; Visca, Paolo; Fratoddi, Ilaria; Venditti, Iole; Meneghini, Carlo; Simonelli, Laura; Marini, Carlo; Olszewski, Wojciech; Ramanan, Nitya; Luisetto, Igor; Battocchio, Chiara

2016-01-01

The synthesis, characterization and assessment of the antibacterial properties of hydrophilic silver nanoparticles (AgNPs) were investigated with the aim to probe their suitability for innovative applications in the field of nanobiotechnology. First, silver nanoparticles were synthetized and functionalized with two capping agents, namely 3-mercapto-1-propansulfonate (3MPS) and 1-β-thio-d-glucose (TG). The investigation of the structural and electronic properties of the nano-systems was carried out by means of X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS). XPS data provided information about the system stability and the interactions between the metallic surface and the organic ligands. In addition, XPS data allowed us to achieve a deep understanding of the influence of the thiols stoichiometric ratio on the electronic properties and stability of AgNPs. In order to shed light on the structural and electronic local properties at Ag atoms sites, XAS at Ag K-Edge was successfully applied; furthermore, the combination of Dynamic Light Scattering (DLS) and XAS results allowed determining AgNPs sizes, ranging between 3 and 13 nm. Finally, preliminary studies on the antibacterial properties of AgNPs showed promising results on four of six multidrug-resistant bacteria belonging to the ESKAPE group (Enterococcus faecium, Staphylococcus aureus, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa, and Enterobacter sp.). PMID:28774148

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farrokhzadeh, Abdolkarim; Modarresi-Alam, Ali Reza, E-mail: modaresi@chem.usb.ac.ir

Poly [(±)-2-(sec-butyl) aniline]/silica-supported perchloric acid composites were synthesized by combination of poly[(±)-2-sec-butylaniline] base (PSBA) and the silica-supported perchloric acid (SSPA) as dopant solid acid in solid-state. The X-ray photoelectron spectroscopy (XPS) and CHNS results confirm nigraniline oxidation state and complete doping for composites (about 75%) and non-complete for the PSBA·HCl salt (about 49%). The conductivity of samples was (≈0.07 S/cm) in agreement with the percent of doping obtained of the XPS analysis. Also, contact resistance was determined by circular-TLM measurement. The morphology of samples by the scanning electron microscopy (SEM) and their coating were investigated by XPS, SEM-map and energy-dispersivemore » X-ray spectroscopy (EDX). The key benefits of this work are the preparation of conductive chiral composite with the delocalized polaron structure under green chemistry and solid-state condition, the improvement of the processability by inclusion of the 2-sec-butyl group and the use of dopant solid acid (SSPA) as dopant. - Highlights: • The solid-state synthesis of the novel chiral composites of poly[(±)-2-(sec-butyl)aniline] (PSBA) and silica-supported perchloric acid (SSPA). • It takes 120 h for complete deprotonation of PSBA.HCl salt. • Use of SSPA as dopant solid acid for the first time to attain the complete doping of PSBA. • The coating of silica surface with PSBA.« less

Incorporation of low energy activated nitrogen onto HOPG surface: Chemical states and thermal stability studies by in-situ XPS and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Chandran, Maneesh; Shasha, Michal; Michaelson, Shaul; Hoffman, Alon

2016-09-01

In this paper we report the chemical states analysis of activated nitrogen incorporated highly oriented pyrolytic graphite (HOPG) surface under well-controlled conditions. Nitrogen incorporation is carried out by two different processes: an indirect RF nitrogen plasma and low energy (1 keV) N2+ implantation. Bonding configuration, concentration and thermal stability of the incorporated nitrogen species by aforesaid processes are systematically compared by in-situ X-ray photoelectron spectroscopy (XPS). Relatively large concentration of nitrogen is incorporated onto RF nitride HOPG surface (16.2 at.%), compared to N2+ implanted HOPG surface (7.7 at.%). The evolution of N 1s components (N1, N2, N3) with annealing temperature is comprehensively discussed, which indicates that the formation and reorganization of local chemical bonding states are determined by the process of nitridation and not by the prior chemical conditioning (i.e., amorphization or hydrogenation) of the HOPG surface. A combined XPS and Raman spectroscopy studies revealed that N2+ implantation process resulted in a high level of defects to the HOPG surface, which cannot be annealed-out by heat treatment up to 1000 °C. On the other hand, the RF nitrogen plasma process did not produce a high level of surface defects, while incorporating nearly the same amount of stable nitrogen species.

Americium(III) capture using phosphonic acid-functionalized silicas with different mesoporous morphologies: adsorption behavior study and mechanism investigation by EXAFS/XPS.

PubMed

Zhang, Wen; He, Xihong; Ye, Gang; Yi, Rong; Chen, Jing

2014-06-17

Efficient capture of highly toxic radionuclides with long half-lives such as Americium-241 is crucial to prevent radionuclides from diffusing into the biosphere. To reach this purpose, three different types of mesoporous silicas functionalized with phosphonic acid ligands (SBA-POH, MCM-POH, and BPMO-POH) were synthesized via a facile procedure. The structure, surface chemistry, and micromorphology of the materials were fully characterized by (31)P/(13)C/(29)Si MAS NMR, XPS, and XRD analysis. Efficient adsorption of Am(III) was realized with a fast rate to reach equilibrium (within 10 min). Influences including structural parameters and functionalization degree on the adsorption behavior were investigated. Slope analysis of the equilibrium data suggested that the coordination with Am(III) involved the exchange of three protons. Moreover, extended X-ray absorption fine structure (EXAFS) analysis, in combination with XPS survey, was employed for an in-depth probe into the binding mechanism by using Eu(III) as a simulant due to its similar coordination behavior and benign property. The results showed three phosphonic acid ligands were coordinated to Eu(III) in bidentate fashion, and Eu(P(O)O)3(H2O) species were formed with the Eu-O coordination number of 7. These phosphonic acid-functionalized mesoporous silicas should be promising for the treatment of Am-containing radioactive liquid waste.

The effect of simulated low earth orbit radiation on polyimides (UV degradation study)

NASA Technical Reports Server (NTRS)

Forsythe, John S.; George, Graeme A.; Hill, David J. T.; Odonnell, James H.; Pomery, Peter J.; Rasoul, Firas A.

1995-01-01

UV degradation of polyimide films in air and vacuum were studied using UV-visible, ESR, FTIR, and XPS spectroscopies. The UV-visible spectra of polyimide films showed a blue shift in the absorption compared to Kapton. This behavior was attributed to the presence of bulky groups and kinks along the polymer chains which disrupt the formation of a charge transfer complex. The UV-visible spectra showed also that UV irradiation of polyimides result extensively in surface degradation, leaving the bulk of the polymer intact. ESR spectra of polyimides irradiated in vacuum revealed the formation of stable carbon-centered radicals which give a singlet ESR spectrum, while polyimides irradiated in air produced an asymmetric signal shifted to a lower magnetic field, with a higher g value and line width. This signal was attributed to oxygen-cenetered radicals of peroxy and/or alkoxy type. The rate of radical formation in air was two fold higher than for vacuum irradiation, and reached a plateau after a short time. This suggests a continuous depletion of radicals on the surface via an ablative degradation process. FTIR, XPS, and weight loss studies supported this postulate. An XPS study of the surface indicated a substantial increase in the surface oxidation after irradiation in air. The sharp increase in the C-O binding energy peak relative to the C-C peak was believed to be associated with an aromatic ring opening reaction.

Characterization of Natural Dyes and Traditional Korean Silk Fabric by Surface Analytical Techniques

PubMed Central

Lee, Jihye; Kang, Min Hwa; Lee, Kang-Bong; Lee, Yeonhee

2013-01-01

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS) are well established surface techniques that provide both elemental and organic information from several monolayers of a sample surface, while also allowing depth profiling or image mapping to be carried out. The static TOF-SIMS with improved performances has expanded the application of TOF-SIMS to the study of a variety of organic, polymeric and biological materials. In this work, TOF-SIMS, XPS and Fourier Transform Infrared (FTIR) measurements were used to characterize commercial natural dyes and traditional silk fabric dyed with plant extracts dyes avoiding the time-consuming and destructive extraction procedures necessary for the spectrophotometric and chromatographic methods previously used. Silk textiles dyed with plant extracts were then analyzed for chemical and functional group identification of their dye components and mordants. TOF-SIMS spectra for the dyed silk fabric showed element ions from metallic mordants, specific fragment ions and molecular ions from plant-extracted dyes. The results of TOF-SIMS, XPS and FTIR are very useful as a reference database for comparison with data about traditional Korean silk fabric and to provide an understanding of traditional dyeing materials. Therefore, this study shows that surface techniques are useful for micro-destructive analysis of plant-extracted dyes and Korean dyed silk fabric. PMID:28809257

DOE Office of Scientific and Technical Information (OSTI.GOV)

Häusler, I., E-mail: ines.haeusler@bam.de; Dörfel, I., E-mail: Ilona.doerfel@bam.de; Peplinski, B., E-mail: Burkhard.peplinski@bam.de

A model system was used to simulate the properties of tribofilms which form during automotive braking. The model system was prepared by ball milling of a blend of 70 vol.% iron oxides, 15 vol.% molybdenum disulfide and 15 vol.% graphite. The resulting mixture was characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and various transmission electron microscopic (TEM) methods, including energy dispersive X-ray spectroscopy (EDXS), high resolution investigations (HRTEM) with corresponding simulation of the HRTEM images, diffraction methods such as scanning nano-beam electron diffraction (SNBED) and selected area electron diffraction (SAED). It could be shown that the ballmore » milling caused a reduction of the grain size of the initial components to the nanometer range. Sometimes even amorphization or partial break-down of the crystal structure was observed for MoS{sub 2} and graphite. Moreover, chemical reactions lead to a formation of surface coverings of the nanoparticles by amorphous material, molybdenum oxides, and iron sulfates as derived from XPS. - Highlights: • Ball milling of iron oxides, MoS{sub 2}, and graphite to simulate a tribofilm • Increasing coefficient of friction after ball milling of the model blend • Drastically change of the diffraction pattern of the powder mixture • TEM & XPS showed the components of the milled mixture and the process during milling. • MoS{sub 2} and graphite suffered a loss in translation symmetry or became amorphous.« less

Quantitative analysis of Ni2+/Ni3+ in Li[NixMnyCoz]O2 cathode materials: Non-linear least-squares fitting of XPS spectra

NASA Astrophysics Data System (ADS)

Fu, Zewei; Hu, Juntao; Hu, Wenlong; Yang, Shiyu; Luo, Yunfeng

2018-05-01

Quantitative analysis of Ni2+/Ni3+ using X-ray photoelectron spectroscopy (XPS) is important for evaluating the crystal structure and electrochemical performance of Lithium-nickel-cobalt-manganese oxide (Li[NixMnyCoz]O2, NMC). However, quantitative analysis based on Gaussian/Lorentzian (G/L) peak fitting suffers from the challenges of reproducibility and effectiveness. In this study, the Ni2+ and Ni3+ standard samples and a series of NMC samples with different Ni doping levels were synthesized. The Ni2+/Ni3+ ratios in NMC were quantitatively analyzed by non-linear least-squares fitting (NLLSF). Two Ni 2p overall spectra of synthesized Li [Ni0.33Mn0.33Co0.33]O2(NMC111) and bulk LiNiO2 were used as the Ni2+ and Ni3+ reference standards. Compared to G/L peak fitting, the fitting parameters required no adjustment, meaning that the spectral fitting process was free from operator dependence and the reproducibility was improved. Comparison of residual standard deviation (STD) showed that the fitting quality of NLLSF was superior to that of G/L peaks fitting. Overall, these findings confirmed the reproducibility and effectiveness of the NLLSF method in XPS quantitative analysis of Ni2+/Ni3+ ratio in Li[NixMnyCoz]O2 cathode materials.

Carbon monoxide reaction with UO2(111) single crystal surfaces: A theoretical and experimental study

NASA Astrophysics Data System (ADS)

Senanayake, S. D.; Soon, A.; Kohlmeyer, A.; Söhnel, T.; Idriss, H.

2005-07-01

The reaction of CO has been investigated on the surfaces of UO2(111) single crystal. Over the stoichiometric surface CO does not adsorb at 300 K and no further reaction is noticed. Over UO2-x (prepared by Ar+ bombardment), CO molecules adsorb and in presence of traces of H2 they couple to form acetylene molecules that desorb in two temperature domains during temperature programmed desorption (TPD). In the presence of excess H2 the coupling product is found to be ethylene. X-ray photoelectron spectroscopy (XPS) of the core level shows the presence of an U 4f line at 377 eV on the UO2-x surface, attributed to U metal. This line disappears upon CO adsorption (5 L and above) at 300 K indicating oxidation of U metal atoms by O from dissociatively adsorbed CO. XPS C 1s shows that the only C containing species formed is carbide. Computation of a α-U metal 2d-periodic slab was also conducted using plane-wave pseudopotential in the density functional theoretical framework. Two modes of CO adsorption were considered: molecular and dissociative. The dissociative adsorption was found more energetically favoured by 0.46 eV. From TPD, XPS and computation results it is strongly suggested that CO is dissociatively adsorbed on UO2-x and that a stable U-C species is formed at 300 K.

Surface chemical study on the covalent attachment of hydroxypropyltrimethyl ammonium chloride chitosan to titanium surfaces

NASA Astrophysics Data System (ADS)

Xu, Xiaofen; Wang, Ling; Guo, Shengrong; Lei, Lei; Tang, Tingting

2011-10-01

An anti-microbial and bioactive coating could not only reduce the probability of infection related to titanium implants but also support the growth of surrounding osteogenic cells. Our previous study has showed that hydroxypropyltrimethyl ammonium chloride chitosan (HACC) with a DS (degrees of substitution) of 18% had improved solubility and significantly higher antibacterial activities against three bacteria which were usually associated with infections in orthopaedics. In the current study, HACC with a DS of 18% coating was bonded to titanium surface by a three-step process. The titanium surface after each individual reaction step was analyzed by X-ray photoelectron spectroscopy (XPS) and attenuated total reflection (ATR) of Fourier-transformed infrared (FT-IR) spectroscopy. The XPS results demonstrated that there were great changes in the atomic ratios of C/Ti, O/Ti, and N/Ti after each reaction step. The XPS high resolution and corresponding devolution spectra of carbon, oxygen, nitrogen, and titanium were also in good coordination with the anticipated reaction steps. Additionally, the absorption bands around 3365 cm -1 (-OH vibration), 1664 cm -1 (Amide I), 1165 cm -1 ( νas, C-O-C bridge), and the broad absorption bands between 958 cm -1 and 1155 cm -1 (skeletal vibrations involving the C-O stretching of saccharide structure of HACC) verified that HACC was successfully attached to titanium surface.

A Novel Approach for the Treatment of Radiation-Induced Hemorrhagic Cystitis with the GreenLight™ XPS Laser

PubMed Central

Martinez, Daniel Roberto; Ercole, Cesar E; Lopez, Juan Gabriel; Parker, Justin; Hall, Mary K

2015-01-01

ABSTRACT Introduction: The treatment of pelvic malignancies with radiotherapy can develop severe sequelae, especially radiation-induced hemorrhagic cystitis. It is a progressive disease that can lead to the need for blood transfusion, hospitalizations, and surgical interventions. This tends to affect the quality of life of these patients, and management can at times be difficult. We have evaluated the GreenLight Xcelerated Performance System (XPS) with TruCoag, although primarily used for management of benign prostatic hypertrophy (BPH), for the treatment of radiation-induced hemorrhagic cystitis. Materials and Methods: After International Review Board (IRB) approval, a retrospective chart review was performed in addition to a literature search. A series of four male patients, mean age of 81 years, with radiation-induced hemorrhagic cystitis secondary to radiotherapy for pelvic malignancies (3 prostate cancer, 1 rectal cancer) were successfully treated with the GreenLight laser after unsuccessful treatment with current therapies described in the literature. Results: All four patients treated with the GreenLight laser had resolution of their hematuria after one treatment and were discharge from the hospital with clear urine. Conclusion: The GreenLight XPS laser shows promising results for the treatment of patients with radiation-induced hemorrhagic cystitis, and deserves further evaluation and validation, especially since there is limited data available in the literature regarding the use of this technology for the treatment of this devastating condition. PMID:26200555

Local Fine Structural Insight into Mechanism of Electrochemical Passivation of Titanium.

PubMed

Wang, Lu; Yu, Hongying; Wang, Ke; Xu, Haisong; Wang, Shaoyang; Sun, Dongbai

2016-07-20

Electrochemically formed passive film on titanium in 1.0 M H2SO4 solution and its thickness, composition, chemical state, and local fine structure are examined by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure. AES analysis reveals that the thickness and composition of oxide film are proportional to the reciprocal of current density in potentiodynamic polarization. XPS depth profiles of the chemical states of titanium exhibit the coexistence of various valences cations in the surface. Quantitative X-ray absorption near edge structure analysis of the local electronic structure of the topmost surface (∼5.0 nm) shows that the ratio of [TiO2]/[Ti2O3] is consistent with that of passivation/dissolution of electrochemical activity. Theoretical calculation and analysis of extended X-ray absorption fine structure spectra at Ti K-edge indicate that both the structures of passivation and dissolution are distorted caused by the appearance of two different sites of Ti-O and Ti-Ti. And the bound water in the topmost surface plays a vital role in structural disorder confirmed by XPS. Overall, the increase of average Ti-O coordination causes the electrochemical passivation, and the dissolution is due to the decrease of average Ti-Ti coordination. The structural variations of passivation in coordination number and interatomic distance are in good agreement with the prediction of point defect model.

Structural and mechanical properties of hydroxyapatite coatings formed by ion-beam assisted deposition

NASA Astrophysics Data System (ADS)

Zykova, A.; Safonov, V.; Dudin, S.; Yakovin, S.; Donkov, N.; Ghaemi, M. H.; Szkodo, M.; Antoszkiewicz, M.; Szyfelbain, M.; Czaban, A.

2018-03-01

The ion-beam assisted deposition (IBAD) is an advanced method capable of producing crystalline coatings at low temperatures. We determined the characteristics of hydroxyapatite Ca10(PO4)6(OH)2 target and coatings formed by IBAD using X-ray photoemission spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and energy dispersive X-ray (EDX). The composition of the coatings’ cross-section and surface was close to those of the target. The XPS spectra showed that the binding energy values of Ca (2p1/2, 2p3/2), P (2p3/2), and O 1s levels are related to the hydroxyapatite phase. The coatings demonstrate an optimal H/E ratio, and a good resistance to scratch tests.

Pinus Pinaster surface treatment realized in spatial and temporal afterglow DBD conditions

NASA Astrophysics Data System (ADS)

Lecoq, E.; Clément, F.; Panousis, E.; Loiseau, J.-F.; Held, B.; Castetbon, A.; Guimon, C.

2008-04-01

This experimental work deals with the exposition of Pinus Pinaster wood samples to a DBD afterglow. Electrical parameters like duty cycle and injected energy in the gas are being varied and the modifications induced by the afterglow on the wood are analysed by several macroscopic and microscopic ways like wettability, XPS analyses and also soaking tests of treated wood in a commercial fungicide solution. Soaking tests show that plasma treatment could enhance the absorption of fungicide into the wood. The wettability results point out that the plasma treatment can inflict on the wood different surface properties, making it hydrophilic or hydrophobic, when varying electrical parameters. XPS analyses reveal several chemical modifications like an increase of the O/C ratio and the presence of carboxyl groups on the surface after plasma treatments.

Gallium-containing polymer brush film as efficient supported Lewis acid catalyst in a glass microreactor.

PubMed

Munirathinam, Rajesh; Ricciardi, Roberto; Egberink, Richard J M; Huskens, Jurriaan; Holtkamp, Michael; Wormeester, Herbert; Karst, Uwe; Verboom, Willem

2013-01-01

Polystyrene sulfonate polymer brushes, grown on the interior of the microchannels in a microreactor, have been used for the anchoring of gallium as a Lewis acid catalyst. Initially, gallium-containing polymer brushes were grown on a flat silicon oxide surface and were characterized by FTIR, ellipsometry, and X-ray photoelectron spectroscopy (XPS). XPS revealed the presence of one gallium per 2-3 styrene sulfonate groups of the polymer brushes. The catalytic activity of the Lewis acid-functionalized brushes in a microreactor was demonstrated for the dehydration of oximes, using cinnamaldehyde oxime as a model substrate, and for the formation of oxazoles by ring closure of ortho-hydroxy oximes. The catalytic activity of the microreactor could be maintained by periodic reactivation by treatment with GaCl3.

Intensity analysis of XPS spectra to determine oxide uniformity - Application to SiO2/Si interfaces

NASA Technical Reports Server (NTRS)

Vasquez, R. P.; Grunthaner, F. J.

1980-01-01

A simple method of determining oxide uniformity is derived which requires no knowlege of film thickness, escape depth, or film composition. The method involves only the measurement of oxide and substrate intensities and is illustrated by analysis of XPS spectral data for thin SiO2 films grown both thermally and by low-temperature chemical vapor deposition on monocrystalline Si. A region 20-30 A thick is found near the SiO2/Si interface on thermally oxidized samples which has an inelastic mean free path 35% less than that found in the bulk oxide. This is interpreted as being due to lattice mismatch resulting in a strained region which is structurally, but not stoichiometrically, distinct from the bulk oxide.

A novel X-ray photoelectron spectroscopy study of the Al/SiO2 interface

NASA Technical Reports Server (NTRS)

Hecht, M. H.; Vasquez, R. P.; Grunthaner, F. J.; Zamani, N.; Maserjian, J.

1985-01-01

The nondestructive measurement of the chemical and physical characteristics of the interface between bulk SiO2 and thick aluminum films is reported. Both X-ray phototelectron spectroscopy (XPS) and electrical measurements of unannealed, resistively evaporated Al films on thermal SiO2 indicate an atomically abrupt interface. Post metallization annealing at 450 C induces reduction of the SiO2 by the aluminum, at a rate consistent with the bulk reaction rate. The XPS measurement is performed from the SiO2 side after the removal of the Si substrate with XeF2 gas and thinning of the SiO2 layer with HF:ETOH. This represents a powerful new approach to the study of metal-insulator and related interfaces.

Functionalization of biodegradable magnesium alloy implants with alkylphosphonate self-assembled films.

PubMed

Grubač, Z; Metikoš-Huković, M; Babić, R; Rončević, I Škugor; Petravić, M; Peter, R

2013-05-01

Mg and Mg-alloys are promising materials for biodegradable implants. In order to slowdown the Mg-alloy (AZ91D) degradation and enhance its biocompatibility, the alloy surface was modified with alkylphosphonate self-assembling films. The binding configuration and the structural organization of alkylphosphonate monolayers on the Mg-alloy surface were investigated using contact angle measurements, FTIR, and XPS. Combination of FTIR and XPS data indicated the presence of several different bonding modes (mono-, di-, and tri dentate) of phosphonate head groups with the alloy surface. The existence of well organized and ordered self-assembled alkylphosphonate monolayers with good barrier protecting properties in a physiological solution is a key step in the development of biocompatible Mg-alloy implants. Copyright © 2013 Elsevier B.V. All rights reserved.

A Study of Ziegler–Natta Propylene Polymerization Catalysts by Spectroscopic Methods

PubMed Central

Tkachenko, Olga P.; Kucherov, Alexey V.; Kustov, Leonid M.; Virkkunen, Ville; Leinonen, Timo; Denifl, Peter

2017-01-01

Ziegler–Natta polymerization catalysts were characterized by a complex of surface- and bulk-sensitive methods (DRIFTS, XPS, ESR, and XAS = XANES + EXAFS). A diffuse-reflectance Fourier-transform IR spectroscopy (DRIFTS) study showed the presence of strong Lewis acid sites in different concentrations and absence of strong basic sites in the polymerization catalysts. X-ray photoelectron spectroscopy (XPS), electron-spin resonance (ESR), and (X-ray absorption near-edge structure (XANES) analysis revealed the presence of Ti4+, Ti3+, Ti2+, and Ti1+ species in the surface layers and in the bulk of catalysts. The samples under study differ drastically in terms of the number of ESR-visible paramagnetic sites. The EXAFS study shows the presence of a Cl atom as a nearest neighbor of the absorbing Ti atom. PMID:28772850

Raman enhancement by graphene-Ga2O3 2D bilayer film

PubMed Central

2014-01-01

2D β-Ga2O3 flakes on a continuous 2D graphene film were prepared by a one-step chemical vapor deposition on liquid gallium surface. The composite was characterized by optical microscopy, scanning electron microscopy, Raman spectroscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy (XPS). The experimental results indicate that Ga2O3 flakes grew on the surface of graphene film during the cooling process. In particular, tenfold enhancement of graphene Raman scattering signal was detected on Ga2O3 flakes, and XPS indicates the C-O bonding between graphene and Ga2O3. The mechanism of Raman enhancement was discussed. The 2D Ga2O3-2D graphene structure may possess potential applications. PMID:24472433

Chrome-free Samarium-based Protective Coatings for Magnesium Alloys

NASA Astrophysics Data System (ADS)

Hou, Legan; Cui, Xiufang; Yang, Yuyun; Lin, Lili; Xiao, Qiang; Jin, Guo

The microstructure of chrome-free samarium-based conversion coating on magnesium alloy was investigated and the corrosion resistance was evaluated as well. The micro-morphology, transverse section, crystal structure and composition of the coating were observed by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive spectroscopy (EDS) and X- ray photoelectron spectroscopy (XPS), respectively. The corrosion resistance was evaluated by potentiodynamic polarization curve and electrochemical impedance spectroscopy (EIS). The results reveal that the morphology of samarium conversion coating is of crack-mud structure. Tiny cracks distribute in the compact coating deposited by samarium oxides. XRD, EDS and XPS results characterize that the coating is made of amorphous and trivalent-samarium oxides. The potentiodynamic polarization curve, EIS and OCP indicate that the samarium conversion coating can improve the corrosion resistance of magnesium alloys.

Electronic structure and fine structural features of the air-grown UNxOy on nitrogen-rich uranium nitride

NASA Astrophysics Data System (ADS)

Long, Zhong; Zeng, Rongguang; Hu, Yin; Liu, Jing; Wang, Wenyuan; Zhao, Yawen; Luo, Zhipeng; Bai, Bin; Wang, Xiaofang; Liu, Kezhao

2018-06-01

Oxide formation on surface of nitrogen-rich uranium nitride film/particles was investigated using X-ray photoelectron spectroscopy (XPS), auger electron spectroscopy (AES), aberration-corrected transmission electron microscopy (TEM), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) coupled with electron energy-loss spectroscopy (EELS). XPS and AES studies indicated that the oxidized layer on UN2-x film is ternary compound uranium oxynitride (UNxOy) in 5-10 nm thickness. TEM/HAADF-STEM and EELS studies revealed the UNxOy crystallizes in the FCC CaF2-type structure with the lattice parameter close to the CaF2-type UN2-x matrix. The work can provide further information to the oxidation mechanism of uranium nitride.

Compositions of surface layers formed on amalgams in air, water, and saline.

PubMed

Hanawa, T; Gnade, B E; Ferracane, J L; Okabe, T; Watari, F

1993-12-01

The surface layers formed on both a zinc-free and a zinc-containing dental amalgam after polishing and aging in air, water, or saline, were characterized using x-ray photoelectron spectroscopy (XPS) to determine the compositions of the surface layers which might govern the release of mercury from amalgam. The XPS data revealed that the formation of the surface layer on the zinc-containing amalgam was affected by the environment in which the amalgam was polished and aged, whereas that on the zinc-free amalgam was not affected. In addition, among the elements contained in amalgam, zinc was the most reactive with the environment, and was preferentially dissolved from amalgam into water or saline. Mercury atoms existed in the metallic state in the surface layer.

Observation of GaSe-SnO2 Heterostructure by XPS and AES

NASA Astrophysics Data System (ADS)

Tatsuyama, Chiei; Ichimura, Shoji; Iwakuro, Hiroaki

1982-01-01

The depth profile of the elemental composition of the GaSe-SnO2 heterostructure has been studied by XPS and AES. The SnO2 layer was prepared by spraying a solution of SnCl4 and SbCl3 in ethyl alcohol on to the the cleaved surface of GaSe heated to ˜400°C in air. After the solution had been sprayed on for about 5 secs., an SnO2 layer of thickness ˜460 Å formed, and a Ga2O3 layer of thickness ˜120 Å formed under the SnO2 layer. The Ga2O3 layer is a likely origin of the high-resistivity layer observed in the GaSe-SnO2 heterostructure.

Dysprosium electrodeposition from a hexaalkylguanidinium-based ionic liquid

NASA Astrophysics Data System (ADS)

Berger, Claudia A.; Arkhipova, Maria; Maas, Gerhard; Jacob, Timo

2016-07-01

The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important elements for high-tech industries and is mainly used in permanent magnetic applications, for example in electric vehicles, industrial motors and direct-drive wind turbines. In an effort to develop a more efficient electrochemical technique for depositing Dy on Nd-magnets in contrast to commonly used costly physical vapor deposition, we investigated the electrochemical behavior of dysprosium(iii) trifluoromethanesulfonate in a custom-made guanidinium-based room-temperature ionic liquid (RTIL). We first examined the electrodeposition of Dy on an Au(111) model electrode. The investigation was carried out by means of cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). CV measurements revealed a large cathodic reduction peak, which corresponds to the growth of monoatomic high islands, based on STM images taken during the initial stages of deposition. XPS identified these deposited islands as dysprosium. A similar reduction peak was also observed on an Nd-Fe-B substrate, and positively identified as deposited Dy using XPS. Finally, we varied the concentration of the Dy precursor, electrolyte flow and temperature during Dy deposition and demonstrated that each of these parameters could be used to increase the thickness of the Dy deposit, suggesting that these parameters could be tuned simultaneously in a temperature-controlled flow cell to enhance the thickness of the Dy layer.The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important elements for high-tech industries and is mainly used in permanent magnetic applications, for example in electric vehicles, industrial motors and direct-drive wind turbines. In an effort to develop a more efficient electrochemical technique for depositing Dy on Nd-magnets in contrast to commonly used costly physical vapor deposition, we investigated the electrochemical behavior of dysprosium(iii) trifluoromethanesulfonate in a custom-made guanidinium-based room-temperature ionic liquid (RTIL). We first examined the electrodeposition of Dy on an Au(111) model electrode. The investigation was carried out by means of cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). CV measurements revealed a large cathodic reduction peak, which corresponds to the growth of monoatomic high islands, based on STM images taken during the initial stages of deposition. XPS identified these deposited islands as dysprosium. A similar reduction peak was also observed on an Nd-Fe-B substrate, and positively identified as deposited Dy using XPS. Finally, we varied the concentration of the Dy precursor, electrolyte flow and temperature during Dy deposition and demonstrated that each of these parameters could be used to increase the thickness of the Dy deposit, suggesting that these parameters could be tuned simultaneously in a temperature-controlled flow cell to enhance the thickness of the Dy layer. Electronic supplementary information (ESI) available. See DOI: 10.1039/C6NR01351A

Etude Spectroscopique des Surfaces des Couches Minces de Silicium Amorphe Hydrogene

NASA Astrophysics Data System (ADS)

Bekkay, Touhami

In this work, we have studied the surface of hydrogenated a-Si and phosphorous doped a-Si:H,P. Due to the presence of unstable dangling bonds, these films are oxidized in the air after their preparation. XPS and UPS have been used to study these oxidized surfaces before and after plasma sputtering and wet chemical cleaning. We used deconvolution technique for the analysis of the spectra. First, the composition of a-Si:H films, prepared by plasma deposition at various power levels, has been determined by XPS. It has been found that films deposited using 5 W power contain SiH_4 molecules. This is confirmed by IR measurements. These molecules have not been seen in films prepared with a plasma power above 5 W. The XPS spectra of the surface oxide, before and after 3 keV sputtering by argon show that is impossible to completely remove these surface oxide ions. During sputtering, some oxygen atoms are forward scattered into the silicon substrat and form new oxidation states. UPS has been used to study the valence bands of the oxidized surfaces before and after HF cleaning. Prior to a chemical etch, the valence band analysis of the native SiO_2 indicates the presence of three O(2p) orbitals, in agreement with theory. Two are non-bonding orbitals and the third is associated with weak bonding to Si(3p). Two other orbitals have been identified at 10 eV and 11.8 eV. They correspond to O(2p)-Si(3p) and O(2p)-Si(3s) bonds respectively. A residual film containing -SiH, -SiO, SiOH and non-bonding orbitals has been found, after HF cleaning. A series of a-Si:H films have been doped with phosphine (PH_3). Their corresponding XPS spectra around 130 eV are dominated by the surface and bulk plasmon peaks. Numerical filtering has been used to distinguish between the phosphorous P(2p) peak located at 129.5 eV and the phosphorous oxide peak located at 134 eV. The increase in the intensity of these peaks as the (PH_3) increases indicates that a certain proportion of phosphorous is incorporated into the Si matrix and that the rest is oxidized. The shifts of the bulk Fermi level, E_{rm F}, and the surface Fermi level, E _{rm FS}, vary linearly with (PH_3). The difference between these two straight lines give the potential responsible for the bulk band bending. Close to the surface, the band bending is deduced by varying the detection angle in XPS measurements; a maximum value of 0.2 eV has been found in a depth range of 38 A to 105 A.

New insights into micro/nanoscale combined probes (nanoAuger, μXPS) to characterize Ag/Au@SiO2 core-shell assemblies

NASA Astrophysics Data System (ADS)

Ledeuil, J. B.; Uhart, A.; Soulé, S.; Allouche, J.; Dupin, J. C.; Martinez, H.

2014-09-01

This work has examined the elemental distribution and local morphology at the nanoscale of core@shell Ag/Au@SiO2 particles. The characterization of such complex metal/insulator materials becomes more efficient when using an initial cross-section method of preparation of the core@shell nanoparticles (ion milling cross polisher). The originality of this route of preparation allows one to obtain undamaged, well-defined and planar layers of cross-cut nano-objects. Once combined with high-resolution techniques of characterization (XPS, Auger and SEM), the process appears as a powerful way to minimize charging effects and enhance the outcoming electron signal (potentially affected by the topography of the material) during analysis. SEM experiments have unambiguously revealed the hollow-morphology of the metal core, while Auger spectroscopy observations showed chemical heterogeneity within the particles (as silver and gold are randomly found in the core ring). To our knowledge, this is the first time that Auger nano probe spectroscopy has been used and successfully optimized for the study of some complex metal/inorganic interfaces at such a high degree of resolution (~12 nm). Complementarily, XPS Au 4f and Ag 3d peaks were finally detected attesting the possibility of access to the whole chemistry of such nanostructured assemblies.This work has examined the elemental distribution and local morphology at the nanoscale of core@shell Ag/Au@SiO2 particles. The characterization of such complex metal/insulator materials becomes more efficient when using an initial cross-section method of preparation of the core@shell nanoparticles (ion milling cross polisher). The originality of this route of preparation allows one to obtain undamaged, well-defined and planar layers of cross-cut nano-objects. Once combined with high-resolution techniques of characterization (XPS, Auger and SEM), the process appears as a powerful way to minimize charging effects and enhance the outcoming electron signal (potentially affected by the topography of the material) during analysis. SEM experiments have unambiguously revealed the hollow-morphology of the metal core, while Auger spectroscopy observations showed chemical heterogeneity within the particles (as silver and gold are randomly found in the core ring). To our knowledge, this is the first time that Auger nano probe spectroscopy has been used and successfully optimized for the study of some complex metal/inorganic interfaces at such a high degree of resolution (~12 nm). Complementarily, XPS Au 4f and Ag 3d peaks were finally detected attesting the possibility of access to the whole chemistry of such nanostructured assemblies. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03211j

Dielectric relaxation and electronic structure of double perovskite Sr{sub 2}FeSbO{sub 6}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutta, Alo; Sinha, T. P.; Shannigrahi, Santiranjan

2008-09-15

The dielectric property and the electronic structure of a double perovskite, Sr{sub 2}FeSbO{sub 6} (SFS) synthesized by solid state reaction technique are investigated. The x-ray diffraction of the sample taken at room temperature shows cubic phase. The scanning electron micrograph of the sample also confirms the formation of the single phase of the material. We have measured the capacitance and conductance of SFS in a frequency range from 50 Hz to 1 MHz and in a temperature range from 163 to 463 K. A relaxation is observed in the entire temperature range as a gradual decrease in {epsilon}{sup '}({omega}) andmore » as a broad peak in {epsilon}{sup ''}({omega}). The frequency dependent electrical data are analyzed in the framework of conductivity and electric modulus formalisms. The frequencies corresponding to the maxima of the imaginary electric modulus at various temperatures are found to obey an Arrhenius law with an activation energy of 0.74 eV. The Cole-Cole model is used to study the dielectric relaxation of SFS. The scaling behavior of imaginary part of electric modulus suggests that the relaxation describes the same mechanism at various temperatures. The frequency dependent conductivity spectra follow the universal power law. The electronic structure of the SFS is studied by x-ray photoemission spectroscopy (XPS). Its valence band consists mainly of the oxygen 2p-states hybridized with the Fe 3d-states. The XPS spectra are investigated by the first principles full potential linearized augmented plane wave method. The angular momentum projected total and partial density of states obtained from first principles calculation are used to analyze the XPS results of the sample. The calculated electronic structures of SFS are qualitatively similar to those of the XPS spectra in terms of spectral features, energy positions, and relative intensities. The electronic structure calculation reveals that the electrical properties of SFS are dominated by the interaction between transition-metal and oxygen ions.« less

Physical and Chemical Behaviors of HCl on Ice Surface: Insights from an XPS and NEXAFS Study

NASA Astrophysics Data System (ADS)

Kong, X.; Waldner, A.; Orlando, F.; Birrer, M.; Artiglia, L.; Ammann, M.; Bartels-Rausch, T.

2016-12-01

Ice and snow play active roles for the water cycle, the energy budget of the Earth, and environmental chemistry in the atmosphere and cryosphere. Trace gases can be taken up by ice, and physical and chemical fates of the impurities could modify surface properties significantly and consequently influence atmospheric chemistry and the climate system. However, the understanding of chemical behaviour of impurities on ice surface are very poor, which is largely limited by the difficulties to apply high sensitivity experimental approaches to ambient air conditions, e.g. studies of volatile surfaces, because of the strict requirements of vacuum experimental conditions. In this study, we employed synchrotron-based X-ray photoelectron spectroscopy (XPS) and partial electron yield Near Edge X-ray Absorption Fine Structure (NEXAFS) in a state-of-the-art near-ambient pressure photoelectron (NAPP) spectroscopy end station. The NAPP enables to utilize the surface sensitive experimental methods, XPS and NEXAFS, on volatile surfaces, i.e. ice at temperatures approaching 0°C. XPS and NEXAFS together provide unique information of hydrogen bonding network, dopants surface concentration, dopant depth profile, and acidic dissociation on the surfaces1. Taking the advantages of the highly sensitive techniques, the adsorption, dissociation and depth profile of Hydrogen Chloride (HCl) on ice were studied. In brief, two states of Chloride on ice surface are identified from the adsorbed HCl, and they are featured with different depth profiles along the ice layers. Combining our results and previously reported constants from literatures (e.g. HCl diffusion coefficients in ice)2, a layered kinetic model has been constructed to fit the depth profiles of two states of Chloride. On the other side, pure ice and doped ice are compared for their surface structure change caused by temperature and the presence of HCl, which shows how the strong acid affect the ice surface in turn. 1. Orlando, F., et al., Top Catal 2016, 59, 591-604. 2. Huthwelker, T.; Malmstrom, M. E.; Helleis, F.; Moortgat, G. K.; Peter, T., J Phys Chem A 2004, 108, 6302-6318.

X-ray photoelectron spectroscopic and morphologic studies of Ru nanoparticles deposited onto highly oriented pyrolytic graphite

NASA Astrophysics Data System (ADS)

Bavand, R.; Yelon, A.; Sacher, E.

2015-11-01

Ruthenium nanoparticles (Ru NPs) function as effective catalysts in specific reactions, such as methanation and Fischer-Tropsch syntheses. It is our purpose to physicochemically characterize their surfaces, at which catalysis occurs, by surface-sensitive X-ray photoelectron spectroscopy (XPS), using the symmetric peak component anaylsis technique developed in our laboratory to reveal previously hidden components. Ru NPs were deposited by evaporation (0.25-1.5 nm nominal deposition range) onto highly oriented pyrolytic graphite (HOPG). In addition to their surfaces being characterized by XPS, an indication of morphology was obtained from transmission electron microscopy (TEM). Our use of symmetric peak component XPS analysis has revealed detailed information on a previously unidentified surface oxide initially formed, as well as on the valence electronic structure and its variation with NP size, information that is of potential importance in the use of these NPs in catalysis. Each of the several Ru core XPS spectra characterized (3d, 3p and 3s) was found to be composed of three symmetric components. Together with two metal oxide O1s components, these give evidence of a rather complex, previously unidentified oxide that is initially formed. The Ru valence band (4d and 5s) spectra clearly demonstrate a loss of metallicity, a simultaneous increase of the Kubo gap, and an abrupt transfer in valence electron density from the 4d to the 5s orbitals (known as electron spill-over), as the NP size decreases below 0.5 nm. TEM photomicrographs, as a function of deposition rate, show that, at a rate that gives insufficient time for the NP condensation energy to dissipate, the initially well-separated NPs are capable of diffusing laterally and aggregating. This indicates weak NP bonding to the HOPG substrate. Carbide is formed, at both high and low deposition rates, at Ru deposition thicknesses greater than 0.25 nm, its formation explained by Ru NPs reacting with residual hydrocarbon vapor, under the influence of the heat of condensation released on Ru deposition, and not by Ru reacting with the HOPG substrate.

An XPS study on the impact of relative humidity on the aging of UO 2 powders

DOE PAGES

Donald, Scott B.; Dai, Zurong R.; Davisson, M. Lee; ...

2017-02-10

High resolution x-ray photoemission spectroscopy (XPS) was used to characterize the chemical speciation of high purity uranium dioxide (UO 2) powder samples following aging for periods of up to one year under controlled conditions with relative humidity ranging from 34% to 98%. A systematic shift to higher uranium oxidation states, and thus an increase in the mean uranium valence, was found to directly correlate with the dose of water received (i.e. the product of exposure time and relative humidity). Exposure duration was found to have a greater impact on sample aging than relative humidity. Lastly, the sample aged at 98%more » relative humidity was found to have unique structural differences for exposure time beyond 180 days when observed by scanning electron microscopy (SEM).« less

Surface chemical properties of eutectic and frozen NaCl solutions probed by XPS and NEXAFS.

PubMed

Křepelová, Adéla; Huthwelker, Thomas; Bluhm, Hendrik; Ammann, Markus

2010-12-17

We study the surface of sodium chloride-water mixtures above, at, and below the eutectic temperature using X-ray photoelectron spectroscopy (XPS) and electron-yield near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NaCl frozen solutions are mimicking sea-salt deposits in ice or snow. Sea-salt particles emitted from the oceans are a major contributor to the global aerosol burden and can act as a catalyst for heterogeneous chemistry or as cloud condensation nuclei. The nature of halogen ions at ice surfaces and their influence on surface melting of ice are of significant current interest. We found that the surface of the frozen solution, depending on the temperature, consists of ice and different NaCl phases, that is, NaCl, NaCl·2H(2)O, and surface-adsorbed water.

Structure and magnetic properties of mono- and bi-layer graphene films on ultraprecision figured 4H-SiC(0001) surfaces.

PubMed

Hattori, Azusa N; Okamoto, Takeshi; Sadakuni, Shun; Murata, Junji; Oi, Hideo; Arima, Kenta; Sano, Yasuhisa; Hattori, Ken; Daimon, Hiroshi; Endo, Katsuyoshi; Yamauchi, Kazuto

2011-04-01

Monolayer and bilayer graphene films with a few hundred nm domain size were grown on ultraprecision figured 4H-SiC(0001) on-axis and 8 degrees -off surfaces by annealing in ultra-high vacuum. Using X-ray photoelectron spectroscopy (XPS), atomic force microscopy, reflection high-energy electron diffraction, low-energy electron diffraction (LEED), Raman spectroscopy, and scanning tunneling microscopy, we investigated the structure, number of graphene layers, and chemical bonding of the graphene surfaces. Moreover, the magnetic property of the monolayer graphene was studied using in-situ surface magneto-optic Kerr effect at 40 K. LEED spots intensity distribution and XPS spectra for monolayer and bilayer graphene films could become an obvious and accurate fingerprint for the determination of graphene film thickness on SiC surface.

Interactions of N,N'-dimethylaminoethanol with steel surfaces in alkaline and chlorine containing solutions

NASA Astrophysics Data System (ADS)

Welle, A.; Liao, J. D.; Kaiser, K.; Grunze, M.; Mäder, U.; Blank, N.

1997-10-01

Formulations based on dilute aqueous solutions of N,N'-dimethylethanolamine (DMEA) are used to protect reinforcement steel bars ('rebar') in concrete from corrosion. In a previous paper we discussed the usefulness of X-ray photoelectron spectroscopy (XPS) to detect DMEA adsorbed from solution and the application of secondary neutral mass spectrometry (SNMS) to study migration of DMEA through a cement matrix. In this report we present XPS data of DMEA adsorbed on steel surfaces from alkaline and chlorine containing solutions of variable concentration range and discuss models for the interaction of DMEA with the oxidized steel surface and the mechanism of corrosion inhibition of DMEA. DMEA is strongly bonded to the steel surface and displaces ionic species from the substrate/solution interface hence protecting the ironoxide surface from ionic attack.

Gallium-containing polymer brush film as efficient supported Lewis acid catalyst in a glass microreactor

PubMed Central

Munirathinam, Rajesh; Ricciardi, Roberto; Egberink, Richard J M; Huskens, Jurriaan; Holtkamp, Michael; Wormeester, Herbert; Karst, Uwe

2013-01-01

Summary Polystyrene sulfonate polymer brushes, grown on the interior of the microchannels in a microreactor, have been used for the anchoring of gallium as a Lewis acid catalyst. Initially, gallium-containing polymer brushes were grown on a flat silicon oxide surface and were characterized by FTIR, ellipsometry, and X-ray photoelectron spectroscopy (XPS). XPS revealed the presence of one gallium per 2–3 styrene sulfonate groups of the polymer brushes. The catalytic activity of the Lewis acid-functionalized brushes in a microreactor was demonstrated for the dehydration of oximes, using cinnamaldehyde oxime as a model substrate, and for the formation of oxazoles by ring closure of ortho-hydroxy oximes. The catalytic activity of the microreactor could be maintained by periodic reactivation by treatment with GaCl3. PMID:24062830

Novel protocol for highly efficient gas-phase chemical derivatization of surface amine groups using trifluoroacetic anhydride

NASA Astrophysics Data System (ADS)

Duchoslav, Jiri; Kehrer, Matthias; Hinterreiter, Andreas; Duchoslav, Vojtech; Unterweger, Christoph; Fürst, Christian; Steinberger, Roland; Stifter, David

2018-06-01

In the current work, chemical derivatization of amine (NH2) groups with trifluoroacetic anhydride (TFAA) as an analytical method to improve the information scope of X-ray photoelectron spectroscopy (XPS) is investigated. TFAA is known to successfully label hydroxyl (OH) groups. With the introduction of a newly developed gas-phase derivatization protocol conducted at ambient pressure and using a catalyst also NH2 groups can now efficiently be labelled with a high yield and without the formation of unwanted by-products. By establishing a comprehensive and self-consistent database of reference binding energies for XPS a promising approach for distinguishing hydroxyl from amine groups is presented. The protocol was verified on different polymers, including poly(allylamine), poly(ethyleneimine), poly(vinylalcohol) and chitosan, the latter one containing both types of addressed chemical groups.

An XPS study on the impact of relative humidity on the aging of UO 2 powders

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donald, Scott B.; Dai, Zurong R.; Davisson, M. Lee

High resolution x-ray photoemission spectroscopy (XPS) was used to characterize the chemical speciation of high purity uranium dioxide (UO 2) powder samples following aging for periods of up to one year under controlled conditions with relative humidity ranging from 34% to 98%. A systematic shift to higher uranium oxidation states, and thus an increase in the mean uranium valence, was found to directly correlate with the dose of water received (i.e. the product of exposure time and relative humidity). Exposure duration was found to have a greater impact on sample aging than relative humidity. Lastly, the sample aged at 98%more » relative humidity was found to have unique structural differences for exposure time beyond 180 days when observed by scanning electron microscopy (SEM).« less

Sliding friction and wear behaviors of surface-coated natural serpentine mineral powders as lubricant additive

NASA Astrophysics Data System (ADS)

Zhang, Baosen; Xu, Yi; Gao, Fei; Shi, Peijing; Xu, Binshi; Wu, Yixiong

2011-01-01

This work aims to investigate the friction and wear properties of surface-coated natural serpentine powders (SP) suspended in diesel engine oil using an Optimal SRV oscillating friction and wear tester. The worn surface was characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy (EDS). Results indicated that the additives can improve the wear resistance and decrease friction coefficient of carbon steel friction couples. The 0.5 wt% content of serpentine powders is found most efficient in reducing friction and wear at the load of 50 N. The SEM and XPS analysis results demonstrate that a tribofilm forms on the worn surface, which is responsible for the decrease in friction and wear, mainly with iron oxides, silicon oxides, graphite and organic compounds.

Local electrical properties of thermally grown oxide films formed on duplex stainless steel surfaces

NASA Astrophysics Data System (ADS)

Guo, L. Q.; Yang, B. J.; He, J. Y.; Qiao, L. J.

2018-06-01

The local electrical properties of thermally grown oxide films formed on ferrite and austenite surfaces of duplex stainless steel at different temperatures were investigated by Current sensing atomic force microscopy, X-ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES). The current maps and XPS/AES analyses show that the oxide films covering austenite and ferrite surfaces formed at different temperatures exhibit different local electrical characteristics, thickness and composition. The dependence of electrical conductivity of oxide films covering austenite and ferrite surface on the formation temperature is attributed to the film thickness and semiconducting structures, which is intrinsically related to thermodynamics and kinetics process of film grown at different temperature. This is well elucidated by corresponding semiconductor band structures of oxide films formed on austenite and ferrite phases at different temperature.

Controlling interface oxygen for forming Ag ohmic contact to semi-polar (1 1 -2 2) plane p-type GaN

NASA Astrophysics Data System (ADS)

Park, Jae-Seong; Han, Jaecheon; Seong, Tae-Yeon

2014-11-01

Low-resistance Ag ohmic contacts to semi-polar (1 1 -2 2) p-GaN were developed by controlling interfacial oxide using a Zn layer. The 300 °C-annealed Zn/Ag samples showed ohmic behavior with a contact resistivity of 6.0 × 10-4 Ω cm2 better than that of Ag-only contacts (1.0 × 10-3 Ω cm2). The X-ray photoemission spectroscopy (XPS) results showed that annealing caused the indiffusion of oxygen at the contact/GaN interface, resulting in the formation of different types of interfacial oxides, viz. Ga-oxide and Ga-doped ZnO. Based on the XPS and electrical results, the possible mechanisms underlying the improved electrical properties of the Zn/Ag samples are discussed.

Tribochemistry of contact interfaces of nanocrystalline molybdenum carbide films

NASA Astrophysics Data System (ADS)

Kumar, D. Dinesh; Kumar, N.; Panda, Kalpataru; Kamalan Kirubaharan, A. M.; Kuppusami, P.

2018-07-01

Transition metal carbides (TMC) are known for their improved tribological properties and are sensitive to the tribo-atmospheric environment. Nanocrystalline molybdenum carbide (MoC) thin films were deposited by DC magnetron sputtering technique using reactive CH4 gas. The friction and wear resistance properties of MoC thin films were significantly improved in humid-atmospheric condition as compared to high-vacuum tribo-condition. A comprehensive chemical analysis of deformed contact interfaces was carried out by X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX) and Raman spectroscopy. XPS and Raman spectroscopy showed the formation of stable molybdenum-oxide (MoO), molybdenum carbide (MoC) and amorphous carbon (a-C) tribo-phases. Moreover, during the sliding in humid-atmospheric condition, these phases were extensively deposited on the sliding steel ball counter body which significantly protected against undesirable friction and wear.

Electrochemical and XPS study of LiFePO4 cathode nanocomposite with PPy/PEG conductive network

NASA Astrophysics Data System (ADS)

Fedorková, A.; Oriňáková, R.; Oriňák, A.; Kupková, M.; Wiemhöfer, H.-D.; Audinot, J. N.; Guillot, J.

2012-08-01

High performance PPy/PEG-LiFePO4 nanocomposites as cathode materials were synthesized by solvothermal method and simple chemical oxidative polymerization of pyrrole (Py) monomer on the surface of LiFePO4 particles. The samples were characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectrometry (XPS) and charge-discharge tests. PPyPEG hybrid layers decrease particle to particle contact resistance while the impedance measurements confirmed that the coating of PPy-PEG significantly decreases the charge transfer resistance of the electrode material. The initial discharge capacities of this sample at C/5 and 1C are 150 and 128 mAh/g, respectively. The results show that PPy/PEGLiFePO4 composites are more effective than bare LiFePO4 as cathode material.

Auger electron diffraction study of the growth of Fe(001) films on ZnSe(001)

NASA Astrophysics Data System (ADS)

Jonker, B. T.; Prinz, G. A.

1991-03-01

The growth of Fe films on ZnSe(001) epilayers and bulk GaAs(001) substrates has been studied to determine the mode of film growth, the formation of the interface, and the structure of the overlayer at the 1-10 monolayer level. Auger electron diffraction (AED), x-ray photoelectron spectroscopy (XPS), and reflection high-energy electron diffraction data are obtained for incremental deposition of the Fe(001) overlayer. The coverage dependence of the AED forward scattering peaks reveals a predominantly layer-by-layer mode of film growth at 175 °C on ZnSe, while a more three-dimensional growth mode occurs on the oxide-desorbed GaAs(001) substrate. XPS studies of the semiconductor 3d levels indicate that the Fe/ZnSe interface is less reactive than the Fe/GaAs interface.

X-ray photoelectron spectroscopy characterization of a nonsuperconducting Y-Ba-Cu-O superconductor-normal-metal-superconductor barrier material

NASA Technical Reports Server (NTRS)

Vasquez, R. P.; Hunt, B. D.; Foote, M. C.; Bajuk, L. J.

1992-01-01

A film of a novel nonsuperconducting Y-Ba-Cu-O (YBCO) barrier material was grown using conditions similar to those reported by Agostinelli et al. (1991) for forming a cubic semiconducting (c-YBCO) phase, and the material was characterized using X-ray photoelectron spectroscopy (XPS). A comparison of the XPS spectra of this material to those obtained from the orthorhombic and tetragonal phases of YBCO (o-YBCO and t-YBCO, respectively) showed that the barrier material had spectral characteristics different from those of o-YBCO and t-YBCO, particularly in the O 1s region. Features associated with the Cu-O chain and surface-reconstructed Cu-O planes were absent, consistent with expectations for the simple perovskite crystal structure of c-YBCO proposed by Agostinelli et al.

Electrochemical and thermal grafting of alkyl grignard reagents onto (100) silicon surfaces.

PubMed

Vegunta, Sri Sai S; Ngunjiri, Johnpeter N; Flake, John C

2009-11-03

Passivation of (100) silicon surfaces using alkyl Grignard reagents is explored via electrochemical and thermal grafting methods. The electrochemical behavior of silicon in methyl or ethyl Grignard reagents in tetrahydrofuran is investigated using cyclic voltammetry. Surface morphology and chemistry are investigated using atomic force microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS). Results show that electrochemical pathways provide an efficient and more uniform passivation method relative to thermal methods, and XPS results demonstrate that electrografted terminations are effective at limiting native oxide formation for more than 55 days in ambient conditions. A two-electron per silicon mechanism is proposed for electrografting a single (1:1) alkyl group per (100) silicon atom. The mechanism includes oxidation of two Grignard species and subsequent hydrogen abstraction and alkylation reaction resulting in a covalent attachment of alkyl groups with silicon.

X-Ray photoelectron spectroscopy study of radiofrequency-sputtered titanium, carbide, molybdenum carbide, and titanium boride coatings and their friction properties

NASA Technical Reports Server (NTRS)

Brainard, W. A.; Wheeler, D. R.

1977-01-01

Radiofrequency sputtered coatings of titanium carbide, molybdenum carbide and titanium boride were tested as wear resistant coatings on stainless steel in a pin on disk apparatus. X-ray photoelectron spectroscopy (XPS) was used to analyze the sputtered films with regard to both bulk and interface composition in order to obtain maximum film performance. Significant improvements in friction behavior were obtained when properly biased films were deposited on deliberately preoxidized substrates. XPS depth profile data showed thick graded interfaces for bias deposited films even when adherence was poor. The addition of 10 percent hydrogen to the sputtering gas produced coatings with thin poorly adherent interfaces. Results suggest that some of the common practices in the field of sputtering may be detrimental to achieving maximum adherence and optimum composition for these refractory compounds.

Synchrotron-based ambient pressure X-ray photoelectron spectroscopy of hydrogen and helium

DOE PAGES

Zhong, Jian-Qiang; Wang, Mengen; Hoffmann, William H.; ...

2018-03-01

Contrary to popular belief, it is possible to obtain X-ray photoelectron spectra for elements lighter than lithium, namely hydrogen and helium. The literature is plagued with claims of this impossibility, which holds true for lab-based X-ray sources. However, this limitation is merely technical and is related mostly to the low X-ray photoionization cross-sections of the 1s orbitals of hydrogen and helium. Here, we show that, using ambient pressure X-ray photoelectron spectroscopy (XPS), a bright-enough X-ray source allows the study of these elusive elements. This has important implications in the understanding of the limitations of one of the most useful techniquesmore » in materials science, and moreover, it potentially opens the possibility of using XPS to directly study the most abundant element in the universe.« less

Semiconductor-metal transition of Se in Ru-Se Catalyst Nanoparticles

NASA Astrophysics Data System (ADS)

Babu, P. K.; Lewera, Adam; Oldfield, Eric; Wieckowski, Andrzej

2009-03-01

Ru-Se composite nanoparticles are promising catalysts for the oxygen reduction reaction (ORR) in fuel cells. Though the role of Se in enhancing the chemical stability of Ru nanoparticles is well established, the microscopic nature of Ru-Se interaction was not clearly understood. We carried out a combined investigation of ^77Se NMR and XPS on Ru-Se nanoparticles and our results indicate that Se, a semiconductor in elemental form, becomes metallic when interacting with Ru. ^77Se spin-lattice relaxation rates are found to be proportional to T, the well-known Korringa behavior characteristic of metals. The NMR results are supported by the XPS binding energy shifts which suggest that a possible Ru->Se charge transfer could be responsible for the semiconductor->metal transition of Se which also makes Ru less susceptible to oxidation during ORR.

Arsenic doped p-type zinc oxide films grown by radio frequency magnetron sputtering

NASA Astrophysics Data System (ADS)

Fan, J. C.; Zhu, C. Y.; Fung, S.; Zhong, Y. C.; Wong, K. S.; Xie, Z.; Brauer, G.; Anwand, W.; Skorupa, W.; To, C. K.; Yang, B.; Beling, C. D.; Ling, C. C.

2009-10-01

As-doped ZnO films were grown by the radio frequency magnetron sputtering method. As the substrate temperature during growth was raised above ˜400 °C, the films changed from n type to p type. Hole concentration and mobility of ˜6×1017 cm-3 and ˜6 cm2 V-1 s-1 were achieved. The ZnO films were studied by secondary ion mass spectroscopy, x-ray photoelectron spectroscopy (XPS), low temperature photoluminescence (PL), and positron annihilation spectroscopy (PAS). The results were consistent with the AsZn-2VZn shallow acceptor model proposed by Limpijumnong et al. [Phys. Rev. Lett. 92, 155504 (2004)]. The results of the XPS, PL, PAS, and thermal studies lead us to suggest a comprehensive picture of the As-related shallow acceptor formation.

Synchrotron-based ambient pressure X-ray photoelectron spectroscopy of hydrogen and helium

NASA Astrophysics Data System (ADS)

Zhong, Jian-Qiang; Wang, Mengen; Hoffmann, William H.; van Spronsen, Matthijs A.; Lu, Deyu; Boscoboinik, J. Anibal

2018-02-01

Contrary to popular belief, it is possible to obtain X-ray photoelectron spectra for elements lighter than lithium, namely hydrogen and helium. The literature is plagued with claims of this impossibility, which holds true for lab-based X-ray sources. However, this limitation is merely technical and is related mostly to the low X-ray photoionization cross-sections of the 1s orbitals of hydrogen and helium. In this letter, we show that, using ambient pressure X-ray photoelectron spectroscopy (XPS), a bright-enough X-ray source allows the study of these elusive elements. This has important implications in the understanding of the limitations of one of the most useful techniques in materials science, and moreover, it potentially opens the possibility of using XPS to directly study the most abundant element in the universe.

Electronic structure evolution of fullerene on CH 3NH 3PbI 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Chenggong; Wang, Congcong; Liu, Xiaoliang

2015-03-19

The thickness dependence of fullerene on CH 3NH 3PbI 3 perovskitefilm surface has been investigated by using ultraviolet photoemission spectroscopy (UPS), X-ray photoemission spectroscopy(XPS), and inverse photoemission spectroscopy (IPES). The lowest unoccupied molecular orbital and highest occupied molecular orbital (HOMO) can be observed directly with IPES and UPS. It is observed that the HOMO level in fullerene shifts to lower binding energy. The XPS results show a strong initial shift of core levels to lower binding energy in the perovskite, which indicates that electrons transfer from the perovskitefilm to fullerene molecules. Further deposition of fullerene forms C 60 solid, accompaniedmore » by the reduction of the electron transfer. As a result, the strongest electron transfer happened at 1/4 monolayer of fullerene.« less

Electronic structure evolution of fullerene on CH{sub 3}NH{sub 3}PbI{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Chenggong; Wang, Congcong; Kauppi, John

2015-03-16

The thickness dependence of fullerene on CH{sub 3}NH{sub 3}PbI{sub 3} perovskite film surface has been investigated by using ultraviolet photoemission spectroscopy (UPS), X-ray photoemission spectroscopy (XPS), and inverse photoemission spectroscopy (IPES). The lowest unoccupied molecular orbital and highest occupied molecular orbital (HOMO) can be observed directly with IPES and UPS. It is observed that the HOMO level in fullerene shifts to lower binding energy. The XPS results show a strong initial shift of core levels to lower binding energy in the perovskite, which indicates that electrons transfer from the perovskite film to fullerene molecules. Further deposition of fullerene forms C{submore » 60} solid, accompanied by the reduction of the electron transfer. The strongest electron transfer happened at 1/4 monolayer of fullerene.« less

Thermal decomposition study of manganese sulfide (MnS) nanoparticles

NASA Astrophysics Data System (ADS)

Tailor, Jiten P.; Khimani, Ankurkumar J.; Chaki, Sunil H.; Deshpande, M. P.

2018-05-01

The as-synthesized manganese sulfide (MnS) nanoparticles were used for the thermal study. The nanoparticles were synthesized by simple wet chemical route at ambient temperature. The photoelectron binding energy and chemical composition of MnS nanoparticles was analyzed by X-ray photoelectron spectroscopy (XPS). The thermogravimetric (TG), differential thermogravimetric (DTG) and differential thermal analysis (DTA) were carried out on the as-synthesized MnS nanoparticles. The thermocurves were recorded in inert N2 atmosphere in the temperature range of ambient to 1173 K. The heating rates employed were 5, 10, 15 and 20 K/min. The thermodynamic parameters like activation energy (Ea), enthalpy change (ΔH), entropy change (ΔS) and change in Gibbs free energy (ΔG) of as-synthesized MnS nanoparticles were determined using Kissinger method. The obtained XPS and thermal results are discussed.

Synchrotron-based ambient pressure X-ray photoelectron spectroscopy of hydrogen and helium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhong, Jian-Qiang; Wang, Mengen; Hoffmann, William H.

Contrary to popular belief, it is possible to obtain X-ray photoelectron spectra for elements lighter than lithium, namely hydrogen and helium. The literature is plagued with claims of this impossibility, which holds true for lab-based X-ray sources. However, this limitation is merely technical and is related mostly to the low X-ray photoionization cross-sections of the 1s orbitals of hydrogen and helium. Here, we show that, using ambient pressure X-ray photoelectron spectroscopy (XPS), a bright-enough X-ray source allows the study of these elusive elements. This has important implications in the understanding of the limitations of one of the most useful techniquesmore » in materials science, and moreover, it potentially opens the possibility of using XPS to directly study the most abundant element in the universe.« less

Catalytic activity of Ru-Sn/Al2O3 in reduction reaction of pollutant 4-Nitrophenol

NASA Astrophysics Data System (ADS)

Rini, A. S.; Radiman, S.; Yarmo, M. A.

2018-03-01

Ru-Sn/Al2O3 bimetallic nanocatalysts have been synthesized by using conventional and microwave impregnation methods. Structure and morphology of the samples were characterized using XRD, XPS, and TEM. XRD and XPS measurement have confirmed the presence of Ru and Sn in the samples. According to TEM results, the morphology of the catalyst strongly depends on the preparation route and stabilizing agent (i.e. PVP). The sample with PVP (polyvinylpyrrolidone) has better nanoparticles distribution over the support. A sample prepared by conventional method has an agglomeration of nanoparticles on the support. Catalytic activities of both samples were examined in the reduction reaction of pollutant, i.e. 4-nitrophenol. Catalytic examination showed that reaction rate of 4-nitrophenol reduction by using microwave-assisted sample has improved 3.5 times faster than conventional impregnation sample.

Ferrocene-functionalized graphene electrode for biosensing applications.

PubMed

Rabti, Amal; Mayorga-Martinez, Carmen C; Baptista-Pires, Luis; Raouafi, Noureddine; Merkoçi, Arben

2016-07-05

A novel ferrocene-functionalized reduced graphene oxide (rGO)-based electrode is proposed. It was fabricated by the drop casting of ferrocene-functionalized graphene onto polyester substrate as the working electrode integrated within screen-printed reference and counter electrodes. The ferrocene-functionalized rGO has been fully characterized using FTIR, XPS, contact angle measurements, SEM and TEM microscopy, and cyclic voltammetry. The XPS and EDX analysis showed the presence of Fe element related to the introduced ferrocene groups, which is confirmed by a clear CV signal at ca. 0.25 V vs. Ag/AgCl (0.1 KCl). Mediated redox catalysis of H2O2 and bio-functionalization with glucose oxidase for glucose detection were achieved by the bioelectrode providing a proof for potential biosensing applications. Copyright © 2016 Elsevier B.V. All rights reserved.

XPS analysis of activated carbon supported ionic liquids: Enhanced purity and reduced charging

NASA Astrophysics Data System (ADS)

Foelske-Schmitz, A.; Weingarth, D.; Kötz, R.

2011-12-01

Herein we report on XPS measurements on five different [EMIM] based ionic liquids (IL) prepared on activated carbon and aluminium supports. The anions were [TFSI], [BF4], [FAP], [B(CN)4] and [EtOSO3]. The results show that impurities such as O, Si or hydrocarbons were significantly reduced or no longer detected when preparation was performed on the high surface area carbon support. All core level spectra were fitted and for [EMIM][FAP], [EMIM][B(CN)4] and [EMIM][EtOSO3] de-convolution procedures of the C 1s lines are suggested. Comparison of the determined binding energies with published data strongly suggests that sample charging is irrelevant when preparation is performed on the activated carbon support. This observation is supposed to refer to the high capacitance of the high surface area carbon.

The application of thermodynamic and spectroscopic techniques to adhesion in the polyimide/Ti 6-4 and polyphenylquinoxaline/Ti 6-4 systems

NASA Technical Reports Server (NTRS)

Dias, S.; Wightman, J. P.

1984-01-01

The results of calorimetric measurements of Ti adherend surfaces are presented. The measurements were carried out after several chemical pretreatments and after fracture of several lap shear samples aged at high temperature. The exact composition of the Ti samples was Ti(6 percent Al-4 percent V). The adhesives used were polyimides and polyphenylquinoxalines (PPQ). Each chemical pretreatment was accompanied by a unique spectroscopic feature which was characterized by XPS, SEM, and specular reflectance infrared spectroscopy. The energetics of the interaction between primer solutions and the Ti adherend were evaluated by microcalorimetry. Changes in the structure of the surface oxide layer upon heating of the adherend were deduced from immersion temperatures of the PI and PPQ solutions. The XPS and SEM data are given is a table.

Probing the interaction of Rh, Co and bimetallic Rh-Co nanoparticles with the CeO2 support: catalytic materials for alternative energy generation.

PubMed

Varga, E; Pusztai, P; Óvári, L; Oszkó, A; Erdőhelyi, A; Papp, C; Steinrück, H-P; Kónya, Z; Kiss, J

2015-10-28

The interaction of CeO2-supported Rh, Co and bimetallic Rh-Co nanoparticles, which are active catalysts in hydrogen production via steam reforming of ethanol, a process related to renewable energy generation, was studied by X-ray diffraction (XRD), high resolution electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and low energy ion scattering (LEIS). Furthermore, diffuse reflectance infrared spectroscopy (DRIFTS) of adsorbed CO as a probe molecule was used to characterize the morphology of metal particles. At small loadings (0.1%), Rh is in a much dispersed state on ceria, while at higher contents (1-5%), Rh forms 2-8 nm particles. Between 473-673 K pronounced oxygen transfer from ceria to Rh is observed and at 773 K significant agglomeration of Rh occurs. On reduced ceria, XPS indicates a possible electron transfer from Rh to ceria. The formation of smaller ceria crystallites upon loading with Co was concluded from XRD and HRTEM; for 10% Co, the CeO2 particle size decreased from 27.6 to 10.7 nm. A strong dissolution of Co into ceria and a certain extent of encapsulation by ceria were deduced by XRD, XPS and LEIS. In the bimetallic system, the presence of Rh enhances the reduction of cobalt and ceria. During thermal treatments, reoxidation of Co occurs, and Rh agglomeration as well as oxygen migration from ceria to Rh are hindered in the presence of cobalt.

Passivation of InGaAs(001)-(2 × 4) by Self-Limiting Chemical Vapor Deposition of a Silicon Hydride Control Layer.

PubMed

Edmonds, Mary; Kent, Tyler; Chagarov, Evgueni; Sardashti, Kasra; Droopad, Ravi; Chang, Mei; Kachian, Jessica; Park, Jun Hong; Kummel, Andrew

2015-07-08

A saturated Si-Hx seed layer for gate oxide or contact conductor ALD has been deposited via two separate self-limiting and saturating CVD processes on InGaAs(001)-(2 × 4) at substrate temperatures of 250 and 350 °C. For the first self-limiting process, a single silicon precursor, Si3H8, was dosed at a substrate temperature of 250 °C, and XPS results show the deposited silicon hydride layer saturated at about 4 monolayers of silicon coverage with hydrogen termination. STS results show the surface Fermi level remains unpinned following the deposition of the saturated silicon hydride layer, indicating the InGaAs surface dangling bonds are electrically passivated by Si-Hx. For the second self-limiting process, Si2Cl6 was dosed at a substrate temperature of 350 °C, and XPS results show the deposited silicon chloride layer saturated at about 2.5 monolayers of silicon coverage with chlorine termination. Atomic hydrogen produced by a thermal gas cracker was subsequently dosed at 350 °C to remove the Si-Cl termination by replacing with Si-H termination as confirmed by XPS, and STS results confirm the saturated Si-Hx bilayer leaves the InGaAs(001)-(2 × 4) surface Fermi level unpinned. Density function theory modeling of silicon hydride surface passivation shows an Si-Hx monolayer can remove all the dangling bonds and leave a charge balanced surface on InGaAs.

Silver deposition on stainless steel container surfaces in contact with disinfectant silver aqueous solutions

NASA Astrophysics Data System (ADS)

Petala, M.; Tsiridis, V.; Mintsouli, I.; Pliatsikas, N.; Spanos, Th.; Rebeyre, P.; Darakas, E.; Patsalas, P.; Vourlias, G.; Kostoglou, M.; Sotiropoulos, S.; Karapantsios, Th.

2017-02-01

Silver is the preservative used on the Russian segment of the International Space Station (ISS) to prevent microbial proliferation within potable water supplies. Yet, in the frame of the European Automated Transfer Vehicle (ATV) missions to ISS, silver depletion from water has been detected during ground transportation of this water to launch site, thereby indicating a degradation of water quality. This study investigates the silver loss from water when in contact with stainless steel surfaces. Experiments are conducted with several types of stainless steel surfaces being exposed to water containing 10 or 0.5 mg/L silver ions. Results show that silver deposits on stainless steel surfaces even when a passivation layer protects the metallic surface. The highest protection to silver deposition is offered by acid passivated and electropolished SS 316L. SEM and XPS experiments were carried out at several locations of the sample area that was in contact with the Ag solution and found similar morphological (SEM) and compositional (sputter-etch XPS) results. The results reveal that silver deposits uniformly across the wetted surface to a thickness larger than 3 nm. Moreover, evidence is provided that silver deposits in its metallic form on all stainless steel surfaces, in line with a galvanic deposition mechanism. Combination of ICP-MS and XPS results suggests a mechanism for Ag deposition/reduction with simultaneous substrate oxidation resulting in oxide growth at the exposed stainless steel surface.

Toward an Improved Understanding of the Role of Soil Organic Matter in NOy Cycling through Investigation of Heterogeneous Reactions with NO2+

NASA Astrophysics Data System (ADS)

Engelhard, M.; Hansen, R. F.; Raff, J. D.

2017-12-01

Molecular level investigation of compositional changes due to heterogeneous reactions of nitrogen oxides (NOx, NOy) with soil organic matter (SOM) is important to develop a fundamental scientific understanding of the soil/atmosphere interface. In addition, interactions between NOx reservoir species and SOM play a more important role in NOx and NOy recycling than previously realized. Despite the importance of soil to the global terrestrial-atmospheric cycling of nitrogen, interactions of N2O5 with SOM are not well understood. Uncertainty in these processes is problematic because it means that NOy is not properly represented in the Earth-systems models used for prediction and regulation. The ultimate objective of this study is to investigate the production of NOy from the reaction of N2O5 with SOM and elucidate the mechanisms that return NOy back to the atmosphere, where NOy can contribute to aerosol and O3 formation. In the initial phase of this study, we reacted SOM standards with NO2+ (produced from concentrated HNO3), which is an intermediate in the heterogeneous reaction of N2O5 with SOM. We then characterized these reaction products using X-ray photoelectron spectroscopy (XPS). XPS was used to measure the nitrogen chemistry before and after reaction of SOM with NO2+. These results will be discussed along with the pros and cons using XPS to characterize SOM chemistry.

Experimental design and analysis of activators regenerated by electron transfer-atom transfer radical polymerization experimental conditions for grafting sodium styrene sulfonate from titanium substrates.

PubMed

Foster, Rami N; Johansson, Patrik K; Tom, Nicole R; Koelsch, Patrick; Castner, David G

2015-09-01

A 2 4 factorial design was used to optimize the activators regenerated by electron transfer-atom transfer radical polymerization (ARGET-ATRP) grafting of sodium styrene sulfonate (NaSS) films from trichlorosilane/10-undecen-1-yl 2-bromo-2-methylpropionate (ester ClSi) functionalized titanium substrates. The process variables explored were: (1) ATRP initiator surface functionalization reaction time; (2) grafting reaction time; (3) CuBr 2 concentration; and (4) reducing agent (vitamin C) concentration. All samples were characterized using x-ray photoelectron spectroscopy (XPS). Two statistical methods were used to analyze the results: (1) analysis of variance with [Formula: see text], using average [Formula: see text] XPS atomic percent as the response; and (2) principal component analysis using a peak list compiled from all the XPS composition results. Through this analysis combined with follow-up studies, the following conclusions are reached: (1) ATRP-initiator surface functionalization reaction times have no discernable effect on NaSS film quality; (2) minimum (≤24 h for this system) grafting reaction times should be used on titanium substrates since NaSS film quality decreased and variability increased with increasing reaction times; (3) minimum (≤0.5 mg cm -2 for this system) CuBr 2 concentrations should be used to graft thicker NaSS films; and (4) no deleterious effects were detected with increasing vitamin C concentration.

Towards nanometric resolution in multilayer depth profiling: a comparative study of RBS, SIMS, XPS and GDOES.

PubMed

Escobar Galindo, Ramón; Gago, Raul; Duday, David; Palacio, Carlos

2010-04-01

An increasing amount of effort is currently being directed towards the development of new functionalized nanostructured materials (i.e., multilayers and nanocomposites). Using an appropriate combination of composition and microstructure, it is possible to optimize and tailor the final properties of the material to its final application. The analytical characterization of these new complex nanostructures requires high-resolution analytical techniques that are able to provide information about surface and depth composition at the nanometric level. In this work, we comparatively review the state of the art in four different depth-profiling characterization techniques: Rutherford backscattering spectroscopy (RBS), secondary ion mass spectrometry (SIMS), X-ray photoelectron spectroscopy (XPS) and glow discharge optical emission spectroscopy (GDOES). In addition, we predict future trends in these techniques regarding improvements in their depth resolutions. Subnanometric resolution can now be achieved in RBS using magnetic spectrometry systems. In SIMS, the use of rotating sample holders and oxygen flooding during analysis as well as the optimization of floating low-energy ion guns to lower the impact energy of the primary ions improves the depth resolution of the technique. Angle-resolved XPS provides a very powerful and nondestructive technique for obtaining depth profiling and chemical information within the range of a few monolayers. Finally, the application of mathematical tools (deconvolution algorithms and a depth-profiling model), pulsed sources and surface plasma cleaning procedures is expected to greatly improve GDOES depth resolution.

Redirected charge transport arising from diazonium grafting of carbon coated LiFePO4.

PubMed

Madec, L; Seid, K A; Badot, J-C; Humbert, B; Moreau, P; Dubrunfaut, O; Lestriez, B; Guyomard, D; Gaubicher, J

2014-11-07

The morphological and the electrical properties of carbon coated LiFePO4 (LFPC) active material functionalized by 4-ethynylbenzene tetrafluoroboratediazonium salt were investigated. For this purpose, FTIR, Raman, XPS, High Resolution Transmission Electron Microscopy (HRTEM) and Broadband Dielectric Spectroscopy (BDS) were considered. Electronic conductivities of LFPC samples at room temperature were found to decrease in a large frequency range upon simple immersion in polar solvents and to decrease further upon functionalization. Due to their high dipole moment, strongly physisorbed molecules detected by XPS likely add barriers to electron hopping. Significant alteration of the carbon coating conductivity was only observed, however, upon functionalization. This effect is most presumably associated with an increase in the sp(3) content determined by Raman spectroscopy, which is a strong indication of the formation of a covalent bond between the organic layer and the carbon coating. In this case, the electron flux appears to be redirected and relayed by short-range (intra chain) and long-range (inter chain) electron transport through molecular oligomers anchored at the LFPC surface. The latter are controlled by tunnelling and slightly activated hopping, which enable higher conductivity at low temperature (T < 250 K). Alteration of the electron transport within the carbon coating also allows detection of a relaxation phenomenon that corresponds to small polaron hopping in bulk LiFePO4. XPS and HRTEM images allow a clear correlation of these findings with the island type oligomeric structure of grafted molecules.

Long-Term Stability of Photovoltaic Hybrid Perovskites achieved by Graphene Passivation via a Water- and Polymer-Free Graphene Transfer Method

NASA Astrophysics Data System (ADS)

Tseng, W.-S.; Jao, M.-H.; Hsu, C.-C.; Wu, C.-I.; Yeh, N.-C.

Organic-inorganic hybrid perovskites such as CH3NH3PbX3 (X = I, Br) have been intensively studied in recent years because of their rapidly improving photovoltaic power conversion efficiency. However, severe instability of these materials in ambient environment has been a primary challenge for practical applications. To address this issue, we employ high-quality PECVD-grown graphene to passivate the hybrid perovskites. In contrast to existing processes for transferring graphene from the growth substrates to other surfaces that involve either polymer or water, which are incompatible with photovoltaic applications of these water-sensitive hybrid perovskites, we report here a new water- and polymer-free graphene transferring method. Studies of the Raman, x-ray and ultraviolet photoemission spectroscopy (XPS and UPS) demonstrated excellent quality of monolayer PECVD-grown graphene samples after their transfer onto different substrates with the water- and polymer-free processing method. In particular, graphene was successfully transferred onto the surface of CH3NH3PbI3 thin films with sample quality intact. Moreover, XPS and UPS studies indicated that even after 3 months, the fully graphene-covered perovskite films remained spectroscopically invariant, which was in sharp contrast to the drastic changes, after merely one week, in both the XPS and UPS of a control CH3NH3PbI3 sample without graphene protection. Beckman Inst. in Caltech. Dragon Gate Program in Taiwan.

Biocatalyzed approach for the surface functionalization of poly(L-lactic acid) films using hydrolytic enzymes.

PubMed

Pellis, Alessandro; Acero, Enrique Herrero; Weber, Hansjoerg; Obersriebnig, Michael; Breinbauer, Rolf; Srebotnik, Ewald; Guebitz, Georg M

2015-09-01

Poly(lactic acid) as a biodegradable thermoplastic polyester has received increasing attention. This renewable polyester has found applications in a wide range of products such as food packaging, textiles and biomedical devices. Its major drawbacks are poor toughness, slow degradation rate and lack of reactive side-chain groups. An enzymatic process for the grafting of carboxylic acids onto the surface of poly(L-lactic acid) (PLLA) films was developed using Candida antarctica lipase B as a catalyst. Enzymatic hydrolysis of the PLLA film using Humicola insolens cutinase in order to increase the number of hydroxyl and carboxylic groups on the outer polymer chains for grafting was also assessed and showed a change of water contact angle from 74.6 to 33.1° while the roughness and waviness were an order of magnitude higher in comparison to the blank. Surface functionalization was demonstrated using two different techniques, (14) C-radiochemical analysis and X-ray photoelectron spectroscopy (XPS) using (14) C-butyric acid sodium salt and 4,4,4-trifluorobutyric acid as model molecules, respectively. XPS analysis showed that 4,4,4-trifluorobutyric acid was enzymatically coupled based on an increase of the fluor content from 0.19 to 0.40%. The presented (14) C-radiochemical analyses are consistent with the XPS data indicating the potential of enzymatic functionalization in different reaction conditions. Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Colloidal diatomite, radionickel, and humic substance interaction: a combined batch, XPS, and EXAFS investigation.

PubMed

Sheng, Guodong; Shen, Runpu; Dong, Huaping; Li, Yimin

2013-06-01

This work determined the influence of humic acid (HA) and fulvic acid (FA) on the interaction mechanism and microstructure of Ni(II) onto diatomite by using batch experiments, X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS) methods. Macroscopic and spectroscopic experiments have been combined to see the evolution of the interaction mechanism and microstructure of Ni(II) in the presence of HA/FA as compared with that in the absence of HA/FA. The results indicated that the interaction of Ni(II) with diatomite presents the expected solution pH edge at 7.0, which is modified by addition of HA/FA. In the presence of HA/FA, the interaction of Ni(II) with diatomite increased below solution pH 7.0, while Ni(II) interaction decreased above solution pH 7.0. XPS analysis suggested that the enrichment of Ni(II) onto diatomite may be due to the formation of (≡SO)2Ni. EXAFS results showed that binary surface complexes and ternary surface complexes of Ni(II) can be simultaneously formed in the presence of HA/FA, whereas only binary surface complexes of Ni(II) are formed in the absence of HA/FA, which contribute to the enhanced Ni(II) uptake at low pH values. The results observed in this work are important for the evaluation of Ni(II) and related radionuclide physicochemical behavior in the natural soil and water environment.

XPS studies of MgO based magnetic tunnel junction structures

NASA Astrophysics Data System (ADS)

Read, John; Mather, Phil; Tan, Eileen; Buhrman, Robert

2006-03-01

The very high tunneling magnetoresistance (TMR) obtained in MgO magnetic tunnel junctions (MTJ)^(1,2) motivates the investigation of the electronic properties of the MgO barrier layer and the study of the ferromagnetic metal - MgO interface chemistry. Such large TMR values are predicted by theory due to the high degree of order apparent in the barrier and electrode materials. However, as grown ultra-thin MgO films generally contain defects that can influence electron transport properties through the creation of low energy states within the bulk MgO band-gap. We will report the results of x-ray photoelectron spectroscopy (XPS) studies of (001) textured ultra-thin MgO layers that are prepared by RF magnetron sputtering and electron beam evaporation on ordered ferromagnetic electrodes and in ordered MTJ structures with and without post growth vacuum annealing. XPS spectra for both MgO deposition techniques clearly indicate a surface oxygen species that is likely bound by defects in the oxide^(3) in half-formed junctions and improvements in MgO quality after counter electrode deposition. We will discuss our results regarding the chemical properties of the oxide and its interfaces directed towards possibly providing guidance to engineer improved MgO MTJ devices. [1] S.S.P. Parkin et. al., Nature Materials, 3, 862 (2004). [2] S. Yuasa et. al., Nature Materials, 3, 868 (2004). [3] E. Tan et. al. , Phys. Rev. B. , 71, 161401 (2005).

Atomic layer deposited TaCy metal gates: Impact on microstructure, electrical properties, and work function on HfO2 high-k dielectrics

NASA Astrophysics Data System (ADS)

Triyoso, D. H.; Gregory, R.; Schaeffer, J. K.; Werho, D.; Li, D.; Marcus, S.; Wilk, G. D.

2007-11-01

TaCy has been reported to have the appropriate work function for negative metal-oxide semiconductor metal in high-k metal-oxide field-effect transistors. As device size continues to shrink, a conformal deposition for metal gate electrodes is needed. In this work, we report on the development and characterization of a novel TaCy process by atomic layer deposition (ALD). Detailed physical properties of TaCy films are studied using ellipsometry, a four-point probe, Rutherford backscattering spectrometry (RBS), x-ray photoelectron spectroscopy (XPS), and x-ray diffraction (XRD). RBS and XPS analysis indicate that TaCy films are near-stoichiometric, nitrogen free, and have low oxygen impurities. Powder XRD spectra showed that ALD films have a cubic microstructure. XPS carbon bonding studies revealed that little or no glassy carbon is present in the bulk of the film. Excellent electrical properties are obtained using ALD TaCy as a metal gate electrode. Well-behaved capacitance-voltage characteristics with ALD HfO2 gate dielectrics are demonstrated for TaCy thicknesses of 50, 100, and 250 Å. A low fixed charge (˜2-4×10-11 cm-2) is observed for all ALD HfO2/ALD TaCy devices. Increasing the thickness of ALD TaCy results in a decrease in work function (4.77 to 4.54 eV) and lower threshold voltages.

Reactivity of formic acid (HCOOD and DCOOH) at uranium and UO 2.0 surfaces

NASA Astrophysics Data System (ADS)

Manner, William L.; Lloyd, Jane A.; Paffett, Mark T.

1999-10-01

Interactions of DCOOH and HCOOD with uranium and UO 2.0 surfaces have been examined using surface-specific techniques of thermal desorption mass spectroscopy (TDMS), X-ray photoelectron spectroscopy (XPS), and static secondary ion mass spectroscopy (SSIMS). On the clean uranium surface, formate is the predominant product following formic acid adsorption at 100 K. A wide range of products is observed after annealing to 200 K, including formate, hydroxyl, O ads, and H ads (D ads) groups. Adsorbed formate decomposes by 300 K increasing the concentration of the remaining surface products. Surface-adsorbed carbon following TDMS measurements remains as the carbide, as indicated from XPS and SSIMS measurements. The only gaseous species created in high yields from the clean surface upon annealing are H 2, HD, and D 2. On the oxide surface (UO 2.0), adsorbed formate groups are more stable toward dissociation in comparison with the clean uranium surface. Between 100 and 300 K the predominant species on the UO 2.0 surface are surface formate and hydroxyl groups. Hydroxyl groups react between 300 and 350 K to release water from the surface. Adsorbed formate groups decompose between 400 and 500 K to release CO and H 2CO (D 2CO) groups from the oxide surface. Carbon was not detected on the oxide surface by XPS or SSIMS after annealing to 500 K, indicating that all carbon-containing species either desorb in the form of CO-containing products or migrate into the surface.

Electronic structure and phase separation of superconducting and nonsuperconducting KxFe2-ySe2 revealed by x-ray photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Oiwake, M.; Ootsuki, D.; Noji, T.; Hatakeda, T.; Koike, Y.; Horio, M.; Fujimori, A.; Saini, N. L.; Mizokawa, T.

2013-12-01

We have investigated the electronic structure of superconducting (SC) and nonsuperconducting (non-SC) KxFe2-ySe2 using x-ray photoemission spectroscopy (XPS). The spectral shape of the Fe 2p XPS is found to depend on the amount of Fe vacancies. The Fe 2p3/2 peak of the SC and non-SC Fe-rich samples is accompanied by a shoulder structure on the lower binding energy side, which can be attributed to the metallic phase embedded in the Fe2+ insulating phase. The absence of the shoulder structure in the non-SC Fe-poor sample allows us to analyze the Fe 2p spectra using a FeSe4 cluster model. The Fe 3d-Se 4p charge-transfer energy of the Fe2+ insulating phase is found to be ˜2.3 eV which is smaller than the Fe 3d-Fe 3d Coulomb interaction of ˜3.5 eV. This indicates that the Fe2+ insulating state is the charge-transfer type in the Zaanen-Sawatzky-Allen scheme. We also find a substantial change in the valence-band XPS as a function of Fe content and temperature. The metallic state at the Fermi level is seen in the SC and non-SC Fe-rich samples and tends to be enhanced with cooling in the SC sample.

Thickness measurement of a thin hetero-oxide film with an interfacial oxide layer by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Kim, Kyung Joong; Lee, Seung Mi; Jang, Jong Shik; Moret, Mona

2012-02-01

The general equation Tove = L cos θ ln(Rexp/R0 + 1) for the thickness measurement of thin oxide films by X-ray photoelectron spectroscopy (XPS) was applied to a HfO2/SiO2/Si(1 0 0) as a thin hetero-oxide film system with an interfacial oxide layer. The contribution of the thick interfacial SiO2 layer to the thickness of the HfO2 overlayer was counterbalanced by multiplying the ratio between the intensity of Si4+ from a thick SiO2 film and that of Si0 from a Si(1 0 0) substrate to the intensity of Si4+ from the HfO2/SiO2/Si(1 0 0) film. With this approximation, the thickness levels of the HfO2 overlayers showed a small standard deviation of 0.03 nm in a series of HfO2 (2 nm)/SiO2 (2-6 nm)/Si(1 0 0) films. Mutual calibration with XPS and transmission electron microscopy (TEM) was used to verify the thickness of HfO2 overlayers in a series of HfO2 (1-4 nm)/SiO2 (3 nm)/Si(1 0 0) films. From the linear relation between the thickness values derived from XPS and TEM, the effective attenuation length of the photoelectrons and the thickness of the HfO2 overlayer could be determined.

X-ray Photoelectron Spectroscopy Study of Argon-Plasma-Treated Fluoropolymers

NASA Technical Reports Server (NTRS)

Golub, Morton A.; Lopata, Eugene S.; Finney, Lorie S.

1994-01-01

Films of poly(tetrafluoroethylene) (PTFE) and of a tetrafluoroethylene-perfluoroalkyl vinyl ether (approximately 49:1) copolymer (PFA) were exposed to a radio-frequency argon plasma and then examined by X-ray photoelectron spectroscopy (XPS). The use of fluoropolymer films nearly free of surface hydrocarbon contamination as well as the use of a monochromatized X-ray source for XPS removed two factors contributing to conflicting reports on the effect of exposure time on the fluorine-to-carbon (F/C) and oxygen-to-carbon (O/C) ratios for several Ar-plasma-treated fluoropolymers. Contrary to literature indications, a common pattern was found for PTFE and PFA: a moderate decrease in F/C ratio (from 1.99 to 1.40, and from 1.97 to 1.57, respectively), together with a moderate increase in O/C ratio (from negligible to about 0.10, and from 0.012 to about O.10, respectively) at very short exposures, after which the F/C ratios remained essentially constant on prolonged exposures, while the O/C ratios for PTFE and PFA leveled off at 0.11 and 0.15, respectively. The XPS C(sub 1s), spectra for these polymers exposed to the Ar plasma for 20 min were similar and presented, besides a prominent peak at 292.0 eV (CF2,) and a minor peak at 294.0 or 294.1 eV (CF3), a composite band of four curve-resolved peaks (approximately 285-290 eV) representing various CH, CC, CO, CN, and CF functionalities.

MBE growth of few-layer 2H-MoTe2 on 3D substrates

NASA Astrophysics Data System (ADS)

Vishwanath, Suresh; Sundar, Aditya; Liu, Xinyu; Azcatl, Angelica; Lochocki, Edward; Woll, Arthur R.; Rouvimov, Sergei; Hwang, Wan Sik; Lu, Ning; Peng, Xin; Lien, Huai-Hsun; Weisenberger, John; McDonnell, Stephen; Kim, Moon J.; Dobrowolska, Margaret; Furdyna, Jacek K.; Shen, Kyle; Wallace, Robert M.; Jena, Debdeep; Xing, Huili Grace

2018-01-01

MoTe2 is the least explored material in the Molybdenum-chalcogen family. Molecular beam epitaxy (MBE) provides a unique opportunity to tackle the small electronegativity difference between Mo and Te while growing layer by layer away from thermodynamic equilibrium. We find that for a few-layer MoTe2 grown at a moderate rate of ∼6 min per monolayer, a narrow window in temperature (above Te cell temperature) and Te:Mo ratio exists, where we can obtain pure phase 2H-MoTe2. This is confirmed using reflection high-energy electron diffraction (RHEED), Raman spectroscopy and X-ray photoemission spectroscopy (XPS). For growth on CaF2, Grazing incidence X-ray diffraction (GI-XRD) reveals a grain size of ∼90 Å and presence of twinned grains. In this work, we hypothesis the presence of excess Te incorporation in MBE grown few layer 2H-MoTe2. For film on CaF2, it is based on >2 Te:Mo stoichiometry using XPS as well as 'a' and 'c' lattice spacing greater than bulk 2H-MoTe2. On GaAs, its based on observations of Te crystallite formation on film surface, 2 × 2 superstructure observed in RHEED and low energy electron diffraction, larger than bulk c-lattice spacing as well as the lack of electrical conductivity modulation by field effect. Finally, thermal stability and air sensitivity of MBE 2H-MoTe2 is investigated by temperature dependent XRD and XPS, respectively.

Electron Inelastic-Mean-Free-Path Database

National Institute of Standards and Technology Data Gateway

SRD 71 NIST Electron Inelastic-Mean-Free-Path Database (PC database, no charge)   This database provides values of electron inelastic mean free paths (IMFPs) for use in quantitative surface analyses by AES and XPS.

Experimental study of the effect of local atomic ordering on the energy band gap of melt grown InGaAsN alloys

NASA Astrophysics Data System (ADS)

Milanova, M.; Donchev, V.; Kostov, K. L.; Alonso-Álvarez, D.; Valcheva, E.; Kirilov, K.; Asenova, I.; Ivanov, I. G.; Georgiev, S.; Ekins-Daukes, N.

2017-08-01

We present a study of melt grown dilute nitride InGaAsN layers by x-ray photoelectron spectroscopy (XPS), Raman and photoluminescence (PL) spectroscopy. The purpose of the study is to determine the degree of atomic ordering in the quaternary alloy during the epitaxial growth at near thermodynamic equilibrium conditions and its influence on band gap formation. Despite the low In concentration (˜3%) the XPS data show a strong preference toward In-N bonding configuration in the InGaAsN samples. Raman spectra reveal that most of the N atoms are bonded to In instead of Ga atoms and the formation of N-centred In3Ga1 clusters. PL measurements reveal smaller optical band gap bowing as compared to the theoretical predictions for random alloy and localised tail states near the conduction band minimum.

Energy level alignment at the methylammonium lead iodide/copper phthalocyanine interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Shi; Goh, Teck Wee; Sum, Tze Chien, E-mail: Alfred@ntu.edu.sg, E-mail: Tzechien@ntu.edu.sg

2014-08-01

The energy level alignment at the CH{sub 3}NH{sub 3}PbI{sub 3}/copper phthalocyanine (CuPc) interface is investigated by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). XPS reveal a 0.3 eV downward band bending in the CuPc film. UPS validate this finding and further reveal negligible interfacial dipole formation – verifying the viability of vacuum level alignment. The highest occupied molecular orbital of CuPc is found to be closer to the Fermi level than the valance band maximum of CH{sub 3}NH{sub 3}PbI{sub 3}, facilitating hole transfer from CH{sub 3}NH{sub 3}PbI{sub 3} to CuPc. However, subsequent hole extraction from CuPc may bemore » impeded by the downward band bending in the CuPc layer.« less

Hexadecylamine Adsorption at the Iron Oxide–Oil Interface

PubMed Central

2013-01-01

The adsorption behavior of a model additive, hexadecylamine, onto an iron surface from hexadecane oil has been characterized using polarized neutron reflectometry, sum-frequency generation spectroscopy, solution depletion isotherm, and X-ray photoelectron spectroscopy (XPS). The amine showed a strong affinity for the metal surface, forming a dense monolayer at relatively low concentrations; a layer thickness of 16 (±3) Å at low concentrations, increasing to 20 (±3) Å at greater amine concentrations, was determined from the neutron data. These thicknesses suggest that the molecules in the layer are tilted. Adsorption was also indicated by sum-frequency generation spectroscopy and XPS, the latter indicating that the most dominant amine–surface interaction was via electron donation from the nitrogen lone pair to the positively charged iron ions. Sum-frequency generation spectroscopy was used to determine the alkyl chain conformation order and orientation on the surface. PMID:24106786

Hierarchically porous carbon/polyaniline hybrid for use in supercapacitors.

PubMed

Joo, Min Jae; Yun, Young Soo; Jin, Hyoung-Joon

2014-12-01

A hierarchically porous carbon (HPC)/polyaniline (PANI) hybrid electrode was prepared by the polymerization of PANI on the surface of the HPC via rapid-mixing polymerization. The surface morphologies and chemical composition of the HPC/PANI hybrid electrode were characterized using transmission electron microscopy and X-ray photoelectron spectroscopy (XPS), respectively. The surface morphologies and XPS results for the HPC, PANI and HPC/PANI hybrids indicate that PANI is coated on the surface of HPC in the HPC/PANI hybrids which have two different nitrogen groups as a benzenoid amine (-NH-) peak and positively charged nitrogen (N+) peak. The electrochemical performances of the HPC/PANI hybrids were analyzed by performing cyclic voltammetry and galvanostatic charge-discharge tests. The HPC/PANI hybrids showed a better specific capacitance (222 F/g) than HPC (111 F/g) because of effect of pseudocapacitor behavior. In addition, good cycle stabilities were maintained over 1000 cycles.

Observing Graphene Grow: Catalyst–Graphene Interactions during Scalable Graphene Growth on Polycrystalline Copper

PubMed Central

2013-01-01

Complementary in situ X-ray photoelectron spectroscopy (XPS), X-ray diffractometry, and environmental scanning electron microscopy are used to fingerprint the entire graphene chemical vapor deposition process on technologically important polycrystalline Cu catalysts to address the current lack of understanding of the underlying fundamental growth mechanisms and catalyst interactions. Graphene forms directly on metallic Cu during the high-temperature hydrocarbon exposure, whereby an upshift in the binding energies of the corresponding C1s XPS core level signatures is indicative of coupling between the Cu catalyst and the growing graphene. Minor carbon uptake into Cu can under certain conditions manifest itself as carbon precipitation upon cooling. Postgrowth, ambient air exposure even at room temperature decouples the graphene from Cu by (reversible) oxygen intercalation. The importance of these dynamic interactions is discussed for graphene growth, processing, and device integration. PMID:24041311

Extraction of agar from Gelidium sesquipedale (Rhodopyta) and surface characterization of agar based films.

PubMed

Guerrero, P; Etxabide, A; Leceta, I; Peñalba, M; de la Caba, K

2014-01-01

The chemical structure of the agar obtained from Gelidium sesquipedale (Rhodophyta) has been determined by (13)C nuclear magnetic resonance ((13)C NMR) and Fourier transform infrared spectroscopy (FTIR). Agar (AG) films with different amounts of soy protein isolate (SPI) were prepared using a thermo-moulding method, and transparent and hydrophobic films were obtained and characterized. FTIR analysis provided a detailed description of the binding groups present in the films, such as carboxylic, hydroxyl and sulfonate groups, while the surface composition was examined using X-ray photoelectron spectroscopy (XPS). The changes observed by FTIR and XPS spectra suggested interactions between functional groups of agar and SPI. This is a novel approach to the characterization of agar-based films and provides knowledge about the compatibility of agar and soy protein for further investigation of the functional properties of biodegradable films based on these biopolymers. Copyright © 2013 Elsevier Ltd. All rights reserved.

Investigation of HCl-based surface treatment for GaN devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Okada, Hiroshi, E-mail: okada@ee.tut.ac.jp; Department of Electrical and Electronic Information Engineering, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi 441-8580; Shinohara, Masatohi

2016-02-01

Surface treatments of GaN in HCl-based solutions are studied by X-ray photoelectron spectroscopy (XPS) and electrical characterization of fabricated GaN surfaces. A dilute-HCl treatment (HCl:H{sub 2}O=1:1) at room temperature and a boiled-HCl treatment (undiluted HCl) at 108°C are made on high-temperature annealed n-GaN. From the XPS study, removal of surface oxide by the dilute-HCl treatment was found, and more thoroughly oxide-removal was confirmed in the boiled-HCl treatment. Effect of the surface treatment on electrical characteristics on AlGaN/GaN transistor is also studied by applying treatment processes prior to the surface SiN deposition. Increase of drain current is found in boiled-HCl treatedmore » samples. The results suggest that the boiled-HCl treatment is effective for GaN device fabrication.« less

Analysis of electronic structure of amorphous InGaZnO/SiO{sub 2} interface by angle-resolved X-ray photoelectron spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ueoka, Y.; Ishikawa, Y.; Maejima, N.

2013-10-28

The electronic structures of amorphous indium gallium zinc oxide (a-IGZO) on a SiO{sub 2} layers before and after annealing were observed by constant final state X-ray photoelectron spectroscopy (CFS-XPS) and X-ray adsorption near-edge structure spectroscopy (XANES). From the results of angle-resolved CFS-XPS, the change in the electronic state was clearly observed in the a-IGZO bulk rather than in the a-IGZO/SiO{sub 2} interface. This suggests that the electronic structures of the a-IGZO bulk strongly affected the thin-film transistor characteristics. The results of XANES indicated an increase in the number of tail states upon atmospheric annealing (AT). We consider that the increasemore » in the number of tail states decreased the channel mobility of AT samples.« less

Characterization of BN rich layer on ammonia treated Nextel{trademark}312 fibers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khasgiwale, N.R.; Butler, E.P.; Tsakalakos, L.

A BN rich layer grown on Nextel{trademark}312 fibers by appropriate ammonia treatments was evaluated using various complimentary techniques including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM)/Parallel Electron Energy Loss Spectroscopy (PEELS in TEM). Three different ammonia treatments were studied. Ammonia treatment resulted in crystallization of the Nextel{trademark}312 fiber. The BN rich surface layer formed due to ammonia treatment was clearly detected in XPS and PEELS both before and after oxidation. The layer thickness was estimated to be between 5--10 nm. The layer was stable after oxidation treatment at 600 C formore » 100 hours. High resolution TEM observations of the fiber surface revealed a variable BN rich layer thickness. Patches of turbostratic BN were observed under certain conditions, however mostly the layer appeared to be amorphous.« less

VO2 Thermochromic Films on Quartz Glass Substrate Grown by RF-Plasma-Assisted Oxide Molecular Beam Epitaxy

PubMed Central

Zhang, Dong; Sun, Hong-Jun; Wang, Min-Huan; Miao, Li-Hua; Liu, Hong-Zhu; Zhang, Yu-Zhi; Bian, Ji-Ming

2017-01-01

Vanadium dioxide (VO2) thermochromic thin films with various thicknesses were grown on quartz glass substrates by radio frequency (RF)-plasma assisted oxide molecular beam epitaxy (O-MBE). The crystal structure, morphology and chemical stoichiometry were investigated systemically by X-ray diffraction (XRD), atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) analyses. An excellent reversible metal-to-insulator transition (MIT) characteristics accompanied by an abrupt change in both electrical resistivity and optical infrared (IR) transmittance was observed from the optimized sample. Remarkably, the transition temperature (TMIT) deduced from the resistivity-temperature curve was reasonably consistent with that obtained from the temperature-dependent IR transmittance. Based on Raman measurement and XPS analyses, the observations were interpreted in terms of residual stresses and chemical stoichiometry. This achievement will be of great benefit for practical application of VO2-based smart windows. PMID:28772673

Depth Profiling Analysis of Aluminum Oxidation During Film Deposition in a Conventional High Vacuum System

NASA Technical Reports Server (NTRS)

Kim, Jongmin; Weimer, Jeffrey J.; Zukic, Muamer; Torr, Douglas G.

1994-01-01

The oxidation of aluminum thin films deposited in a conventional high vacuum chamber has been investigated using x-ray photoelectron spectroscopy (XPS) and depth profiling. The state of the Al layer was preserved by coating it with a protective MgF2 layer in the deposition chamber. Oxygen concentrations in the film layers were determined as a function of sputter time (depth into the film). The results show that an oxidized layer is formed at the start of Al deposition and that a less extensively oxidized Al layer is deposited if the deposition rate is fast. The top surface of the Al layer oxidizes very quickly. This top oxidized layer may be thicker than has been previously reported by optical methods. Maximum oxygen concentrations measured by XPS at each Al interface are related to pressure to rate ratios determined during the Al layer deposition.

Effect of nitrogen plasma afterglow on the surface charge effect resulted during XPS surface analysis of amorphous carbon nitride thin films

NASA Astrophysics Data System (ADS)

Kayed, Kamal

2018-06-01

The aim of this paper is to investigate the relationship between the micro structure and the surface charge effect resulted during XPS surface analysis of amorphous carbon nitride thin films prepared by laser ablation method. The study results show that the charge effect coefficient (E) is not just a correction factor. We found that the changes in this coefficient value due to incorporation of nitrogen atoms into the carbon network are related to the spatial configurations of the sp2 bonded carbon atoms, order degree and sp2 clusters size. In addition, results show that the curve E vs. C(sp3)-N is a characteristic curve of the micro structure. This means that using this curve makes it easy to sorting the samples according to the micro structure (hexagonal rings or chains).

Model systems in heterogeneous catalysis: towards the design and understanding of structure and electronic properties.

PubMed

Pan, Q; Li, L; Shaikhutdinov, S; Fujimori, Y; Hollerer, M; Sterrer, M; Freund, H-J

2018-05-29

We discuss in this paper two case studies related to nano-particle catalyst systems. One concerns a model system for the Cr/SiO2 Phillips catalyst for ethylene polymerization and here we present XPS data to complement the previously published TPD, IRAS and reactivity studies to elucidate the electronic structure of the system in some detail. The second case study provides additional information on Au nano-particles supported on ultrathin MgO(100)/Ag(100) films where we had observed a specific activity of the particle's rim at the metal-oxide interface with respect to CO2 activation and oxalate formation, obviously connected to electron transfer through the MgO film from the metal substrate underneath. Here we present XPS and Auger data, which allows detailed analysis of the observed chemical shifts. This analysis corroborates previous findings deduced via STM.

The relationship between the surface composition and electrical properties of corrosion films formed on carbon steel in alkaline sour medium: an XPS and EIS study.

PubMed

Galicia, Policarpo; Batina, Nikola; González, Ignacio

2006-07-27

This work studies the evolution of 1018 carbon steel surfaces during 3-15 day immersion in alkaline sour medium 0.1 M (NH4)2S and 10 ppm CN(-) as (NaCN). During this period of time, surfaces were jointly characterized by electrochemical techniques in situ (electrochemical impedance spectroscopy, EIS) and spectroscopic techniques ex situ (X-ray photoelectron spectroscopy, XPS). The results obtained by these techniques allowed for a description of electrical and chemical properties of the films of corrosion products formed at the 1018 steel surface. There is an interconversion cycle of chemical species that form films of corrosion products whose conversion reactions favor two different types of diffusions inside the films: a chemical diffusion of iron cations and a typical diffusion of atomic hydrogen. These phenomena jointly control the passivity of the interface attacked by the corrosive medium.

X-ray photoelectron spectroscopic study of the interaction of xanthate with coal pyrite and mineral pyrite surfaces

NASA Astrophysics Data System (ADS)

Khan, S. U. M.; Baltrus, J. P.; Lai, R. W.; Richardson, A. G.

1991-06-01

Coal pyrite and mineral pyrite surfaces were examined by X-ray photoelectron spectroscopy (XPS) before and after treatment in acidic and basic solutions of sodium ethyl xanthate (NaEtX). XPS showed that the degree of oxidation of coal and mineral pyrite surfaces increased when these pyrites were conditioned in basic solutions. However, conditioning in acidic solutions led to partial removal of surface oxidation from the pyrites. Addition of NaEtX to the acidic and basic solutions enhanced the removal of oxidation from pyrite surfaces. Pretreatment with sulfur dioxide further enhanced the removal of surface oxidation in the presence of NaEtX. Surface oxidation was typically less on mineral pyrite than coal pyrite surfaces following identical treatments. The flotation recoveries of the pyrites in the presence of NaEtX are greatest for the pyrites with the least amount of surface oxidation.

Technology Solutions for New and Existing Homes Case Study: Optimized Slab-on-Grade Foundation Insulation Retrofits

DOE Office of Scientific and Technical Information (OSTI.GOV)

T. Schirber; Goldberg, L.; Mosiman, G.

A more accurate assessment of SOG foundation insulation energy savings than traditionally possible is now feasible. This has been enabled by advances in whole building energy simulation with 3-dimensional foundation modelling integration at each time step together with an experimental measurement of the site energy savings of SOG foundation insulation. Ten SOG insulation strategies were evaluated on a test building to identify an optimum retrofit insulation strategy in a zone 6 climate (Minneapolis, MN). The optimum insulation strategy in terms of energy savings and cost effectiveness consisted of two components: (a) R-20 XPS insulation above grade, and, (b) R-20 insulationmore » at grade (comprising an outer layer of R-10 insulation and an interior layer of R-12 poured polyurethane insulation) tapering to R-10 XPS insulation at half the below-grade wall height (the lower half of the stem wall was uninsulated).« less

High-Performance Slab-on-Grade Foundation Insulation Retrofits

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goldberg, Louise F.; Mosiman, Garrett E.

A more accurate assessment of slab-on-grade foundation insulation energy savings than traditionally possible is now feasible. This has been enabled by advances in whole building energy simulation with 3-dimensional foundation modelling integration at each time step together with an experimental measurement of the site energy savings of SOG foundation insulation. Ten SOG insulation strategies were evaluated on a test building to identify an optimum retrofit insulation strategy in a zone 6 climate (Minneapolis, MN). The optimum insulation strategy in terms of energy savings and cost effectiveness consisted of two components: (a) R-20 XPS insulation above grade, and, (b) R-20 insulationmore » at grade (comprising an outer layer of R-10 insulation and an interior layer of R-12 poured polyurethane insulation) tapering to R-10 XPS insulation at half the below-grade wall height (the lower half of the stem wall was uninsulated).« less

The origin of the residual conductivity of GaN films on ferroelectric materials

NASA Astrophysics Data System (ADS)

Lee, Kyoung-Keun; Cai, Zhuhua; Ziemer, Katherine; Doolittle, William Alan

2009-08-01

In this paper, the origin of the conductivity of GaN films grown on ferroelectric materials was investigated using XPS, AES, and XRD analysis tools. Depth profiles confirmed the existence of impurities in the GaN film originating from the substrates. Bonding energy analysis from XPS and AES verified that oxygen impurities from the substrates were the dominant origin of the conductivity of the GaN film. Furthermore, Ga-rich GaN films have a greater chance of enhancing diffusion of lithium oxide from the substrates, resulting in more substrate phase separation and a wider inter-mixed region confirmed by XRD. Therefore, the direct GaN film growth on ferroelectric materials causes impurity diffusion from the substrates, resulting in highly conductive GaN films. Future work needs to develop non-conductive buffer layers for impurity suppression in order to obtain highly resistive GaN films.

Characterization and human gingival fibroblasts biocompatibility of hydroxyapatite/PMMA nanocomposites for provisional dental implant restoration

NASA Astrophysics Data System (ADS)

Zhang, Jingchao; Liao, Juan; Mo, Anchun; Li, Yubao; Li, Jidong; Wang, Xuejiang

2008-11-01

The aim of this study was to determine nHA/PMMA composites (H/P) in an optimal ratio with improved cytocompatibility as well as valid physical properties for provisional dental implant restoration. 20 wt.%, 30 wt.%, 40 wt.% and 50 wt.% H/P were developed and characterized using XPS, bending strength test and SEM. Human gingival fibroblasts cultured in extracts or directly on sample discs were investigated by fluorescent staining and MTT assay. Chemical integration in nHA/PMMA interface was indicated by XPS. Typical fusiform cells with adhesion spots were detected on H/P discs. MTT results also indicated higher cell viability in 30 wt.% and 40 wt.% H/P discs ( P < 0.05). We conclude that nHA addition to PMMA enhances cytocompatibility and the optimal nHA/PMMA ratio for provisional fixed crowns (PFC) is 0.4:1.

The influence of methanol on the chemical state of PtRu anodes in a high-temperature direct methanol fuel cell studied in situ by synchrotron-based near-ambient pressure x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Saveleva, Viktoriia A.; Daletou, Maria K.; Savinova, Elena R.

2017-01-01

Synchrotron radiation-based near-ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) has recently become a powerful tool for the investigation of interfacial phenomena in electrochemical power sources such as batteries and fuel cells. Here we present an in situ NAP-XPS study of the anode of a high-temperature direct methanol fuel cell with a phosphoric acid-doped hydrocarbon membrane, which reveals an enhanced flooding of the Pt3Ru anode with phosphoric acid in the presence of methanol. An analysis of the electrode surface composition depending on the cell voltage and on the presence of methanol reveals the strong influence of the latter on the extent of Pt oxidation and on the transformation of Ru into Ru (IV) hydroxide.

Response to Comment on “Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts”

DOE PAGES

Kattel, Shyam; Ramírez, Pedro J.; Chen, Jingguang G.; ...

2017-09-01

In their Comment on our recent paper, Nakamura et al. argue that our x-ray photoelectron spectroscopy (XPS) analysis was affected by the presence of formate species on the catalyst surface. This argument is not valid because the reactant gases were evacuated at temperatures from 525 to 575 kelvin, conditions under which formate is not stable on the catalyst surface. An analysis of the XPS results obtained after exposing zinc oxide/copper (111) [ZnO/Cu(111)] surfaces to hydrogen (H 2) and mixtures of carbon dioxide (CO 2)/H 2 show an absence of carbon (C) 1s signal, no asymmetries in the oxygen (O) 1smore » peak, and a Zn:O intensity close to 1:1. Thus and finally, the most active phase of these catalysts contained a ZnO-Cu interface.« less

Composition measurement of epitaxial Sc x Ga1-x N films

NASA Astrophysics Data System (ADS)

Tsui, H. C. L.; Goff, L. E.; Barradas, N. P.; Alves, E.; Pereira, S.; Palgrave, R. G.; Davies, R. J.; Beere, H. E.; Farrer, I.; Ritchie, D. A.; Moram, M. A.

2016-06-01

Four different methods for measuring the compositions of epitaxial Sc x Ga1-x N films were assessed and compared to determine which was the most reliable and accurate. The compositions of epitaxial Sc x Ga1-x N films with 0 ≤ x ≤ 0.26 were measured directly using Rutherford backscattering (RBS) and x-ray photoelectron spectroscopy (XPS), and indirectly using c lattice parameter measurements from x-ray diffraction and c/a ratio measurements from electron diffraction patterns. RBS measurements were taken as a standard reference. XPS was found to underestimate the Sc content, whereas c lattice parameter and c/a ratio were not reliable for composition determination due to the unknown degree of strain relaxation in the film. However, the Sc flux used during growth was found to relate linearly with x and could be used to estimate the Sc content.

Metallization of ultra-thin, non-thiol SAMs with flat-lying molecular units: Pd on 1, 4-dicyanobenzene.

PubMed

Eberle, Felix; Metzler, Martin; Kolb, Dieter M; Saitner, Marc; Wagner, Patrick; Boyen, Hans-Gerd

2010-09-10

Self-assembled monolayers of 1,4-dicyanobenzene on Au(111) electrodes are studied by cyclic voltammetry, in-situ STM and ex-situ XPS. High-resolution STM images reveal a long-range order of propeller-like assemblies each of which consists of three molecules, all lying flat on the gold substrate with the cyano groups oriented parallel to the metal surface. It is demonstrated that both functional groups can act as complexation sites for metal ions from solution. Surprisingly, such arrangements still allow the metal to be deposited on top of the molecules by electrochemical reduction despite the close vicinity to the Au surface. The latter is demonstrated by angle-resolved XPS which unequivocally shows that the metal indeed resides on top of the organic layer rather than underneath, despite the flat arrangement of the molecules.

Induced Contamination Predictions for JAXA's MPAC&SEED Devices

NASA Technical Reports Server (NTRS)

Steagall, Courtney; Smith, Kendall; Huang, Alvin; Soares, Carlos; Mikatarian, Ron

2008-01-01

Externally mounted ISS payloads are exposed to the induced ISS environment, including material outgassing and thruster plume contamination. The Boeing Space Environments Team developed analytical and semiempirical models to predict material outgassing and thruster plume induced contamination. JAXA s SM/MPAC&SEED experiment provides an unique opportunity to compare induced contamination predications with measurements. Analysis results are qualitatively consistent with XPS measurements. Calculated depth of contamination within a factor of 2-3 of measured contamination. Represents extremely good agreement, especially considering long duration of experiment and number of outgassing sources. Despite XPS limitations in quantifying plume contamination, the measured and predicted results are of similar scale for the wake-facing surfaces. JAXA s JEM/MPAC&SEED experiment will also be exposed to induced contamination due to JEM and ISS hardware. Predicted material outgassing induced contamination to JEM/MPAC&SEED ranges from 44 to 262 (depending on surface temperature) for a 3 year exposure duration.

X-ray photoelectron spectroscopy study of para-substituted benzoic acids chemisorbed to aluminum oxide thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kreil, Justin; Ellingsworth, Edward; Szulczewski, Greg

A series of para-substituted, halogenated (F, Cl, Br, and I) benzoic acid monolayers were prepared on the native oxide of aluminum surfaces by solution self-assembly and spin-coating techniques. The monolayers were characterized by x-ray photoelectron spectroscopy (XPS) and water contact angles. Several general trends are apparent. First, the polarity of the solvent is critical to monolayer formation. Protic polar solvents produced low coverage monolayers; in contrast, nonpolar solvents produced higher coverage monolayers. Second, solution deposition yields a higher surface coverage than spin coating. Third, the thickness of the monolayers determined from XPS suggests the plane of the aromatic ring ismore » perpendicular to the surface with the carboxylate functional group most likely binding in a bidentate chelating geometry. Fourth, the saturation coverage (∼2.7 × 10{sup 14} molecules cm{sup −2}) is independent of the para-substituent.« less

Surface chemical composition of human maxillary first premolar as assessed by X-ray photoelectron spectroscopy (XPS)

NASA Astrophysics Data System (ADS)

Lou, Leo; Nelson, Alan E.; Heo, Giseon; Major, Paul W.

2008-08-01

The surface chemical composition of dental enamel has been postulated as a contributing factor in the variation of bond strength of brackets bonded to teeth, and hence, the probability of bracket failure during orthodontic treatment. This study systematically investigated the chemical composition of 98 bonding surfaces of human maxillary premolars using X-ray photoelectron spectroscopy (XPS) to ascertain compositional differences between right and left first premolars. The major elements detected in all samples were calcium, phosphorus, oxygen, nitrogen and carbon. Surface compositions were highly variable between samples and several elements were found to be highly correlated. No statistical significant difference in the chemical composition of the maxillary right and left first premolars was found ( p > 0.05). Knowledge of the chemical composition of enamel surfaces will facilitate future studies that relate this information to the variations in dental enamel bond strength.

Surface Modification of Polyimide for Improving Adhesion Strength by Inductively Coupled Plasma

NASA Astrophysics Data System (ADS)

Byun, Tae Joon; Kim, Sung Il; Kim, Youn Joon; Choi, Yoon Suk; Choi, In Sik; Setsuhara, Yuichi; Geon Han, Jeon

2009-08-01

This study examined the effect of an inductively coupled plasma (ICP) treatment using an argon and helium gas mixture on the adhesion between polyimide and a copper film. Optical emission spectroscopy (OES) of the ICP revealed the emission intensity of helium and argon at various intensities with the helium mixing ratio. The treated polyimide surface was analyzed using a contact angle analyzer, Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The contact angle and RMS roughness ranged from 66 to 31° and 2.3 to 4.1 nm, respectively. XPS showed an increase in C-O bonding. The highest peel strength was 0.43 kgf/cm at a 40% of helium mixing ratio, which contained the highest level of activate species. Overall, an ICP treatment of a polyimide surface with a 40% helium gas mixture improves the adhesion strength between copper and polyimide significantly.

Study of the kinetics and mechanism of the thermal nitridation of SiO2

NASA Technical Reports Server (NTRS)

Vasquez, R. P.; Madhukar, A.; Grunthaner, F. J.; Naiman, M. L.

1985-01-01

X-ray photoelectron spectroscopy (XPS) has been used to study the nitridation time and temperature dependence of the nitrogen distribution in thermally nitrided SiO2 films. The XPS data show that the maximum nitrogen concentration near the (SiO(x)N(y)/Si interface is initially at the interface, but moves 20-25 A away from the interface with increasing nitridation time. Computer modeling of the kinetic processes involved is carried out and reveals a mechanism in which diffusing species, initially consisting primarily of nitrogen, react with the substrate, followed by formation of the oxygen-rich oxynitride due to reaction of the diffusing oxygen displaced by the slower nitridation of the SiO2. The data are consistent with this mechanism provided the influence of the interfacial strain on the nitridation and oxidation kinetics is explicitly accounted for.

XPS investigation of depth profiling induced chemistry

NASA Astrophysics Data System (ADS)

Pratt, Quinn; Skinner, Charles; Koel, Bruce; Chen, Zhu

2017-10-01

Surface analysis is an important tool for understanding plasma-material interactions. Depth profiles are typically generated by etching with a monatomic argon ion beam, however this can induce unintended chemical changes in the sample. Tantalum pentoxide, a sputtering standard, and PEDOT:PSS, a polymer that was used to mimic the response of amorphous carbon-hydrogen co-deposits, were studied. We compare depth profiles generated with monatomic and gas cluster argon ion beams (GCIB) using X-ray photoelectron spectroscopy (XPS) to quantify chemical changes. In both samples, monatomic ion bombardment led to beam-induced chemical changes. Tantalum pentoxide exhibited preferential sputtering of oxygen and the polymer experienced significant bond modification. Depth profiling with clusters is shown to mitigate these effects. We present sputtering rates for Ta2O5 and PEDOT:PSS as a function of incident energy and flux. Support was provided through DOE Contract Number DE-AC02-09CH11466.

Thickness Influence on In Vitro Biocompatibility of Titanium Nitride Thin Films Synthesized by Pulsed Laser Deposition

PubMed Central

Duta, Liviu; Stan, George E.; Popa, Adrian C.; Husanu, Marius A.; Moga, Sorin; Socol, Marcela; Zgura, Irina; Miculescu, Florin; Urzica, Iuliana; Popescu, Andrei C.; Mihailescu, Ion N.

2016-01-01

We report a study on the biocompatibility vs. thickness in the case of titanium nitride (TiN) films synthesized on 410 medical grade stainless steel substrates by pulsed laser deposition. The films were grown in a nitrogen atmosphere, and their in vitro cytotoxicity was assessed according to ISO 10993-5 [1]. Extensive physical-chemical analyses have been carried out on the deposited structures with various thicknesses in order to explain the differences in biological behavior: profilometry, scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction and surface energy measurements. XPS revealed the presence of titanium oxynitride beside TiN in amounts that vary with the film thickness. The cytocompatibility of films seems to be influenced by their TiN surface content. The thinner films seem to be more suitable for medical applications, due to the combined high values of bonding strength and superior cytocompatibility. PMID:28787846

Intrinsic stress modulation in diamond like carbon films with incorporation of gold nanoparticles by PLA

NASA Astrophysics Data System (ADS)

Panda, Madhusmita; Krishnan, R.; Krishna, Nanda Gopala; Madapu, Kishore K.; Kamruddin, M.

2018-04-01

Intrinsic stress modulation in the diamond-like carbon (DLC) coatings with incorporation of gold nanoparticles was studied qualitatively from Raman shift. The films were deposited on Si (1 0 0) substrates by using Pulsed laser ablation (PLA) of pure pyrolytic graphite target and with a gold foil on it. Films compositional and chemical behavior was studied by X-ray photoelectron spectroscopy (XPS) and Visible Raman spectroscopy, respectively. The sp3 content obtained from XPS shows dramatic variation in DLC, DLC-Au(100), DLC-Au(200) and DLC-Au(300) as 39%, 41%, 47% and 66% with various gold contentsas 0%, 12%, 7.3% and 4.7%, respectively. The Raman spectra of DLC/Au films showed G-peak shift towards lower wavenumber indicating the reduction of intrinsic stress (internal compressive stress). The sp2, sp3 fraction in the films are also determined from FWHM (G-Peak).

Effects of M=Si, Ga and Al for Co substitution on the electronic properties of RCo4M as probed by XPS

NASA Astrophysics Data System (ADS)

Laslo, A.; Dudric, R.; Neumann, M.; Isnard, O.; Coldea, M.; Pop, V.

2014-12-01

The electronic properties of RCo5-xMx (R=Er, Sm, Tm; M=Si, Ga, Al; x=0 and 1) compounds were investigated by X-ray photoelectron spectroscopy (XPS). The study was focused on the Co 3s exchange splitting, the valence bands and chemical shifts of the elements from the analyzed compounds. The Co 2p3/2 core-level chemical shifts were described by means of the Auger parameters and Wagner plot. The hybridization between the R 5d6s and M 3sp and 4sp states and Co 3d states leads to a partial filling of the Co 3d band and to a decrease of the Co magnetic moments in comparison with the value in pure Co metal, in good agreement with the magnetic measurements.

Unraveling the Molecular Weight Dependence of Interfacial Interactions in Poly(2-vinylpyridine)/Silica Nanocomposites

DOE PAGES

Voylov, Dmitry N.; Holt, Adam P.; Doughty, Benjamin; ...

2017-01-10

In this paper, the structure and polymer–nanoparticle interactions among physically adsorbed poly(2-vinylpyridine) chains on the surface of silica nanoparticles (NPs) were systematically studied as a function of molecular weight (MW) by sum frequency generation (SFG) and X-ray photoelectron (XPS) spectroscopies. Analysis of XPS data identified hydrogen bonds between the polymer and NPs, while SFG evaluated the change in the number of free OH sites on the NP’s surface. Our data revealed that the hydrogen bonds and amount of the free ¯OH sites have a significant dependence on the polymer’s MW. Finally, these results provide clear experimental evidence that the interactionmore » of physically adsorbed chains with nanoparticles is strongly MW dependent and aids in unraveling the microscopic mechanism responsible for the strong MW dependence of dynamics of the interfacial layer in polymer nanocomposites.« less

Simple quantification of surface carboxylic acids on chemically oxidized multi-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Gong, Hyejin; Kim, Seong-Taek; Lee, Jong Doo; Yim, Sanggyu

2013-02-01

The surface of multi-walled carbon nanotube (MWCNT) was chemically oxidized using nitric acid and sulfuric-nitric acid mixtures. Thermogravimetric analysis, transmission electron microscopy and infrared spectroscopy revealed that the use of acid mixtures led to higher degree of oxidation. More quantitative identification of surface carboxylic acids was carried out using X-ray photoelectron spectroscopy (XPS) and acid-base titration. However, these techniques are costly and require very long analysis times to promptly respond to the extent of the reaction. We propose a much simpler method using pH measurements and pre-determined pKa value in order to estimate the concentration of carboxylic acids on the oxidized MWCNT surfaces. The results from this technique were consistent with those obtained from XPS and titration, and it is expected that this simple quantification method can provide a cheap and fast way to monitor and control the oxidation reaction of MWCNT.

Surface Propensity of Atmospherically Relevant Amino Acids Studied by XPS.

PubMed

Mocellin, Alexandra; Gomes, Anderson Herbert de Abreu; Araújo, Oscar Cardoso; de Brito, Arnaldo Naves; Björneholm, Olle

2017-04-27

Amino acids constitute an important fraction of the water-soluble organic nitrogen (WSON) compounds in aerosols and are involved in many processes in the atmosphere. In this work, we applied X-ray photoelectron spectroscopy (XPS) to study aqueous solutions of four amino acids, glycine, alanine, valine, and methionine, in their zwitterionic forms. We found that amino acids with hydrophilic side chains and smaller size, GLY and ALA, tend to stay in the bulk of the liquid, while the hydrophobic and bigger amino acids, VAL and MET, are found to concentrate more on the surface. We found experimental evidence that the amino acids have preferential orientation relative to the surface, with the hydrophobic side chain being closer to the surface than the hydrophilic carboxylate group. The observed amino acid surface propensity has implications in atmospheric science as the surface interactions play a central role in cloud droplet formation, and they should be considered in climate models.

Structure of mono- and bimetallic heterogeneous catalysts based on noble metals obtained by means of fluid technology and metal-vapor synthesis

NASA Astrophysics Data System (ADS)

Said-Galiev, E. E.; Vasil'kov, A. Yu.; Nikolaev, A. Yu.; Lisitsyn, A. I.; Naumkin, A. V.; Volkov, I. O.; Abramchuk, S. S.; Lependina, O. L.; Khokhlov, A. R.; Shtykova, E. V.; Dembo, K. A.; Erkey, C.

2012-10-01

Monometallic nanocomposites are obtained with the use of supercritical carbon dioxide (fluid technique) and metal-vapor synthesis (MVS), while bimetallic nanocomposites of Pt and Au noble metals and γ-Al2O3 oxide matrix are synthesized by a combination of these two methods. The structures, concentrations, and chemical states of metal atoms in composites are studied by means of small-angle X-ray scattering (SAXS), transparent electron microscopy (TEM), X-ray fluorescent analysis (XFA), and X-ray photoelectron spectroscopy (XPS). The neutral state of metal atoms in clusters is shown by XPS and their size distribution is found according to SAXS; as is shown, it is determined by the pore sizes of the oxide matrices and lies in the range of 1 to 50 nm. The obtained composites manifest themselves as effective catalysts in the oxidation of CO to CO2.

Roles of oxyanions in promoting the partial oxidation of styrene on Ag(110): nitrate, carbonate, sulfite, and sulfate.

PubMed

Zhou, Ling; Madix, Robert J

2010-11-02

The promotion roles of nitrate, carbonate, sulfite, and sulfate in oxidation of styrene on Ag(110) have been studied by means of temperature-programmed reaction spectroscopy (TPRS) and X-ray photoelectron spectroscopy (XPS). While isolated nitrate leads only to the secondary oxidation of styrene, a surface co-covered by nitrate, oxygen, and 0.1 ML cesium promotes a low-temperature epoxidation pathway. XPS indicates that adsorbed surface oxygen is the oxidant in this selective reaction pathway, and, though it affects the reactivity of the surface oxygen, nitrate is a spectator. Carbonate acts as an oxygen transfer agent and exhibits similar reactivity and selectivity as an oxidant for styrene as does atomic oxygen on Ag(110). The reactivities of sulfite and sulfate are strongly dependent on their surface structures, the c(6 × 2) sulfite showing the capacity to transfer oxygen to styrene.

Initial stages of microbiologically influenced tarnishing on titanium after 20 months of immersion in freshwater.

PubMed

Moreno, D A; Cano, E; Ibars, J R; Polo, J L; Montero, F; Bastidas, J M

2004-05-01

This paper studies the initial stages of iridescent tarnishes on titanium heat exchanger tubes in contact with running freshwater on the river Tagus in Spain for up to 20 months. Electrochemical impedance spectroscopy (EIS), scanning electron microscopy [(SEM with energy dispersive X-ray (EDX)] and X-ray photoelectron spectroscopy (XPS) in conjunction with argon-ion sputtering were the techniques used. The EIS data indicated a capacitive behavior, showing a semicircle that was better defined as the experimental time increased, indicating a decreasing tarnishing resistance of titanium. XPS and EDX results indicated that the main elements identified were calcium, phosphorus, nitrogen, and iron. The amount of these elements was higher on the tarnished titanium specimens than on the untarnished specimens. SEM analysis showed the presence of diatoms in the iridescent tarnishes on titanium tubes. Copyright 2003 Springer-Verlag

Response to Comment on "Active sites for CO2 hydrogenation to methanol on Cu/ZnO catalysts".

PubMed

Kattel, Shyam; Ramírez, Pedro J; Chen, Jingguang G; Rodriguez, José A; Liu, Ping

2017-09-01

In their Comment on the our recent Report, Nakamura et al argue that our x-ray photoelectron spectroscopy (XPS) analysis was affected by the presence of formate species on the catalyst surface. This argument is not valid because the reactant gases were evacuated at temperatures from 525 to 575 kelvin, conditions under which formate is not stable on the catalyst surface. An analysis of the XPS results obtained after exposing zinc oxide/copper (111) [ZnO/Cu(111)] surfaces to hydrogen (H 2 ) and mixtures of carbon dioxide (CO 2 )/H 2 show an absence of carbon (C) 1s signal, no asymmetries in the oxygen (O) 1s peak, and a Zn:O intensity close to 1:1. Thus, the most active phase of these catalysts contained a ZnO-Cu interface. Copyright © 2017, American Association for the Advancement of Science.

Stability of boron-doped graphene/copper interface: DFT, XPS and OSEE studies

NASA Astrophysics Data System (ADS)

Boukhvalov, D. W.; Zhidkov, I. S.; Kukharenko, A. I.; Slesarev, A. I.; Zatsepin, A. F.; Cholakh, S. O.; Kurmaev, E. Z.

2018-05-01

Two different types of boron-doped graphene/copper interfaces synthesized using two different flow rates of Ar through the bubbler containing the boron source were studied. X-ray photoelectron spectra (XPS) and optically stimulated electron emission (OSEE) measurements have demonstrated that boron-doped graphene coating provides a high corrosion resistivity of Cu-substrate with the light traces of the oxidation of carbon cover. The density functional theory calculations suggest that for the case of substitutional (graphitic) boron-defect only the oxidation near boron impurity is energetically favorable and creation of the vacancies that can induce the oxidation of copper substrate is energetically unfavorable. In the case of non-graphitic boron defects oxidation of the area, a nearby impurity is metastable that not only prevent oxidation but makes boron-doped graphene. Modeling of oxygen reduction reaction demonstrates high catalytic performance of these materials.

Nitridation of silicon by nitrogen neutral beam

NASA Astrophysics Data System (ADS)

Hara, Yasuhiro; Shimizu, Tomohiro; Shingubara, Shoso

2016-02-01

Silicon nitridation was investigated at room temperature using a nitrogen neutral beam (NB) extracted at acceleration voltages of less than 100 V. X-ray photoelectron spectroscopy (XPS) analysis confirmed the formation of a Si3N4 layer on a Si (1 0 0) substrate when the acceleration voltage was higher than 20 V. The XPS depth profile indicated that nitrogen diffused to a depth of 36 nm for acceleration voltages of 60 V and higher. The thickness of the silicon nitrided layer increased with the acceleration voltages from 20 V to 60 V. Cross-sectional transmission electron microscopy (TEM) analysis indicated a Si3N4 layer thickness of 3.1 nm was obtained at an acceleration voltage of 100 V. Moreover, it was proved that the nitrided silicon layer formed by the nitrogen NB at room temperature was effective as the passivation film in the wet etching process.

Physicochemical properties of chars at different treatment temperatures.

PubMed

Kim, Sung Su; Kang, Youn Suk; Lee, Hyun Dong; Kim, Jae Kwan; Hong, Sung Chang

2012-02-01

In this study, the physicochemical properties of the char of Indonesian SM coal following heat treatment at various temperatures were evaluated using X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and morphological and specific surface area analysis. Based on these analyses, heat treatment of coal was determined to be the most effective in increasing the coal rank. In the XPS analysis, the C-O and C-O-C groups and quaternary-N species were found to be of a lower grade coal when the pretreatment temperature decreased, meanwhile the C-C group and pyridinic species increased. In the FT-IR analysis, the collapse of the C-O and C-O-C group was observed due to the collapse of the ether group. In SEM and Brunauer-Emmett-Teller (BET) analysis, a decrease in the ether group was shown to be accompanied with the formation of micropores.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Mingyi; Xu, Xiaoyang, E-mail: xiaoyangxu2012@163.com; Wu, Tao

Highlights: • Graphene oxide (GO) was modified by chemical reactions to functionalized GO (FGO). • The FGOs and the GO were then subjected to in situ free radical polymerization. • Hydroxyl groups of GO were the most reactive grafting sites. - Abstract: Graphene oxide (GO) was modified using chemical reactions to obtain three types of functionalized GO sheets (FGO). The FGO sheets and the GO were then subjected to in situ free radical polymerization in order to study the grafting polymerization. The FGO and grafted-.FGO were analyzed with Fourier transform infrared spectroscopy, scanning electronic microscopy, thermo-gravimetric analysis (TGA) and X-raymore » photoelectron spectroscopy (XPS). The grafting percentages in the materials were calculated using the TGA and XPS results. The FGO sheets with different functional groups exhibited different grafting abilities, and hydroxyl groups were proven to be the most reactive grafting sites for the in situ free radical grafting polymerization of polyacrylamide.« less

Corrosion product layers on magnesium alloys AZ31 and AZ61: Surface chemistry and protective ability

NASA Astrophysics Data System (ADS)

Feliu, S.; Llorente, I.

2015-08-01

This paper studies the chemical composition of the corrosion product layers formed on magnesium alloys AZ31 and AZ61 following immersion in 0.6 M NaCl, with a view to better understanding their protective action. Relative differences in the chemical nature of the layers were quantified by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDX) and low-angle X-ray diffraction (XRD). Corrosion behavior was investigated by Electrochemical Impedance Spectroscopy (EIS) and hydrogen evolution measurement. An inhibitive effect from the corrosion product layers was observed from EIS, principally in the case of AZ31, as confirmed by hydrogen evolution tests. A link was found between carbonate enrichment observed by XPS in the surface of the corrosion product layer, concomitant with the increase in the protective properties observed by EIS.

Adsorption and reaction of propene on Ni(100)

NASA Astrophysics Data System (ADS)

Kleyna, R.; Borgmann, D.; Wedler, G.

1998-05-01

Photoelectron spectroscopy (UPS, XPS) and thermal desorption techniques were used to study the chemisorption and decomposition reactions of propene on Ni(100). Propene is molecularly adsorbed at temperatures below 150 K. At saturation coverage the TD spectrum shows two propene desorption peaks at 155 and 225 K and three hydrogen desorption peaks at 300, 330 and 380 K with a shoulder at 420 K. No other desorbing species could be detected. The amount of desorption of propene was determined by XPS to be 20% of the saturation coverage. The electronic structure of adsorbed propene and the chemical nature of its decomposition products were deduced from UP and XP spectra taken at saturation coverage. Adsorption at low temperatures results in a π-bonded species which is stable up to 150 K. At temperatures above 150 K the UP spectra point to a σ-bonded species which decomposes further at temperatures above 260 K.

Reactivity and reaction intermediates for acetic acid adsorbed on CeO 2(111)

DOE PAGES

Calaza, Florencia C.; Chen, Tsung -Liang; Mullins, David R.; ...

2015-05-02

Adsorption and reaction of acetic acid on a CeO 2(1 1 1) surface was studied by a combination of ultra-highvacuum based methods including temperature desorption spectroscopy (TPD), soft X-ray photoelectronspectroscopy (sXPS), near edge X-ray absorption spectroscopy (NEXAFS) and reflection absorption IRspectroscopy (RAIRS), together with density functional theory (DFT) calculations. TPD shows that thedesorption products are strongly dependent upon the initial oxidation state of the CeO 2 surface, includingselectivity between acetone and acetaldehyde products. The combination of sXPS and NEXAFS demon-strate that acetate forms upon adsorption at low temperature and is stable to above 500 K, above whichpoint ketene, acetone andmore » acetic acid desorb. Furthermore, DFT and RAIRS show that below 500 K, bridge bondedacetate coexists with a moiety formed by adsorption of an acetate at an oxygen vacancy, formed bywater desorption.« less

Characteristics of polyaniline cobalt supported catalysts for epoxidation reactions.

PubMed

Kowalski, Grzegorz; Pielichowski, Jan; Grzesik, Mirosław

2014-01-01

A study of polyaniline (PANI) doping with various cobalt compounds, that is, cobalt(II) chloride, cobalt(II) acetate, and cobalt(II) salen, is presented. The catalysts were prepared by depositing cobalt compounds onto the polymer surface. PANI powders containing cobalt ions were obtained by one- or two-step method suspending PANI in the following acetonitrile/acetic acid solution or acetonitrile and then acetic acid solution. Moreover different ratios of Co(II) : PANI were studied. Catalysts obtained with both methods and at all ratios were investigated using various techniques including AAS and XPS spectroscopy. The optimum conditions for preparation of PANI/Co catalysts were established. Catalytic activity of polyaniline cobalt(II) supported catalysts was tested in dec-1-ene epoxidation with molecular oxygen at room temperature. The relationship between the amount of cobalt species, measured with both AAS and XPS techniques, and the activity of PANI-Co catalysts has been established.

Characteristics of Polyaniline Cobalt Supported Catalysts for Epoxidation Reactions

PubMed Central

Kowalski, Grzegorz; Pielichowski, Jan; Grzesik, Mirosław

2014-01-01

A study of polyaniline (PANI) doping with various cobalt compounds, that is, cobalt(II) chloride, cobalt(II) acetate, and cobalt(II) salen, is presented. The catalysts were prepared by depositing cobalt compounds onto the polymer surface. PANI powders containing cobalt ions were obtained by one- or two-step method suspending PANI in the following acetonitrile/acetic acid solution or acetonitrile and then acetic acid solution. Moreover different ratios of Co(II) : PANI were studied. Catalysts obtained with both methods and at all ratios were investigated using various techniques including AAS and XPS spectroscopy. The optimum conditions for preparation of PANI/Co catalysts were established. Catalytic activity of polyaniline cobalt(II) supported catalysts was tested in dec-1-ene epoxidation with molecular oxygen at room temperature. The relationship between the amount of cobalt species, measured with both AAS and XPS techniques, and the activity of PANI-Co catalysts has been established. PMID:24701183

Synthesis and characterization of porous CaCO3 micro/nano-particles

NASA Astrophysics Data System (ADS)

Achour, A.; Arman, A.; Islam, M.; Zavarian, A. A.; Basim Al-Zubaidi, A.; Szade, J.

2017-06-01

Porous CaCO3 particles, both micro and nano sized, were synthesized in a mixture of Ca(OH)2, hyaluronic acid (HA), glycine, NaOH and NaCl solution with supercritical carbon dioxide. The particles were characterized using X-Ray Diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscope, Raman spectroscope (RS), X-ray photoelectron spectroscope (XPS) and scanning electron microscope techniques. All these techniques showed that the particles crystallize into only one CaCO3 structure, namely the vaterite phase. In addition, FTIR, RS and XPS indicated the presence of residual reactive species i.e. glycine, NaCl, and HA. The XRD results confirmed the presence of NaCl and γ-glycine, which is a crystalline material. Moreover, the HA seems to be mostly embedded in the bulk of the micro-particles. Such materials are promising for biomedical applications such as drug delivery.

Solar Absorber Cu 2 ZnSnS 4 and its Parent Multilayers ZnS/SnS 2 /Cu 2 S Synthesized by Atomic Layer Deposition and Analyzed by X-ray Photoelectron Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baryshev, Sergey V.; Riha, Shannon C.; Zinovev, Alexander V.

2015-06-01

Presented here are results of x-ray photoelectron spectroscopy (XPS) on multilayers of metal-sulfide binaries ZnS, SnS2, and Cu2S grown by atomic layer deposition (ALD) on Si substrates, and of Cu2ZnSnS4 (CZTS) formed upon 450 °C annealing of the parent multilayer ZnS/SnS2/Cu2S. Survey and detailed spectral analysis of the multilayer ZnS/SnS2/Cu2S are presented step-wise, as each layer was sequentially added by ALD. The set of data is finalized with spectra of the resulting alloy CZTS. XPS analyses indicate significant mixing between SnS2 and Cu2S, which favors CZTS formation within the ALD approach.

X-Ray Photoelectron Spectroscopic Characterization of Iron Oxide Nanoparticles

NASA Astrophysics Data System (ADS)

Radu, T.; Iacovita, C.; Benea, D.; Turcu, R.

2017-05-01

We report X-ray photoelectron spectroscopy (XPS) results on iron oxide magnetic nanoparticle (Fe3O4) synthesized using solvothermal reduction in the presence of polyethylene glycol. The magnetite obtained was employed as precursor for the synthesis of γ-Fe2O3 (by oxygen dissociation) which in turn was transformed into α-Fe2O3. We confirmed the magnetite, maghemite and hematite structure by Fourier Transformed Spectroscopy (FTIR) and X-ray diffraction (XRD). The analysis of the XPS core level and valence band (VB) photoemission spectra for all investigated samples is discussed in terms of the degree of iron oxidation. This is of fundamental importance to better understand the electronic structure of the obtained iron oxide nanoparticles in order to control and improve their quality for specific biomedical applications. Moreover, theoretical band structure calculations are performed for magnetite and the separate contributions of Fe in tetragonal and octahedral environment are shown.

A spectroscopic study for understanding the speciation of Cr on palm shell based adsorbents and their application for the remediation of chrome plating effluents.

PubMed

Kushwaha, Shilpi; Sreedhar, B; Sudhakar, Padmaja P

2012-07-01

Palm shell based adsorbents prepared under five different thermochemical conditions have been shown to be quite effective for removal of chromium (III and VI) from aqueous solutions. X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FT-IR) have been used to determine information about the speciation and binding of chromium on the adsorbents under study. X-ray photoelectron spectroscopy (XPS) studies indicate that oxidation of lignin moieties takes place concurrently to Cr(VI) reduction and leads to the formation of hydroxyl and carboxyl functions. The maximum adsorption capacity for hexavalent chromium was found to be about 313 mg/g in an acidic medium using PAPSP. This is comparable to other natural substrates and ordinary adsorbents. The efficacy of the adsorbents under study to remove chromium from plating waste water has been demonstrated. Copyright © 2012 Elsevier Ltd. All rights reserved.

InP/ZnS nanocrystals: coupling NMR and XPS for fine surface and interface description.

PubMed

Virieux, Héloïse; Le Troedec, Marianne; Cros-Gagneux, Arnaud; Ojo, Wilfried-Solo; Delpech, Fabien; Nayral, Céline; Martinez, Hervé; Chaudret, Bruno

2012-12-05

Advanced (1)H, (13)C, and (31)P solution- and solid-state NMR studies combined with XPS were used to probe, at the molecular scale, the composition (of the core, the shell, and the interface) and the surface chemistry of InP/ZnS core/shell quantum dots prepared via a non-coordinating solvent strategy. The interface between the mismatched InP and ZnS phases is composed of an amorphous mixed oxide phase incorporating InPO(x) (with x = 3 and predominantly 4), In(2)O(3), and InO(y)(OH)(3-2y) (y = 0, 1). Thanks to the analysis of the underlying reaction mechanisms, we demonstrate that the oxidation of the upper part of the InP core is the consequence of oxidative conditions brought by decarboxylative coupling reactions (ketonization). These reactions occur during both the core preparation and the coating process, but according to different mechanisms.

Unraveling the Molecular Weight Dependence of Interfacial Interactions in Poly(2-vinylpyridine)/Silica Nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Voylov, Dmitry N.; Holt, Adam P.; Doughty, Benjamin

In this paper, the structure and polymer–nanoparticle interactions among physically adsorbed poly(2-vinylpyridine) chains on the surface of silica nanoparticles (NPs) were systematically studied as a function of molecular weight (MW) by sum frequency generation (SFG) and X-ray photoelectron (XPS) spectroscopies. Analysis of XPS data identified hydrogen bonds between the polymer and NPs, while SFG evaluated the change in the number of free OH sites on the NP’s surface. Our data revealed that the hydrogen bonds and amount of the free ¯OH sites have a significant dependence on the polymer’s MW. Finally, these results provide clear experimental evidence that the interactionmore » of physically adsorbed chains with nanoparticles is strongly MW dependent and aids in unraveling the microscopic mechanism responsible for the strong MW dependence of dynamics of the interfacial layer in polymer nanocomposites.« less

Dependence of LTX plasma performance on surface conditions as determined by in situ analysis of plasma facing components

NASA Astrophysics Data System (ADS)

Lucia, M.; Kaita, R.; Majeski, R.; Bedoya, F.; Allain, J. P.; Abrams, T.; Bell, R. E.; Boyle, D. P.; Jaworski, M. A.; Schmitt, J. C.

2015-08-01

The Materials Analysis and Particle Probe (MAPP) diagnostic has been implemented on the Lithium Tokamak Experiment (LTX) at PPPL, providing the first in situ X-ray photoelectron spectroscopy (XPS) surface characterization of tokamak plasma facing components (PFCs). MAPP samples were exposed to argon glow discharge conditioning (GDC), lithium evaporations, and hydrogen tokamak discharges inside LTX. Samples were analyzed with XPS, and alterations to surface conditions were correlated against observed LTX plasma performance changes. Argon GDC caused the accumulation of nm-scale metal oxide layers on the PFC surface, which appeared to bury surface carbon and oxygen contamination and thus improve plasma performance. Lithium evaporation led to the rapid formation of a lithium oxide (Li2O) surface; plasma performance was strongly improved for sufficiently thick evaporative coatings. Results indicate that a 5 h argon GDC or a 50 nm evaporative lithium coating will both significantly improve LTX plasma performance.

Enhancing Electrochemical Water-Splitting Kinetics by Polarization-Driven Formation of Near-Surface Iron(0): An In Situ XPS Study on Perovskite-Type Electrodes**

PubMed Central

Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Rameshan, Raffael; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Fleig, Jürgen; Klötzer, Bernhard

2015-01-01

In the search for optimized cathode materials for high-temperature electrolysis, mixed conducting oxides are highly promising candidates. This study deals with fundamentally novel insights into the relation between surface chemistry and electrocatalytic activity of lanthanum ferrite based electrolysis cathodes. For this means, near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and impedance spectroscopy experiments were performed simultaneously on electrochemically polarized La0.6Sr0.4FeO3−δ (LSF) thin film electrodes. Under cathodic polarization the formation of Fe0 on the LSF surface could be observed, which was accompanied by a strong improvement of the electrochemical water splitting activity of the electrodes. This correlation suggests a fundamentally different water splitting mechanism in presence of the metallic iron species and may open novel paths in the search for electrodes with increased water splitting activity. PMID:25557533

Self-repairing vanadium-zirconium composite conversion coating for aluminum alloys

NASA Astrophysics Data System (ADS)

Zhong, Xin; Wu, Xiaosong; Jia, Yuyu; Liu, Yali

2013-09-01

In this paper, new self-repairing vanadium-zirconium composite conversion coating was prepared and investigated by Electrochemical impedance spectra (EIS), Scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. EIS results showed that V-Zr conversion coating with hydrogen peroxide modified (VZO) revealed an increasing corrosion resistance in corrosive media which meant a certain self-repairing effect. SEM comparison photos also disclosed that VZO treated with scratches was gradually ameliorated from the initial cracked configuration to fewer cracks and more fillers through an immersion of 3.5% NaCl solution. XPS results demonstrated that the content of vanadium on VZO increased and zirconium declined when immersed in the corrosive solution. This explained further that the self-repairing ability could be related to vanadium. From the above results, we inferred possible structures of VZO and proposed that self-repairing effect was achieved through a hydrolysis condensation polymerization process of vanadate in the localized corrosion area.

XPS-nanocharacterization of organic layers electrochemically grafted on the surface of SnO2 thin films to produce a new hybrid material coating

NASA Astrophysics Data System (ADS)

Drevet, R.; Dragoé, D.; Barthés-Labrousse, M. G.; Chaussé, A.; Andrieux, M.

2016-10-01

This work presents the synthesis and the characterization of hybrid material thin films obtained by the combination of two processes. The electrochemical grafting of organic layers made of carboxyphenyl moieties is carried out from the reduction of a diazonium salt on tin dioxide (SnO2) thin films previously deposited on Si substrates by metal organic chemical vapor deposition (MOCVD). Since the MOCVD experimental parameters impact the crystal growth of the SnO2 layer (i.e. its morphology and its texturation), various electrochemical grafting models can occur, producing different hybrid materials. In order to evidence the efficiency of the electrochemical grafting of the carboxyphenyl moieties, X-ray Photoelectron Spectroscopy (XPS) is used to characterize the first nanometers in depth of the synthesized hybrid material layer. Then three electrochemical grafting models are proposed.

Applications of time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS) to study interactions of genetically engineered proteins with noble metal films

NASA Astrophysics Data System (ADS)

Suzuki, Noriaki

Genetically engineered proteins for inorganics (GEPIs) belong to a new class of polypeptides that are designed to have specific affinities to inorganic materials. A "gold binding protein (GBP)" was chosen as a model protein for GEPIs to study the molecular origins of binding specificity to gold using Time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS). TOF-SIMS, a surface-sensitive analytical instrument with extremely high mass resolutions, provides information on specific amino acid-surface interactions. We used "principal component analysis (PCA)" to analyze the data. We also introduced a new multivariate technique, "hierarchical cluster analysis (HCA)" to organize the data into meaningful structures by measuring a degree of "similarity" and "dissimilarity" of the data. This report discusses a combined use of PCA and HCA to elucidate the binding specificity of GBP to Au. Based on the knowledge gained from TOF-SIMS measurements, we further investigated the nature of the interaction between selected amino acids and noble metal surfaces by using X-ray photoelectron spectroscopy (XPS). We developed a unique capability to introduce water vapor during the adsorption of a single amino acid and applied this method to study the intrinsic nature of sidechain/Au interactions. To further apply this unique research protocol, we characterized another type of GEPI, "quartz binding protein (QBP)," to identify the possible binding sites. This thesis research aims to provide experimental protocols for analyzing short peptide-substrate interface from complex spectroscopic data by using multivariate analysis techniques.

The role of cobalt doping on magnetic and optical properties of indium oxide nanostructured thin film prepared by sol–gel method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baqiah, H.; Ibrahim, N.B., E-mail: baayah@ukm.my; Halim, S.A.

2015-03-15

Highlights: • Cobalt doped indium oxide thin films have been prepared by a sol–gel method. • The films have a thickness less than 100 nm and grain size less than 10 nm. • The lattice parameters and grain size of films decrease as Co content increase. • The optical band gap of films increases as the grain size decrease. • The films' magnetic behaviour is sensitive to ratio of oxygen defects per Co ions. - Abstract: The effect of Co doping concentration, (x = 0.025–0.2), in In{sub 2−x}Co{sub x}O{sub 3} thin film was investigated by X-rays diffraction (XRD), transmission electronmore » microscopy, X-ray photoelectron spectroscopy (XPS), Ultraviolet visible spectrophotometer (UV–vis) and vibrating sample magnetometer (VSM). All films were prepared by sol–gel technique followed by spin coating process. The XRD and XPS measurements indicate that Co{sup +2} has been successfully substituted in In{sup +3} site. The TEM measurement shows nanostructure morphology of the films. The doping of Co in indium oxide resulted in a decrease in the lattice parameters and grain size while the band gap increased with increasing Co concentration. Further, by comparing VSM and XPS results, the magnetic behaviour of the films were found to be sensitive to Co concentrations, oxygen vacancies and ratio of oxygen defects to Co concentrations. The magnetic behaviour of the prepared films was explained using bound magnetic polaron (BMP) model.« less

Surface composition XPS analysis of a plasma treated polystyrene: Evolution over long storage periods.

PubMed

Ba, Ousmane M; Marmey, Pascal; Anselme, Karine; Duncan, Anthony C; Ponche, Arnaud

2016-09-01

A polystyrene surface (PS) was initially treated by cold nitrogen and oxygen plasma in order to incorporate in particular amine and hydroxyl functions, respectively. The evolution of the chemical nature of the surface was further monitored over a long time period (580 days) by chemical assay, XPS and contact angle measurements. Surface density quantification of primary amine groups was performed using three chemical amine assays: 4-nitrobenzaldehyde (4-NBZ), Sulfo succinimidyl 6-[3'(2 pyridyldithio)-pionamido] hexanoate (Sulfo-LC-SPDP) and iminothiolane (ITL). The results showed amine densities were in the range of 2 per square nanometer (comparable to the results described in the literature) after 5min of nitrogen plasma treatment. Over the time period investigated, chemical assays, XPS and contact angles suggest a drastic significant evolution of the chemical nature of the surface within the first two weeks. Beyond that time period and up to almost two years, nitrogen plasma modified substrates exhibits a slow and continuous oxidation whereas oxygen plasma modifed polystyrene surface is chemically stable after two weeks of storage. The latter appeared to "ease of" showing relatively mild changes within the one year period. Our results suggest that it may be preferable to wait for a chemical "stabilization" period of two weeks before subsequent covalent immobilization of proteins onto the surface. The originality of this work resides in the study of the plasma treated surface chemistry evolution over long periods of storage time (580 days) considerably exceeding those described in the literature. Copyright © 2016 Elsevier B.V. All rights reserved.

Crystal growth of Bi{sub 2}Te{sub 3} and noble cleaved (0001) surface properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Atuchin, V.V., E-mail: atuchin@thermo.isp.nsc.ru; Functional Electronics Laboratory, Tomsk State University, Tomsk 634050; Golyashov, V.A.

2016-04-15

A high quality Bi{sub 2}Te{sub 3} crystal has been grown by Bridgman method with the use of rotating heat field. The phase purity and bulk structural quality of the crystal have been verified by XRD analysis and rocking curve observation. The atomically smooth Bi{sub 2}Te{sub 3}(0001) surface with an excellent crystallographic quality is formed by cleavage in the air. The chemical and microstructural properties of the surface have been evaluated with RHEED, AFM, STM, SE and XPS. The Bi{sub 2}Te{sub 3}(0001) cleaved surface is formed by atomically smooth terraces with the height of the elemental step of ~1.04±0.1 nm, asmore » estimated by AFM. There is no surface oxidation process detected over a month keeping in the air at normal conditions, as shown by comparative core level photoelectron spectroscopy. - Graphical abstract: A high quality Bi{sub 2}Te{sub 3} crystal has been grown by Bridgman method with the use of rotating heat field and the Bi{sub 2}Te{sub 3}(0001) cleaved surface has been evaluated with RHEED, AFM, STM, SE and XPS. - Highlights: • High-quality Bi{sub 2}Te{sub 3} crystal of 10 mm in diameter and 50 mm long have been grown. • The high-purity cleaved Bi{sub 2}Te{sub 3}(0001) surface has been evaluated by RHEED, AFM, STM and XPS methods. • The Bi{sub 2}Te{sub 3} surface covered by atomically smooth (0001) terraces is chemically stable for a long time.« less

Reaction of Si nanopowder with water investigated by FT-IR and XPS

NASA Astrophysics Data System (ADS)

Imamura, Kentaro; Kobayashi, Yuki; Matsuda, Shinsuke; Akai, Tomoki; Kobayashi, Hikaru

2017-08-01

The initial reaction of Si nanopowder with water to generate hydrogen is investigated using FT-IR and XPS measurements. Si nanopowder is fabricated using the simple beads milling method. For HF-etched Si nanopowder, strong peaks due to Si-H and Si-H2 stretching vibrational modes and a weak shoulder peak due to Si-H3 are observed. Although no peaks due to oxide is observed in the Si 2p XPS spectrum, weak vibrational peaks due to HSiO2 and HSiO3 species are observable. The hydrogen generation rate greatly increases with pH, indicating that the reacting species is hydroxide ions (OH- ions). After the reaction, the intensities of the peaks due to SiH and SiH2 species decrease while those for HSiO, HSiO2, and HSiO3 species increase. This result demonstrates that OH- ions attack Si back-bonds, with surface Si-H bonds remaining. After initial reaction of HF-etched Si nanopowder with heavy water, vibrational peaks for SiD, SiDH, and SiDH2 appear, and then, a peak due to DSiO3 species is observed, but no peaks due to DSiO2 and DSiO species are observable. This result indicates that SiD, SiDH, and SiDH2 species are formed by substitution reactions, followed by oxidation of back-bonds to form DSiO3 species. After immersion in D2O for a day, 37% H atoms on the surface are replaced to D atoms.

Structural, magnetic, dielectric, and electrical properties of NiFe2O4 spinel ferrite nanoparticles prepared by honey-mediated sol-gel combustion

NASA Astrophysics Data System (ADS)

Yadav, Raghvendra Singh; Kuřitka, Ivo; Vilcakova, Jarmila; Havlica, Jaromir; Masilko, Jiri; Kalina, Lukas; Tkacz, Jakub; Enev, Vojtěch; Hajdúchová, Miroslava

2017-08-01

In this study, NiFe2O4 nanoparticles were synthesized using a honey-mediated sol-gel combustion method. The synthesized nanoparticles and samples annealed at 800 °C and 1100 °C were characterized by X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and vibrating sample magnetometry (VSM). XRD and Raman spectroscopy confirmed the formation of a cubic spinel ferrite structure. FE-SEM demonstrated the octahedral morphology of the NiFe2O4 spinel ferrite nanoparticles with sizes ranging from 10 to 70 nm. Quantitative analysis based on XPS suggested a mixed spinel structure comprising NiFe2O4 nanoparticles. XPS analysis determined occupation formulae of (Ni0.212+ Fe0.443+)[Ni0.792+ Fe1.563+]O4 and (Ni0.232+ Fe0.503+)[Ni0.772+ Fe1.503+]O4, for the as-prepared NiFe2O4 nanoparticles and those annealed at 1100 °C, respectively. Magnetic measurements showed that the saturation magnetization increased with the crystallite size from 32.3 emu/g (20 nm) to 49.9 emu/g (163 nm), whereas the coercivity decreased with the crystallite size from 162 Oe (20 nm) to 47 Oe (163 nm). Furthermore, the dielectric constant, dielectric loss tangent, and AC conductivity of the NiFe2O4 nanoparticles were dependent on the frequency (1-107 Hz) and grain size. The influence of the grain size was also observed by modulus spectroscopy based on the Cole-Cole plot.

Ultra-fine structures of Pd-Ag-HAp nanoparticle deposition on protruded TiO2 barrier layer for dental implant

NASA Astrophysics Data System (ADS)

Jang, Jae-Myung; Kim, Seung-Dai; Park, Tae-Eon; Choe, Han-Cheol

2018-02-01

The biocompatibility structure of an implant surface is of great importance to the formation of new bone tissue around the dental implant and also has a significant chemical reaction in the osseointegration process. Thus, ultra-fine Pd-Ag-HAp nanoparticles have been electrodeposited on protruded TiO2 barrier layer in mixed electrolyte solutions. Unusual protrusions patterns, which are assigned to Pd-Ag-HAp nanoparticles, can be clearly differentiated from a TiO2 nanotube oxide layer formed by an anodizing process. In the chemical bonding state, the surface characteristics of Pd/Ag/HAp compounds have been investigated by FE-SEM, EDS mapping analysis, and XPS analysis. The mapping dots of the elements including Ti, Ca, Pd, Ag, and P showed a homogeneous distribution throughout the entire surface when deposited onto the protruded TiO2 barrier layer. The XPS spectra of Ti-2p, O-1S, Pd-3d, and Ag-3d have been investigated, with the major XPS peak indicating Pd-3d. The Ag-3d level was clearly observed with further scanning of the Ca-2p region. Based on the results of the chemical states, the structural properties of the protrusion patterns were also examined after being deposited onto the barrier oxide film, resulting in the representative protrusion patterns being mainly composed of Pd-Ag-HAp compounds. The results of the soaking evaluation showed that the protrusion patterns and the protruded TiO2 barrier layer were all effective in regards to biocompatibility.

A ToF-SIMS and XPS study of protein adsorption and cell attachment across PEG-like plasma polymer films with lateral compositional gradients

NASA Astrophysics Data System (ADS)

Menzies, Donna J.; Jasieniak, Marek; Griesser, Hans J.; Forsythe, John S.; Johnson, Graham; McFarland, Gail A.; Muir, Benjamin W.

2012-12-01

In this work we report a detailed X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) study of poly(ethylene glycol) PEG-like chemical gradients deposited via plasma enhanced chemical vapour deposition (PECVD) at two different load powers using diethylene glycol dimethyl ether (DG) as a monomer. Principal component analysis (PCA) was applied to the ToF-SIMS data both before and after protein adsorption on the plasma polymer thin films. Results of the PCA loadings indicated a higher content of hydrocarbon fragments across the higher load power gradient, which adsorbed higher amounts of proteins. Gradients deposited at a lower load power retained a higher degree of monomer like functionality as did the central region directly underneath the knife edge electrode. Analysis of the adsorption of serum proteins (human serum albumin and fetal bovine serum) was monitored across the gradient films and increased with decreasing ether (PEG-like) film chemistries. The effect of protein incubation time on the levels adsorbed fetal bovine serum on the plasma polymer films was critical, with significantly more protein adsorbing after 24 hour incubation times on both gradient films. The attachment of HeLa cells on the gradients appeared to be dictated not only by the surface chemistry, but also by the adsorption of serum proteins. XPS analysis revealed that at surface ether concentrations of less than 70% in the gradient films, significant increases in protein and cell attachment were observed.

Influence of a cellulosic ether carrier on the structure of biphasic calcium phosphate ceramic particles in an injectable composite material.

PubMed

Dupraz, A; Nguyen, T P; Richard, M; Daculsi, G; Passuti, N

1999-04-01

An injectable composite material based on biphasic calcium phosphate (BCP) and a nonionic cellulose ether has been elaborated for use in percutaneous surgery for spine fusion. This paper reports the characterization results of this material by spectroscopic techniques including X-ray diffraction (XRD), infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) fitted with an energy dispersive X-Ray analysis system and high-resolution transmission electron microscopy (HR-TEM). From FTIR and XPS results, it was observed that the adhesion between the polymer and the ceramic might be insured by oxygen bridging developed through an ionic bonding between calcium ions and (C-O) groups of the polymer. Moreover, XPS showed attraction of Ca2+ ions in the polymer matrix, while the ceramic surface was modified in a HPO4(2-) -rich layer. These results suggest a possible dissolution/precipitation process at the interface ceramic/polymer. HR-TEM observations supported this hypothesis, showing a light contrasted fringe at the surface of the ceramic grains in the composite paste. As well, changes in the XRD spectra could indicate a small decrease in the crystal size of the BCP powder through the contact to polymer solution. In addition, SEM observation showed a decrease of the initial BCP granulometry. Aggregates of 80-200 microm seemed to be mostly dissociated in micrograins. The ceramic grains were coated with and bonded between each other by the polymer matrix, which acted as spacer in between the ceramic grains, creating a macroporous-like material structure.

Arsenopyrite and pyrite bioleaching: evidence from XPS, XRD and ICP techniques.

PubMed

Fantauzzi, Marzia; Licheri, Cristina; Atzei, Davide; Loi, Giovanni; Elsener, Bernhard; Rossi, Giovanni; Rossi, Antonella

2011-10-01

In this work, a multi-technical bulk and surface analytical approach was used to investigate the bioleaching of a pyrite and arsenopyrite flotation concentrate with a mixed microflora mainly consisting of Acidithiobacillus ferrooxidans. X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and X-ray-induced Auger electron spectroscopy mineral surfaces investigations, along with inductively coupled plasma-atomic emission spectroscopy and carbon, hydrogen, nitrogen and sulphur determination (CHNS) analyses, were carried out prior and after bioleaching. The flotation concentrate was a mixture of pyrite (FeS(2)) and arsenopyrite (FeAsS); after bioleaching, 95% of the initial content of pyrite and 85% of arsenopyrite were dissolved. The chemical state of the main elements (Fe, As and S) at the surface of the bioreactor feed particles and of the residue after bioleaching was investigated by X-ray photoelectron and X-ray excited Auger electron spectroscopy. After bioleaching, no signals of iron, arsenic and sulphur originating from pyrite and arsenopyrite were detected, confirming a strong oxidation and the dissolution of the particles. On the surfaces of the mineral residue particles, elemental sulphur as reaction intermediate of the leaching process and precipitated secondary phases (Fe-OOH and jarosite), together with adsorbed arsenates, was detected. Evidence of microbial cells adhesion at mineral surfaces was also produced: carbon and nitrogen were revealed by CHNS, and nitrogen was also detected on the bioleached surfaces by XPS. This was attributed to the deposition, on the mineral surfaces, of the remnants of a bio-film consisting of an extra-cellular polymer layer that had favoured the bacterial action. © Springer-Verlag 2011

4-Mercaptophenylboronic acid SAMs on gold: comparison with SAMs derived from thiophenol, 4-mercaptophenol, and 4-mercaptobenzoic acid.

PubMed

Barriet, David; Yam, Chi Ming; Shmakova, Olga E; Jamison, Andrew C; Lee, T Randall

2007-08-14

We report the formation and characterization of self-assembled monolayers (SAMs) derived from the adsorption of 4-mercaptophenylboronic acid (MPBA) on gold. For comparison, SAMs derived from the adsorption of thiophenol (TP), 4-mercaptophenol (MP), and 4-mercaptobenzoic acid (MBA) were also examined. The structure and properties of the SAMs were evaluated by ellipsometry, contact-angle goniometry, polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS). Specifically, ellipsometry was used to assess the formation of monolayer films, and contact angle measurements were used to determine the surface hydrophilicity and homogeneity. Separately, PM-IRRAS was used to evaluate the molecular composition and orientation as well as the intermolecular hydrogen bonding within the SAMs. Finally, XPS was used to evaluate the film composition and surface coverage (i.e., packing density), which was observed to increase in the following order: TP < MP < MPBA < MBA. A rationalization for the observed packing differences is presented. The XPS data indicate further that ultrahigh vacuum conditions induce the partial dehydration of MPBA SAMs with the concomitant formation of surface boronic anhydride species. Overall, the analytical data collectively show that the MPBA moieties in the SAMs exist in the acid form rather than the anhydride form under ambient laboratory conditions. Furthermore, stability studies find that MPBA SAMs are surprisingly labile in basic solution, where the terminal B-C bonds are cleaved by the attack of hydroxide ion and strongly basic amine nucleophiles. The unanticipated lability observed here should be considered by those wishing to use MPBA moieties in carbohydrate-sensing applications.

Zinc-Containing Magnetic Oxides Stabilized by a Polymer: One Phase or Two?

PubMed

Baird, Nicholas; Losovyj, Yaroslav; Yuzik-Klimova, Ekaterina Yu; Kuchkina, Nina V; Shifrina, Zinaida B; Pink, Maren; Stein, Barry D; Morgan, David Gene; Wang, Tianhao; Rubin, Mikhail A; Sidorov, Alexander I; Sulman, Esther M; Bronstein, Lyudmila M

2016-01-13

Here we developed a new family of Zn-containing magnetic oxides of different structures by thermal decomposition of Zn(acac)2 in the reaction solution of preformed magnetite nanoparticles (NPs) stabilized by polyphenylquinoxaline. Upon an increase of the Zn(acac)2 loading from 0.15 to 0.40 mmol (vs 1 mmol of Fe(acac)3), the Zn content increases, and the Zn-containing magnetic oxide NPs preserve a spinel structure of magnetite and an initial, predominantly multicore NP morphology. X-ray photoelectron spectroscopy (XPS) of these samples revealed that the surface of iron oxide NPs is enriched with Zn, although Zn species were also found deep under the iron oxide NP surface. For all the samples, XPS also demonstrates the atom ratio of Fe(3+)/Fe(2+) = 2:1, perfectly matching Fe3O4, but not ZnFe2O4, where Fe(2+) ions are replaced with Zn(2+). The combination of XPS with other physicochemical methods allowed us to propose that ZnO forms an ultrathin amorphous layer on the surface of iron oxide NPs and also diffuses inside the magnetite crystals. At higher Zn(acac)2 loading, cubic ZnO nanocrystals coexist with magnetite NPs, indicating a homogeneous nucleation of the former. The catalytic testing in syngas conversion to methanol demonstrated outstanding catalytic properties of Zn-containing magnetic oxides, whose activities are dependent on the Zn loading. Repeat experiments carried out with the best catalyst after magnetic separation showed remarkable catalyst stability even after five consecutive catalytic runs.

Ultra-high vacuum surface analysis study of rhodopsin incorporation into supported lipid bilayers.

PubMed

Michel, Roger; Subramaniam, Varuni; McArthur, Sally L; Bondurant, Bruce; D'Ambruoso, Gemma D; Hall, Henry K; Brown, Michael F; Ross, Eric E; Saavedra, S Scott; Castner, David G

2008-05-06

Planar supported lipid bilayers that are stable under ambient atmospheric and ultra-high-vacuum conditions were prepared by cross-linking polymerization of bis-sorbylphosphatidylcholine (bis-SorbPC). X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were employed to investigate bilayers that were cross-linked using either redox-initiated radical polymerization or ultraviolet photopolymerization. The redox method yields a more structurally intact bilayer; however, the UV method is more compatible with incorporation of transmembrane proteins. UV polymerization was therefore used to prepare cross-linked bilayers with incorporated bovine rhodopsin, a light-activated, G-protein-coupled receptor (GPCR). A previous study (Subramaniam, V.; Alves, I. D.; Salgado, G. F. J.; Lau, P. W.; Wysocki, R. J.; Salamon, Z.; Tollin, G.; Hruby, V. J.; Brown, M. F.; Saavedra, S. S. J. Am. Chem. Soc. 2005, 127, 5320-5321) showed that rhodopsin retains photoactivity after incorporation into UV-polymerized bis-SorbPC, but did not address how the protein is associated with the bilayer. In this study, we show that rhodopsin is retained in supported bilayers of poly(bis-SorbPC) under ultra-high-vacuum conditions, on the basis of the increase in the XPS nitrogen concentration and the presence of characteristic amino acid peaks in the ToF-SIMS data. Angle-resolved XPS data show that the protein is inserted into the bilayer, rather than adsorbed on the bilayer surface. This is the first study to demonstrate the use of ultra-high-vacuum techniques for structural studies of supported proteolipid bilayers.

Dysprosium electrodeposition from a hexaalkylguanidinium-based ionic liquid.

PubMed

Berger, Claudia A; Arkhipova, Maria; Maas, Gerhard; Jacob, Timo

2016-08-07

The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important elements for high-tech industries and is mainly used in permanent magnetic applications, for example in electric vehicles, industrial motors and direct-drive wind turbines. In an effort to develop a more efficient electrochemical technique for depositing Dy on Nd-magnets in contrast to commonly used costly physical vapor deposition, we investigated the electrochemical behavior of dysprosium(iii) trifluoromethanesulfonate in a custom-made guanidinium-based room-temperature ionic liquid (RTIL). We first examined the electrodeposition of Dy on an Au(111) model electrode. The investigation was carried out by means of cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). CV measurements revealed a large cathodic reduction peak, which corresponds to the growth of monoatomic high islands, based on STM images taken during the initial stages of deposition. XPS identified these deposited islands as dysprosium. A similar reduction peak was also observed on an Nd-Fe-B substrate, and positively identified as deposited Dy using XPS. Finally, we varied the concentration of the Dy precursor, electrolyte flow and temperature during Dy deposition and demonstrated that each of these parameters could be used to increase the thickness of the Dy deposit, suggesting that these parameters could be tuned simultaneously in a temperature-controlled flow cell to enhance the thickness of the Dy layer.

As-Received, Ozone Cleaned and Ar+ Sputtered Surfaces of Hafnium Oxide Grown by Atomic Layer Deposition and Studied by XPS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Engelhard, Mark H.; Herman, Jacob A.; Wallace, Robert

2012-06-27

In this study, X-ray photoelectron spectroscopy (XPS) characterization was performed on 47 nm thick hafnium oxide (HfO{sub 2}) films grown by atomic layer deposition using TEMA-Hf/H{sub 2}O at 250 C substrate temperature. HfO{sub 2} is currently being studied as a possible replacement for Silicon Oxide (SiO{sub 2}) as a gate dielectric in electronics transistors. XPS spectra were collected on a Physical Electronics Quantum 2000 Scanning ESCA Microprobe using a monochromatic Al K{sub a} X-ray (1486.7 eV) excitation source. The sample was analyzed under the following conditions: as received, after UV irradiation for five minutes, and after sputter cleaning with 2more » kV Ar{sup +} ions for 180 seconds. Survey scans showed carbon, oxygen, and hafnium as the major species in the film, while the only minor species of argon and carbide was detected after sputtering. Adventitious carbon initially composed approximately 18.6 AT% of the surface, but after UV cleaning it was reduced to 2.4 AT%. This demonstrated that that the majority of carbon was due to adventitious carbon. However, after 2 kV Ar{sup +} sputtering there was still only trace amounts of carbon at {approx}1 AT%, Some of this trace carbon is now in the form of a carbide due to the interaction with Ar{sup +} used for sputter cleaning. Furthermore, the stoiciometric ratio of oxygen and hafnium is consistent with a high quality HfO{sub 2} film.« less

A XPS Study of the Passivity of Stainless Steels Influenced by Sulfate-Reducing Bacteria.

NASA Astrophysics Data System (ADS)

Chen, Guocun

The influence of sulfate-reducing bacteria (SRB) on the passivity of type 304 and 317L stainless steels (SS) was investigated by x-ray photoelectron spectroscopy (XPS), microbiological and electrochemical techniques. Samples were exposed to SRB, and then the resultant surfaces were analyzed by XPS, and the corrosion resistance by potentiodynamic polarization in deaerated 0.1 M HCl. To further understand their passivity, the SRB-exposed samples were analyzed by XPS after potentiostatic polarization at a passive potential in the hydrochloric solution. The characterization was performed under two surface conditions: unrinsed and rinsed by deaerated alcohol and deionized water. Comparisons were made with control samples immersed in uninoculated medium. SRB caused a severe loss of the passivity of 304 SS through sulfide formation and possible additional activation to form hexavalent chromium. The sulfides included FeS, FeS_2, Cr_2S _3, NiS and possibly Fe_ {rm 1-x}S. The interaction took place nonuniformly, resulting in undercutting of the passive film and preferential hydration of inner surface layers. The bacterial activation of the Cr^{6+ }^ecies was magnified by subsequent potentiostatic polarization. In contrast, 317L SS exhibited a limited passivity. The sulfides were formed mainly in the outer layers. Although Cr^{6+}^ecies were observed after the exposure, they were dissolved upon polarization. Since 317L SS has a higher Mo content, its higher passivity was ascribed to Mo existing as molybdate on the surface and Mo^{5+} species in the biofilm. Consequently, the interaction of SRB with Mo was studied. It was observed that molybdate could be retained on the surfaces of Mo coupons by corrosion products. In the presence of SRB, however, a considerable portion of the molybdate interacted with intermediate sulfur -containing proteins, forming Mo(V)-S complexes and reducing bacterial growth and sulfate reduction. The limited insolubility of the Mo(V)-S complexes in 0.1 M HCl provided a certain protection so that the pitting potential of the SRB-exposed Mo coupons was not considerably decreased. The interaction of the sulfur-containing proteins with Mo also provided mechanistic information about the adhesion of biofilm to Mo-bearing steels. Additionally, the interactions of SRB with other alloying elements, Cr and Ni, were investigated.

Inhibition of bacterial adhesion on PVC endotracheal tubes by RF-oxygen glow discharge, sodium hydroxide and silver nitrate treatments.

PubMed

Balazs, D J; Triandafillu, K; Wood, P; Chevolot, Y; van Delden, C; Harms, H; Hollenstein, C; Mathieu, H J

2004-05-01

Medical-grade poly(vinyl chloride) (PVC) was chemically modified to study how the incorporation of monovalent silver influences Pseudomonas aeruginosa adhesion and colonization. The modification investigated consisted of a radio frequency-oxygen (RF-O(2)) glow discharge pre-functionalization, followed by a two-step wet-treatment in sodium hydroxide and silver nitrate solutions. X-ray photoelectron spectroscopy (XPS) analysis and contact angle measurements were used to investigate the chemical nature and surface wettability of the films following each step of the modification. XPS analysis proved that the RF-O(2) plasma pre-functionalization of native PVC reproducibly increased the amount of functional groups representative of PVC additives, including ether/alcohol, esters and carboxyl groups. More specifically, we demonstrated that the O-C=O groups representative of the phthalic ester and zinc carboxylate additives identified for native PVC increased by two-fold following the RF-O(2) plasma pre-functionalization step. Although RF-O(2) pre-functionalization did not have an effect on the silver content of the NaOH/AgNO(3) treated substrates, such a modification was necessary for biomaterial products that did not have reproducible surfaces amongst production lots. XPS analysis also demonstrated that saponification with sodium hydroxide (NaOH) of esters, like those of the phthalic ester additives of PVC is a simple, irreversible method of hydrolysis, which produced sodium carboxylate and sodium phthalate salts. Exposure of native PVC to NaOH resulted in an increased surface hydrophilicity (from ca 90 degrees to ca 60 degrees ) due to dechlorination. XPS analysis following further incubation in silver nitrate demonstrated that silver ions can be trapped when the sodium of sodium carboxylate is replaced by silver after performing a second treatment with a monovalent silver-containing solution. The creation of silver salt on native PVC resulted in an ultra-hydrophobic (>120 degrees ) surface. The chemical modifications using NaOH and AgNO(3) wet treatments completely inhibited bacterial adhesion of four strains of P. aeruginosa to both native and oxygen-pre-functionalized PVC, and efficiently prevented colonization over longer periods (72 h). Our results suggest that surface modifications that incorporate silver ions would be extremely effective at reducing bacterial colonization to medical devices.

Coprecipitation of nickel zinc malonate: A facile and reproducible synthesis route for Ni{sub 1−x}Zn{sub x}O nanoparticles and Ni{sub 1−x}Zn{sub x}O/ZnO nanocomposites via pyrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lontio Fomekong, Roussin, E-mail: lonforou@yahoo.fr; Institut de la Matière Condensée et des Nanosciences, Université Catholique de Louvain, Croix du Sud 1, 1348 Louvain-La-Neuve; Kenfack Tsobnang, Patrice

2015-10-15

Nanoparticles of Ni{sub 1−x}Zn{sub x}O and Ni{sub 1−x}Zn{sub x}O/ZnO, which can be good candidates for selective gas sensors, were successfully obtained via a two-step synthetic route, in which the nickel zinc malonate precursor was first synthesized by co-precipitation from an aqueous solution, followed by pyrolysis in air at a relatively low temperature (~500 °C). The precursor was characterized by ICP-AES, FTIR and TG and the results indicate the molecular structure of the precursor to be compatible with Ni{sub 1−x}Zn{sub x}(OOCCH{sub 2}COO)·2H{sub 2}O. The decomposition product, characterized using various techniques (FTIR, XRD, ToF-SIMS, SEM, TEM and XPS), was established to bemore » a doped nickel oxide (Ni{sub 1−x}Zn{sub x}O for 0.01≤x≤0.1) and a composite material (Ni{sub 1−x}Zn{sub x}O/ZnO for 0.2≤x≤0.5). To elucidate the form in which the Zn is present in the NiO structure, three analytical techniques were employed: ToF-SIMS, XRD and XPS. While ToF SIMS provided a direct evidence of the presence of Zn in the NiO crystal structure, XRD showed that Zn actually substitutes Ni in the structure and XPS is a bit more specific by indicating that the Zn is present in the form of Zn{sup 2+} ions. - Highlights: • Coprecipitation synthesis of nickel zinc malonate single bath precursor was achieved. • The as synthesized precursors are an homogeneous mixture of nickel and zinc malonate. • XRD, ToF-SIMS, XPS, SEM and TEM was used to characterized decomposition products. • Ni{sub 1−x}Zn{sub x}O nanoparticles (0.01≤x≤0.1) formed after pyrolysis (~500 °C) of precursor. • Ni{sub 1−x}Zn{sub x}O/ZnO nanocomposite (0.2≤x≤0.5) formed after pyrolysis at 500 °C of precursor.« less

Functionalization and Characterization of Gold Nanoparticles

NASA Astrophysics Data System (ADS)

Techane, Sirnegeda D.

2011-12-01

Surface characterization of gold nanoparticles (AuNPs) is necessary to obtain a thorough understanding of the AuNP properties and ultimately realize their full potential in applications. The work described in this dissertation strives to the structure and composition of AuNPs using highly surface sensitive techniques such as X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) in addition to the more widely used characterization techniques such as transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FTIR) and UV-VIS spectroscopy. Self-assembled monolayers (SAMs) of alkanethiols were used to modify AuNPs surfaces to create positively and negatively charged surfaces. Functionalization with carboxylic acid terminated alkanethiol SAMs (COON-SAMs) was first optimized to produce clean and stable negatively charged AuNPs. Using 14nm and 40nm diameter AuNPs in combination with C11 and C16 chain length COOH-SAMs, it was found that addition of NH4OH during functionalization coupled with dialysis purification produced AuNPs that did not aggregate and did not have unbound thiols. Effects of AuNP size and COOH-SAM chain lengths were studied using 14, 25 and 40nm average diameter AuNPs functionalized with C6, C8, C11 and C16 COOH-SAMs. Flat Au surfaces were also functionalized with the COOH-SAMs for comparison. It was shown that the 14nm AuNPs with C16 COOH-SAMs were the most stable and had crystalline-like, well-ordered SAM structures. The SAMs on the 40nm AuNPs had similar surface chemistry as the SAMs on the flat Au surfaces. The effective photoelectron take-off angle of the C16 COOH-SAM decreased when the size of the AuNP increased. It was also shown that when using Kratos AxisUltra DLD XPS instrument in the hybrid mode, it was important to consider effects of both the hybrid mode and the AuNPs curvature when calculating overlayer thickness of the SAMs on AuNPs. Using the Kratos in the electrostatic mode, the overlayer thickness of C16 COON-SAM was 21A on a flat Au surface, which was comparable with previously reported values. However, the apparent thickness of the same SAM on the 14nm AuNPs was 31A, indicating the curvature of the AuNPs had an effect on the XPS measurements. To produce the positively charged AuNP surfaces, amine terminated alkanethiols (NH2 -thiols) with a C2 chain length were used in one-step AuNP synthesis and functionalization process followed by a ligand-exchange reaction with C11 chain length NH2-thiols. It was found that 14 days were needed for the ligand-exchange to be complete. After the ligand-exchange, it was found that the AuNPs with C11 NH2-SAMs were stable and could be purified, unlike AuNPs with C2 NH2-SAMs which aggregated upon purification. The C11 NH2-SAMs had both unbound and oxidized sulfur, which could be removed/converted after hydrochloric acid treatment. SESSA (simulation of electron spectra for surface analysis) allowed better interpretation of the XPS data of SAMs on AuNPs and flat Au. Comparing SESSA and experimental XPS data, it was found that C16 COON-SAM on a flat Au surface was 20A thick with a 1.5A hydrocarbon contamination overlayer and 1.05 relative surface roughness. After geometric weighing of angle-resolved XPS and SESSA data, it was found that C16 COOH-SAMs on 14nm AuNPs were 17A thick with a 1.5A hydrocarbon contamination. The decreased SAM thickness on the AuNPs is likely due to an increased tilt angle of the alkane chains or increased disorder in the SAM.

In situ supported MnOx-CeOx on carbon nanotubes for the low-temperature selective catalytic reduction of NO with NH3

NASA Astrophysics Data System (ADS)

Zhang, Dengsong; Zhang, Lei; Shi, Liyi; Fang, Cheng; Li, Hongrui; Gao, Ruihua; Huang, Lei; Zhang, Jianping

2013-01-01

The MnOx and CeOx were in situ supported on carbon nanotubes (CNTs) by a poly(sodium 4-styrenesulfonate) assisted reflux route for the low-temperature selective catalytic reduction (SCR) of NO with NH3. X-Ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature-programmed desorption (NH3-TPD) have been used to elucidate the structure and surface properties of the obtained catalysts. It was found that the in situ prepared catalyst exhibited the highest activity and the most extensive operating-temperature window, compared to the catalysts prepared by impregnation or mechanically mixed methods. The XRD and TEM results indicated that the manganese oxide and cerium oxide species had a good dispersion on the CNT surface. The XPS results demonstrated that the higher atomic concentration of Mn existed on the surface of CNTs and the more chemisorbed oxygen species exist. The H2-TPR results suggested that there was a strong interaction between the manganese oxide and cerium oxide on the surface of CNTs. The NH3-TPD results demonstrated that the catalysts presented a larger acid amount and stronger acid strength. In addition, the obtained catalysts exhibited much higher SO2-tolerance and improved the water-resistance as compared to that prepared by impregnation or mechanically mixed methods.The MnOx and CeOx were in situ supported on carbon nanotubes (CNTs) by a poly(sodium 4-styrenesulfonate) assisted reflux route for the low-temperature selective catalytic reduction (SCR) of NO with NH3. X-Ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature-programmed desorption (NH3-TPD) have been used to elucidate the structure and surface properties of the obtained catalysts. It was found that the in situ prepared catalyst exhibited the highest activity and the most extensive operating-temperature window, compared to the catalysts prepared by impregnation or mechanically mixed methods. The XRD and TEM results indicated that the manganese oxide and cerium oxide species had a good dispersion on the CNT surface. The XPS results demonstrated that the higher atomic concentration of Mn existed on the surface of CNTs and the more chemisorbed oxygen species exist. The H2-TPR results suggested that there was a strong interaction between the manganese oxide and cerium oxide on the surface of CNTs. The NH3-TPD results demonstrated that the catalysts presented a larger acid amount and stronger acid strength. In addition, the obtained catalysts exhibited much higher SO2-tolerance and improved the water-resistance as compared to that prepared by impregnation or mechanically mixed methods. Electronic supplementary information (ESI) available: SEM images and EDS analysis, TEM images, and XPS spectrum of samples. See DOI: 10.1039/c2nr33006g

WEATHERING DEGRADATION OF A POLYURETHANE COATING. (R828081E01)

EPA Science Inventory

The degradation of polyurethane topcoat over a chromate pigmented epoxy primer was examined by atomic force microscopy (AFM), scanning electronic microscopy (SEM), X-ray photo-electron spectroscopy (XPS) and Fourier transform infra-red spectroscopy (FTIR) after the coated pane...

Problems at the Leading Edge of Space Weathering as Revealed by TEM Combined with Surface Science Techniques

NASA Astrophysics Data System (ADS)

Christoffersen, R.; Dukes, C. A.; Keller, L. P.; Rahman, Z.; Baragiola, R. A.

2015-11-01

Analytical field-emission TEM techniques cross-correlated with surface analyses by X-ray photoelectron spectroscopy (XPS) provides a unique two-prong approach for characterizing how solar wind ion processing contributes to space weathering.

Plasma copolymerization of ethylene and tetrafluoroethylene

NASA Technical Reports Server (NTRS)

Golub, Morton A.; Wydeven, Theodore; Cormia, Robert D.

1992-01-01

An IR and XPS study of the low-pressure, radiofrequency, glow-discharge plasma copolymerization of ethylene (ET) and tetrafluoroethylene (TFE) is presented. The potential for creating Tefzel- or Teflon-like coatings on various polymeric substrates for use in advanced life support systems is examined.

Consequences of realistic embedding for the L 2,3 edge XAS of α-Fe 2 O 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bagus, Paul S.; Nelin, Connie J.; Sassi, Michel

Cluster models of condensed systems are often used to simulate the core-level spectra obtained with X-ray Photoelectron Spectroscopy, XPS, or with X-ray Absorption Spectroscopy, XAS, especially for near edge features.

Surface characterisation of ethylene propylene diene rubber upon exposure to aqueous acidic solution

NASA Astrophysics Data System (ADS)

Mitra, Susanta; Ghanbari-Siahkali, Afshin; Kingshott, Peter; Hvilsted, Søren; Almdal, Kristoffer

2006-07-01

Two types of pure ethylene propylene diene rubbers were exposed to two different acids for varying period of time. Surface characterisation was carried out using X-ray photoelectron spectroscopy (XPS). Two EPDM rubbers selected for this study were comparable in co-monomer compositions but significantly different with respect to molar mass and the presence of long chain branching. Both rubbers contained 5-ethylidene-2-norbornene (ENB) as diene. Solution cast films of pure EPDM samples were exposed in two different acidic solutions, viz. chromosulphuric (Cr (VI)/H 2SO 4) and sulphuric acid (H 2SO 4) (20%, v/v) at ambient temperature from 1 to 12 weeks. XPS analysis indicated that several oxygenated species were formed on the surface of both rubbers after exposure. It was postulated from the XPS analyses that both aqueous acidic solutions attacked the olefinic double bonds (C dbnd C) of ENB. Furthermore, 20% Cr (VI)/H 2SO 4 also attacked the allylic carbon-hydrogen (C sbnd H) bonds of ENB resulting in more oxygenated species on the surface compared to 20% H 2SO 4 under identical conditions. Cr (VI) in the 20% Cr (VI)/H 2SO 4 was found to play an important role in alteration of surface chemistry. Studies using a model system consisting of EPDM mixed with Cr (VI) and Cr (III) salts revealed that the change of oxidation state from Cr (VI) to Cr (III) as a consequence of direct involvement of Cr (VI) in the chemical alteration of EPDM surfaces. Interestingly, the presence of long chain branching and molar mass did not significantly influence the chemical processes owing to the acid treatment.

Atomic charges of sulfur in ionic liquids: experiments and calculations.

PubMed

Fogarty, Richard M; Rowe, Rebecca; Matthews, Richard P; Clough, Matthew T; Ashworth, Claire R; Brandt, Agnieszka; Corbett, Paul J; Palgrave, Robert G; Smith, Emily F; Bourne, Richard A; Chamberlain, Thomas W; Thompson, Paul B J; Hunt, Patricia A; Lovelock, Kevin R J

2017-12-14

Experimental near edge X-ray absorption fine structure (NEXAFS) spectra, X-ray photoelectron (XP) spectra and Auger electron spectra are reported for sulfur in ionic liquids (ILs) with a range of chemical structures. These values provide experimental measures of the atomic charge in each IL and enable the evaluation of the suitability of NEXAFS spectroscopy and XPS for probing the relative atomic charge of sulfur. In addition, we use Auger electron spectroscopy to show that when XPS binding energies differ by less than 0.5 eV, conclusions on atomic charge should be treated with caution. Our experimental data provides a benchmark for calculations of the atomic charge of sulfur obtained using different methods. Atomic charges were computed for lone ions and ion pairs, both in the gas phase (GP) and in a solvation model (SMD), with a wide range of ion pair conformers considered. Three methods were used to compute the atomic charges: charges from the electrostatic potential using a grid based method (ChelpG), natural bond orbital (NBO) population analysis and Bader's atoms in molecules (AIM) approach. By comparing the experimental and calculated measures of the atomic charge of sulfur, we provide an order for the sulfur atoms, ranging from the most negative to the most positive atomic charge. Furthermore, we show that both ChelpG and NBO are reasonable methods for calculating the atomic charge of sulfur in ILs, based on the agreement with both the XPS and NEXAFS spectroscopy results. However, the atomic charges of sulfur derived from ChelpG are found to display significant, non-physical conformational dependence. Only small differences in individual atomic charge of sulfur were observed between lone ion (GP) and ion pair IL(SMD) model systems, indicating that ion-ion interactions do not strongly influence individual atomic charges.

Proton transfer and hydrogen bonding in the organic solid state: a combined XRD/XPS/ssNMR study of 17 organic acid-base complexes.

PubMed

Stevens, Joanna S; Byard, Stephen J; Seaton, Colin C; Sadiq, Ghazala; Davey, Roger J; Schroeder, Sven L M

2014-01-21

The properties of nitrogen centres acting either as hydrogen-bond or Brønsted acceptors in solid molecular acid-base complexes have been probed by N 1s X-ray photoelectron spectroscopy (XPS) as well as (15)N solid-state nuclear magnetic resonance (ssNMR) spectroscopy and are interpreted with reference to local crystallographic structure information provided by X-ray diffraction (XRD). We have previously shown that the strong chemical shift of the N 1s binding energy associated with the protonation of nitrogen centres unequivocally distinguishes protonated (salt) from hydrogen-bonded (co-crystal) nitrogen species. This result is further supported by significant ssNMR shifts to low frequency, which occur with proton transfer from the acid to the base component. Generally, only minor chemical shifts occur upon co-crystal formation, unless a strong hydrogen bond is formed. CASTEP density functional theory (DFT) calculations of (15)N ssNMR isotropic chemical shifts correlate well with the experimental data, confirming that computational predictions of H-bond strengths and associated ssNMR chemical shifts allow the identification of salt and co-crystal structures (NMR crystallography). The excellent agreement between the conclusions drawn by XPS and the combined CASTEP/ssNMR investigations opens up a reliable avenue for local structure characterization in molecular systems even in the absence of crystal structure information, for example for non-crystalline or amorphous matter. The range of 17 different systems investigated in this study demonstrates the generic nature of this approach, which will be applicable to many other molecular materials in organic, physical, and materials chemistry.

Determination of oligomeric chain length distributions at surfaces using ToF-SIMS: segregation effects and polymer properties

NASA Astrophysics Data System (ADS)

Gardella, Joseph A.; Mahoney, Christine M.

2004-06-01

While many XPS and SIMS studies of polymers have detected and quantified segregation of low surface energy blocks or components in copolymers and polymer blends [D. Briggs, in: D.R. Clarke, S. Suresh, I.M. Ward (Eds.), Surface Analysis of Polymers by XPS and Static SIMS, Cambridge University Press, Cambridge, 1998 (Chapter 5).], this paper reports ToF-SIMS studies of direct measurement of the segment length distribution at the surface of siloxane copolymers. These data allow insight into the segregation of particular portions of the oligomeric distribution; specifically, in this study, longer PDMS oligomers segregated at the expense of shorter PDMS chains. We have reported XPS analysis of competitive segregation effects for short PDMS chains [Macromolecules 35 (13) (2002) 5256]. In this study, a series of poly(ureaurethane)-poly(dimethylsiloxane) (PUU-PDMS) copolymers have been synthesized containing varying ratios of G-3 and G-9 (G- X describes the average segment length of the PDMS added), while maintaining a constant overall siloxane weight percentage (10, 30, and 60%). These copolymers were utilized as model systems to study the preferential segregation of certain siloxane segment lengths to the surface over others. ToF-SIMS analysis of PUU-PDMS copolymers has yielded high-mass range copolymer fragmentation patterns containing intact PDMS segments. For the first time, this information is utilized to determine PDMS segment length distributions at the copolymer surface as compared to the bulk. The results show that longer siloxane segment lengths are preferentially segregating to the surface over shorter chain lengths. These results also show the importance of ToF-SIMS and mass spectrometry in the development of new materials containing low molecular weight amino-propyl-terminated siloxanes.

Growth, microstructure and electrical properties of sputter-deposited hafnium oxide (HfO2) thin films grown using HfO2 ceramic target

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aguirre, B.; Vemuri, R. S.; Zubia, David

2011-01-01

Hafnium oxide (HfO₂) thin films have been made by radio-frequency (rf) magnetron-sputtering onto Si(100) substrates under varying growth temperature (Ts). HfO₂ ceramic target has been employed for sputtering while varying the Ts from room temperature to 500⁰C during deposition. The effect of Ts on the growth and microstructure of deposited HfO₂ films has been studied using grazing incidence x-ray diffraction (GIXRD), X-ray photoelectron spectroscopy (XPS), and high-resolution scanning electron microscopy (HR-SEM) coupled with energy dispersive x-ray spectrometry (EDS). The results indicate that the effect of Ts is significant on the growth, surface and interface structure, morphology and chemical composition ofmore » the HfO₂ films. Structural characterization indicates that the HfO₂ films grown at Ts<200 ⁰C are amorphous while films grown at Ts>200 ⁰C are nanocrystalline. An amorphous-to-crystalline transition occurs at Ts=200 ⁰C. Nanocrystalline HfO₂ films crystallized in a monoclinic structure with a (-111) orientation. XPS measurements indicated the high surface-chemical quality and stoichiometric nature of the grown HfO₂ films. An interface layer (IL) formation occurs due to reaction at the HfO₂-Si interface for HfO₂ films deposited at Ts>200 ⁰C. The thickness of IL increases with increasing Ts. XPS and EDS at the HfO₂-Si cross-section indicate the IL is a (Hf, Si)-O compound. The electrical characterization using capacitance-voltage measurements indicate that the dielectric constant decreases from 25 to 16 with increasing Ts.« less

Spontaneous desorption and phase transitions of self-assembled alkanethiol and alicyclic thiol monolayers chemisorbed on Au(111) in ultrahigh vacuum at room temperature.

PubMed

Ito, Eisuke; Kang, Hungu; Lee, Dongjin; Park, Joon B; Hara, Masahiko; Noh, Jaegeun

2013-03-15

Scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) were used to examine the surface structure and adsorption conditions of hexanethiol (HT) and cyclohexanethiol (CHT) self-assembled monolayers (SAMs) on Au(111) as a function of storage period in ultrahigh vacuum (UHV) conditions of 3×10(-7) Pa at room temperature (RT). STM imaging revealed that after storage for 7 days, HT SAMs underwent phase transitions from c(4×2) phase to low coverage 4×√3 phase. This transition is due to a structural rearrangement of hexanethiolates that results from the spontaneous desorption of chemisorbed HT molecules on Au(111) surface. XPS measurements showed approximately 28% reduction in sulfur coverage, which indicates desorption of hexanethiolates from the surfaces. Contrary to HT SAMs, the structural order of CHT SAMs with (5×2√3)R35° phase completely disappeared after storage for 3 or 7 days. XPS results show desorption of more than 80% of the cyclohexanethiolates, even after storage for 3 days. We found that spontaneous desorption of CHT molecules on Au(111) in UHV at RT occurred quickly, whereas spontaneous desorption of HT molecules was much slower. Thermal desorption spectroscopy (TDS) results suggest CHT SAMs in UHV at RT can desorb more efficiently than HT SAMs due to formation of thiol desorption fragments that result from chemical reactions between surface hydrogen atoms and thiolates on Au(111) surfaces. This study clearly demonstrated that organic thiols chemisorbed on gold surfaces are desorbed spontaneously in UHV at RT and van der Waals interactions play an important role in determining the structural stability of thiolate SAMs in UHV. Copyright © 2012 Elsevier Inc. All rights reserved.

Molecular-level removal of proteinaceous contamination from model surfaces and biomedical device materials by air plasma treatment.

PubMed

Banerjee, K K; Kumar, S; Bremmell, K E; Griesser, H J

2010-11-01

Established methods for cleaning and sterilising biomedical devices may achieve removal of bioburden only at the macroscopic level while leaving behind molecular levels of contamination (mainly proteinaceous). This is of particular concern if the residue might contain prions. We investigated at the molecular level the removal of model and real-life proteinaceous contamination from model and practical surfaces by air plasma (ionised air) treatment. The surface-sensitive technique of X-ray photoelectron spectroscopy (XPS) was used to assess the removal of proteinaceous contamination, with the nitrogen (N1s) photoelectron signal as its marker. Model proteinaceous contamination (bovine serum albumin) adsorbed on to a model surface (silicon wafer) and the residual proteinaceous contamination resulting from incubating surgical stainless steel (a practical biomaterial) in whole human blood exhibited strong N1s signals [16.8 and 18.5 atomic percent (at.%), respectively] after thorough washing. After 5min air plasma treatment, XPS detected no nitrogen on the sample surfaces, indicating complete removal of proteinaceous contamination, down to the estimated XPS detection limit 10ng/cm(2). Applying the same plasma treatment, the 7.7at.% nitrogen observed on a clinically cleaned dental bur was reduced to a level reflective of new, as-received burs. Contact angle measurements and atomic force microscopy also indicated complete molecular-level removal of the proteinaceous contamination upon air plasma treatment. This study demonstrates the effectiveness of air plasma treatment for removing proteinaceous contamination from both model and practical surfaces and offers a method for ensuring that no molecular residual contamination such as prions is transferred upon re-use of surgical and dental instruments. Crown Copyright © 2010. Published by Elsevier Ltd. All rights reserved.

Chemical and morphological characterization of TSP and PM2.5 by SEM-EDS, XPS and XRD collected in the metropolitan area of Monterrey, Mexico

NASA Astrophysics Data System (ADS)

González, Lucy T.; Rodríguez, F. E. Longoria; Sánchez-Domínguez, M.; Leyva-Porras, C.; Silva-Vidaurri, L. G.; Acuna-Askar, Karim; Kharisov, B. I.; Villarreal Chiu, J. F.; Alfaro Barbosa, J. M.

2016-10-01

Total suspended particles (TSP) and particles smaller than 2.5 μm (PM2.5) were collected at four sites in the metropolitan area of Monterrey (MAM) in Mexico. The samples were characterized by X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), and Scanning Electron Microscopy (SEM). In order to determine the possible sources of emissions of atmospheric particulate matter, a principal component analysis (PCA) was performed. The XRD results showed that the major crystalline compounds found in the TPS were CaCO3 and SiO2; while in the PM2.5 CaSO4 was found. The XPS analysis showed that the main elements found on the surface of the particles were C, O, Si, Ca, S, and N. The deconvolution carried out on the high-resolution spectra for C1s, S2p and N1s, showed that the aromatics, sulfates and pyrrolic-amides were the main groups contributing to the signal of these elements, respectively. The C-rich particles presented a spherical morphology, while the Ca- and Si-based particles mostly showed a prismatic shape. The PCA analysis together with the results obtained from the characterization techniques, suggested that the main contributors to the CaCO3 particles collected in the PM were most probably produced and emitted into the atmosphere by local construction industries and exploitation of rich-deposits of calcite. Meanwhile, the SiO2 found in the MAM originated from the suspension of geological material abundant in the region, and the carbon particles were mainly produced by the combustion of fossil fuels.

Determination of trace metals in TSP and PM2.5 materials collected in the Metropolitan Area of Monterrey, Mexico: A characterization study by XPS, ICP-AES and SEM-EDS

NASA Astrophysics Data System (ADS)

González, Lucy T.; Longoria Rodríguez, F. E.; Sánchez-Domínguez, M.; Cavazos, Aleyda; Leyva-Porras, C.; Silva-Vidaurri, L. G.; Askar, Karim Acuña; Kharissov, B. I.; Villarreal Chiu, J. F.; Alfaro Barbosa, J. M.

2017-11-01

The concentration levels of trace metals of toxicological importance were evaluated in the total suspended particles (TSP) and particulate matter smaller than 2.5 μm (PM2.5) collected in the Metropolitan Area of Monterrey (MAM) in Mexico. Samples were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy with an energy-dispersive spectroscopy system (SEM-EDS). In addition, the data were statistically treated by the methodology of Pearson Correlation (PC) and Principal Components Analysis (PCA) to identify the possible emitting sources. Surface analysis of the particulate matter (PM) by XPS revealed that the most abundant elements were Ca, Al, Na, Zn, Cu and Mg. The deconvolution of the Ca2p, Zn2p and Cu2p signals showed that the main contributors were CaCO3, ZnO and Cu/Cu2O, respectively. The bulk analysis of the PM by ICP-AES showed Fe, Cu and Zn as the most abundant elements. Fe-rich particles presented two different morphologies: the prismatic particles were associated with a natural origin, while the spherical particles with anthropogenic sources. The Zn and Cu were predominantly observed in the sampling stations with high vehicular traffic, and the emitting sources were associated with the burning of fuels from automobiles and the wear of the tires and brakes. The highest concentration of Pb was detected in the sampling station located near the industrial zones, and its cause was associated with the ceramic and glass industries, the burning of fuel oil in power plants and the production of lead-based batteries for automobiles.

Forsterite surface composition in aqueous solutions: a combined potentiometric, electrokinetic, and spectroscopic approach

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques

2000-10-01

Surfaces of natural and synthetic forsterite (Fo 91 and Fo 100) in aqueous solutions at 25°C were investigated using surface titrations in batch and limited residence time reactors, column filtration experiments, electrokinetic measurements (streaming potential and electrophoresis techniques), Diffuse Reflectance Infrared Spectroscopy (DRIFT), and X-ray Photoelectron Spectroscopy (XPS). At pH < 9, a Mg-depleted, Si-rich layer (<20 Å thick) is formed on the forsterite surface due to a Mg 2+ ↔ H + exchange reaction. Electrokinetic measurements yield a pH IEP value of 4.5 corresponding to the dominance of SiO 2 in the surface layer at pH < 9. In contrast, surface titrations of fresh powders give an apparent pH PZC of about 10 with the development of a large positive charge (up to 10 -4 mol/m 2 or 10 C/m 2) in the acid pH region. This may be explained by penetration of H + into the first unit cells of forsterite surface. The surface charge of acid-reacted forsterite is one or two orders of magnitude lower than that of unreacted forsterite with an apparent pH PZC at around 6.5 and a pH IEP value of 2.1 which is close to that for amorphous silica and reflects the formation of a silica-rich layer on the surface. XPS analyses indicate the penetration of hydrogen into the surface and the polymerization of silica tetrahedra in this leached layer. At pH > 10, a Si-deficient, Mg-rich surface layer is formed as shown by XPS analyses and the preferential Si release from the surface during column filtration experiments.

Characterisation of DLC films deposited using titanium isopropoxide (TIPOT) at different flow rates.

PubMed

Said, R; Ali, N; Ghumman, C A A; Teodoro, O M N D; Ahmed, W

2009-07-01

In recent years, there has been growing interest in the search for advanced biomaterials for biomedical applications, such as human implants and surgical cutting tools. It is known that both carbon and titanium exhibit good biocompatibility and have been used as implants in the human body. It is highly desirable to deposit biocompatible thin films onto a range of components in order to impart biocompatibility and to minimise wear in implants. Diamond like carbon (DLC) is a good candidate material for achieving biocompatibility and low wear rates. In this study, thin films of diamond-like-carbon DLC were deposited onto stainless steel (316) substrates using C2H2, argon and titanium isopropoxide (TIPOT) precursors. Argon was used to generate the plasma in the plasma enhanced vapour deposition (PECVD) system. A critical coating feature governing the performance of the component during service is film thickness. The as-grown films were in the thickness range 90-100 nm and were found to be dependent on TIPOT flow rate. Atomic force microscopy (AFM) was used to characterise the surface roughness of the samples. As the flow rate of TIPOT increased the average roughness was found to increase in conjunction with the film thickness. Raman spectroscopy was used to investigate the chemical structure of amorphous carbon matrix. Surface tension values were calculated using contact angle measurements. In general, the trend of the surface tension results exhibited an opposite trend to that of the contact angle. The elemental composition of the samples was characterised using a VG ToF SIMS (IX23LS) instrument and X-ray photoelectron spectroscopy (XPS). Surprisingly, SIMS and XPS results showed that the DLC samples did not show evidence of titanium since no peaks representing to titanium appeared on the SIMS/XPS spectra.

Catalytic activity of bimetallic Zn/TiO2 catalyst for degradation of herbicide paraquat: synthesis and characterization

NASA Astrophysics Data System (ADS)

Sakee, Uthai; Wanchanthuek, Ratchaneekorn

2017-11-01

The preparation and characterization of Zn/TiO2 catalysts were performed and the photocatalytic properties of the resulting catalysts were tested using the paraquat degradation reaction under UV and solar light irradiation. The effect of the preparation method, amount of Zn loading, the calcination temperature and the thermal annealing during the autoclave aging were studied as well as the light irradiation during the testing reaction. The initial concentration of paraquat was 400 ppm, the pH during the catalytic testing was seven and the reaction temperature was 30 °C. The characterization information were obtained from XRD, XPS, UV-vis diffuse reflectance, FTIR, TEM and BET techniques. They were used to explain the expressed catalytic activity of Zn/TiO2. The results showed that the Zn/TiO2 catalyst from the hydrothermal method could remove about 80% of the paraquat from the solution (using 4 g l-1 of catalyst). The characterization data showed that the surface area, porous structure and dispersion of Zn species could affect the ability of the paraquat removal rather than the crystallnity of the TiO2 in the catalyst. The XPS spectra suggested that the preparation method, between the sol gel and hydrothermal, could not affect the state of the Zn and Ti, which presented in the Zn2+ and Ti4+ forms. This primary result will lead us to further study to elucidate the main active site by the XPS technique. Moreover, it clearly showed that the lowering of the band gap energy in the Zn/TiO2 was achieved (compared to bare TiO2), and this phenomena was one of the factors that gave the higher photocatalytic activity of the Zn/TiO2 catalyst.

Reduction of mixed Mn-Zr oxides: in situ XPS and XRD studies.

PubMed

Bulavchenko, O A; Vinokurov, Z S; Afonasenko, T N; Tsyrul'nikov, P G; Tsybulya, S V; Saraev, A A; Kaichev, V V

2015-09-21

A series of mixed Mn-Zr oxides with different molar ratios Mn/Zr (0.1-9) have been prepared by coprecipitation of manganese and zirconium nitrates and characterized by X-ray diffraction (XRD) and BET methods. It has been found that at concentrations of Mn below 30 at%, the samples are single-phase solid solutions (MnxZr1-xO2-δ) based on a ZrO2 structure. X-ray photoelectron spectroscopy (XPS) measurements showed that manganese in these solutions exists mainly in the Mn(4+) state on the surface. An increase in Mn content mostly leads to an increase in the number of Mn cations in the structure of solid solutions; however, a part of the manganese cations form Mn2O3 and Mn3O4 in the crystalline and amorphous states. The reduction of these oxides with hydrogen was studied by a temperature-programmed reduction technique, in situ XRD, and near ambient pressure XPS in the temperature range from 100 to 650 °C. It was shown that the reduction of the solid solutions MnxZr1-xO2-δ proceeds via two stages. During the first stage, at temperatures between 100 and 500 °C, the Mn cations incorporated into the solid solutions MnxZr1-xO2-δ undergo partial reduction. During the second stage, at temperatures between 500 and 700 °C, Mn cations segregate on the surface of the solid solution. In the samples with more than 30 at% Mn, the reduction of manganese oxides was observed: Mn2O3 → Mn3O4 → MnO.

Influence of square wave anodization on the electronic properties and structures of the passive films on Ti in sulfuric acid solution

NASA Astrophysics Data System (ADS)

Long, Y.; Li, D. G.; Chen, D. R.

2017-12-01

Two types of square wave anodization (type 1 and type 2) were employed in this work to form a passive film on Ti in a 0.5 M H2SO4 solution. The influences of the anodization potential and duration on the electronic properties and structures of the passive films were studied by Mott-Schottky plots, auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The results showed that the donor density, ND, of the passive film decreased and the flat band potential, EFB, shifted to the positive direction with the increase of the anodization duration and high anodization potential irrespective of whether type 1 or type 2 was used. Moreover, the passive film that formed on Ti using type 1 had a lower donor density and a more positive flat band potential than that on Ti using type 2 at one fixed anodization duration (only exchanging the anodization order of 1 V and the high potential). XPS analysis revealed that the outmost passive film was only composed of TiO2, the inner passive film was mainly composed of TiO2 with some amount of TiO and Ti2O3, and the TiO2 concentration in the outermost passive film increased with the increase of the anodization duration and the high potential in the case of using type 1 or type 2, implying an increased degree of crystallinity. The AES results showed that the O/Ti atomic ratio of the passive film obviously increased with the increasing anodization duration and high potential, demonstrating the increased homogeneous characteristic of the passive film; this was in agreement with the Mott-Schottky and XPS results.

XPS and NRA investigations during the fabrication of gold nanostructured functionalized screen-printed sensors for the detection of metallic pollutants

NASA Astrophysics Data System (ADS)

Jasmin, Jean-Philippe; Miserque, Frédéric; Dumas, Eddy; Vickridge, Ian; Ganem, Jean-Jacques; Cannizzo, Caroline; Chaussé, Annie

2017-03-01

An all covalent nanostructured lead sensor was built by the successive grafting of gold nanoparticles and carboxylic ligands at the surface of self-adhesive carbon screen-printed electrodes (SPEs). Surface analysis techniques were used in each step in order to investigate the structuration of this sensor. The self-adhesive surfaces were made from the electrochemical grafting of p-phenylenediamine at the surface of the SPEs via diazonium salts chemistry. The quantity of grafted aniline functions, estimated by Nuclear Reaction Analysis (NRA) performed with p-phenylenediamine labelled with 15N isotope, is in agreement with an almost complete coverage of the electrode surface. The subsequent diazotization of the aniline functions at the surface of the SPEs was performed; X-ray Photoelectron Spectroscopy (XPS) allowed us to consider a quantitative conversion of the aniline functions into diazonium moieties. The spontaneous grafting of gold nanoparticles on the as-obtained reactive surfaces ensures the nanostructuration of the material, and XPS studies showed that the covalent bonding of the gold nanoparticles at the surface of the SPEs induces a change both in the Au-4f (gold nanoparticles) and Cl-2p (carbon ink) core level signals. These unusual observations are explained by an interaction between the carbon ink constituting the substrate and the gold nanoparticles. Heavy and toxic metals are considered of major environmental concern because of their non-biodegradability. In a final step, the grafting of the carboxylic ligands at the surface of the SPEs and an accumulation step in the presence of lead(II) cations allowed us to evidence the interest of nanostructured materials as metallic pollutants sensors.

Carbon in olivine single crystals analyzed by the 12C(d, p) 13C method and by photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Oberheuser, Gert; Kathrein, Hendrik; Demortier, Guy; Gonska, Horst; Freund, Friedemann

1983-06-01

Carbon subsurface concentration profiles in olivine single crystals from San Carlos, Arizona, and the Sergebet Island. Red Sea, containing total carbon between 60-180 wt.-ppm, were analyzed by means of the 12C(d. p) 13C nuclear reaction and by x-ray induced photoelectron spectroscopy (XPS) in combination with acid etching and with Ar + ion sputtering respectively, between 200-930 K. The (d, p) analysis reveals equilibrium subsurface C profiles extending 1-2 μm or more into the bulk. Their steepness is a function of temperature. Typical mean C concentrations at 300 K in the resolvable layers, 0-0.6, 0.6-1.2, and 1.2-1.8 μm. are 1.8, and 0.6 wt.-%, corresponding to enrichment factors over the mean bulk C concentration of the order of 100, 40 and 30 respectively. In the topmost atomic layers analyzed by XPS the carbon is enriched by a factor of the order of 1000, decreasing with increasing temperature. The results suggest that the carbon is in a truly dissolved state and highly mobile, subject to a reversible subsurface segregation. Most probably local lattice strain associated with the solute C species provide the driving force for this diffusional process. The C diffusion coefficient was determined from the (d, p) data below 300 K: D= 10 -13 exp(-7.8/RT) [m 2· sec -1; KJ · mole -1] and from XPS data between 450-925 K: D = 10 -14 exp(-6/RT) [m 2 · sec -1; KJ · mole -1] The estimated error of the preexponential factors is ± one order of magnitude, that of the activation energies ±3.5 and ±2 KJ mole -1 respectively.

Effect of sulfur hexafluoride gas and post-annealing treatment for inductively coupled plasma etched barium titanate thin films

PubMed Central

2014-01-01

Aerosol deposition- (AD) derived barium titanate (BTO) micropatterns are etched via SF6/O2/Ar plasmas using inductively coupled plasma (ICP) etching technology. The reaction mechanisms of the sulfur hexafluoride on BTO thin films and the effects of annealing treatment are verified through X-ray photoelectron spectroscopy (XPS) analysis, which confirms the accumulation of reaction products on the etched surface due to the low volatility of the reaction products, such as Ba and Ti fluorides, and these residues could be completely removed by the post-annealing treatment. The exact peak positions and chemicals shifts of Ba 3d, Ti 2p, O 1 s, and F 1 s are deduced by fitting the XPS narrow-scan spectra on as-deposited, etched, and post-annealed BTO surfaces. Compared to the as-deposited BTOs, the etched Ba 3d 5/2 , Ba 3d 3/2 , Ti 2p 3/2 , Ti 2p 1/2 , and O 1 s peaks shift towards higher binding energy regions by amounts of 0.55, 0.45, 0.4, 0.35, and 0.85 eV, respectively. A comparison of the as-deposited film with the post-annealed film after etching revealed that there are no significant differences in the fitted XPS narrow-scan spectra except for the slight chemical shift in the O 1 s peak due to the oxygen vacancy compensation in O2-excessive atmosphere. It is inferred that the electrical properties of the etched BTO film can be restored by post-annealing treatment after the etching process. Moreover, the relative permittivity and loss tangent of the post-annealed BTO thin films are remarkably improved by 232% and 2,695%, respectively. PMID:25249824

Kinetics of electron-induced decomposition of CF2Cl2 coadsorbed with water (ice): A comparison with CCl4

NASA Astrophysics Data System (ADS)

Faradzhev, N. S.; Perry, C. C.; Kusmierek, D. O.; Fairbrother, D. H.; Madey, T. E.

2004-11-01

The kinetics of decomposition and subsequent chemistry of adsorbed CF2Cl2, activated by low-energy electron irradiation, have been examined and compared with CCl4. These molecules have been adsorbed alone and coadsorbed with water ice films of different thicknesses on metal surfaces (Ru; Au) at low temperatures (25 K; 100 K). The studies have been performed with temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and x-ray photoelectron spectroscopy (XPS). TPD data reveal the efficient decomposition of both halocarbon molecules under electron bombardment, which proceeds via dissociative electron attachment (DEA) of low-energy secondary electrons. The rates of CF2Cl2 and CCl4 dissociation increase in an H2O (D2O) environment (2-3×), but the increase is smaller than that reported in recent literature. The highest initial cross sections for halocarbon decomposition coadsorbed with H2O, using 180 eV incident electrons, are measured (using TPD) to be 1.0±0.2×10-15 cm2 for CF2Cl2 and 2.5±0.2×10-15 cm2 for CCl4. RAIRS and XPS studies confirm the decomposition of halocarbon molecules codeposited with water molecules, and provide insights into the irradiation products. Electron-induced generation of Cl- and F- anions in the halocarbon/water films and production of H3O+, CO2, and intermediate compounds COF2 (for CF2Cl2) and COCl2, C2Cl4 (for CCl4) under electron irradiation have been detected using XPS, TPD, and RAIRS. The products and the decomposition kinetics are similar to those observed in our recent experiments involving x-ray photons as the source of ionizing irradiation.

Atomistic characterisation of Li+ mobility and conductivity in Li(7-x)PS(6-x)Ix argyrodites from molecular dynamics simulations, solid-state NMR, and impedance spectroscopy.

PubMed

Pecher, Oliver; Kong, Shiao-Tong; Goebel, Thorsten; Nickel, Vera; Weichert, Katja; Reiner, Christof; Deiseroth, Hans-Jörg; Maier, Joachim; Haarmann, Frank; Zahn, Dirk

2010-07-26

The atomistic mechanisms of Li(+) ion mobility/conductivity in Li(7-x)PS(6-x)I(x) argyrodites are explored from both experimental and theoretical viewpoints. Ionic conductivity in the title compound is associated with a solid-solid phase transition, which was characterised by low-temperature differential scanning calorimetry, (7)Li and (127)I NMR investigations, impedance measurements and molecular dynamics simulations. The NMR signals of both isotopes are dominated by anisotropic interactions at low temperatures. A significant narrowing of the NMR signal indicates a motional averaging of the anisotropic interactions above 177+/-2 K. The activation energy to ionic conductivity was assessed from both impedance spectroscopy and molecular dynamics simulations. The latter revealed that a series of interstitial sites become accessible to the Li(+) ions, whilst the remaining ions stay at their respective sites in the argyrodite lattice. The interstitial positions each correspond to the centres of tetrahedra of S/I atoms, and differ only in terms of their common corners, edges, or faces with adjacent PS(4) tetrahedra. From connectivity analyses and free-energy rankings, a specific tetrahedron is identified as the key restriction to ionic conductivity, and is clearly differentiated from local mobility, which follows a different mechanism with much lower activation energy. Interpolation of the lattice parameters as derived from X-ray diffraction experiments indicates a homogeneity range for Li(7-x)PS(6-x)I(x) with 0.97 < or = x < or = 1.00. Within this range, molecular dynamics simulations predict Li(+) conductivity at ambient conditions to vary considerably.

Surface passivation and aging of InGaAs/InP heterojunction phototransistors

NASA Astrophysics Data System (ADS)

Park, Min-Su; Razaei, Mohsen; Barnhart, Katie; Tan, Chee Leong; Mohseni, Hooman

2017-06-01

We report the effect of different surface treatment and passivation techniques on the stability of InGaAs/InP heterojunction phototransistors (HPTs). An In0.53Ga0.47As surface passivated with aqueous ammonium sulfide ((NH4)2S), aluminum oxide (Al2O3) grown by atomic layer deposition (ALD), and their combination is evaluated by using Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). All samples were kept in the air ambient, and their performances were periodically measured to investigate their long-term stability. Raman spectroscopy revealed that the peak intensity of the GaAs-like longitudinal optical phonon of all passivated samples is decreased compared with that of the control sample. This is attributable to the diminution of the carriers near the passivated surfaces, which was proven by extracted surface potential (Vs). The Vs of all passivated samples was decreased to less than half of that for the control sample. XPS evaluation of As3d spectra showed that arsenic oxides (As2O3 and As2O5) on the surfaces of the samples can be removed by passivation. However, both Raman and XPS spectra show that the (NH4)2S passivated sample reverts back over time and will resemble the untreated control sample. When capped with ALD-grown Al2O3, passivated samples irrespective of the pretreatment show no degradation over the measured time of 4 weeks. Similar conclusions are made from our experimental measurement of the performance of differently passivated HPTs. The ALD-grown Al2O3 passivated devices show an improved optical gain at low optical powers and long-term stability.

Tracking the conversion of nitrogen during pyrolysis of antibiotic mycelial fermentation residues using XPS and TG-FTIR-MS technology.

PubMed

Zhu, Xiangdong; Yang, Shijun; Wang, Liang; Liu, Yuchen; Qian, Feng; Yao, Wenqing; Zhang, Shicheng; Chen, Jianmin

2016-04-01

Antibiotic mycelial fermentation residues (AMFRs), which are emerging solid pollutants, have been recognized as hazardous waste in China since 2008. Nitrogen (N), which is an environmental sensitivity element, is largely retained in AMFR samples derived from fermentation substrates. Pyrolysis is a promising technology for the treatment of solid waste. However, the outcomes of N element during the pyrolysis of AMFRs are still unknown. In this study, the conversion of N element during the pyrolysis of AMFRs was tracked using XPS (X-ray photoelectron spectroscopy) and online TG-FTIR-MS (Thermogravimetry-Fourier transform infrared-Mass spectrometry) technology. In the AMFR sample, organic amine-N, pyrrolic-N, protein-N, pyridinic-N, was the main N-containing species. XPS results indicated that pyrrolic-N and pyridinic-N were retained in the AMFR-derived pyrolysis char. More stable species, such as N-oxide and quaternary-N, were also produced in the char. TG-FTIR-MS results indicated that NH3 and HCN were the main gaseous species, and their contents were closely related to the contents of amine-N and protein-N, and pyrrolic-N and pyridinic-N of AMFRs, respectively. Increases in heating rate enhanced the amounts of NH3 and HCN, but had less of an effect on the degradation degree of AMFRs. N-containing organic compounds, including amine-N, nitrile-N and heterocyclic-N, were discerned from the AMFR pyrolysis process. Their release range was extended with increasing of heating rate and carbon content of AMFR sample. This work will help to take appropriate measure to reduce secondary pollution from the treatment of AMFRs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Measuring Compositions in Organic Depth Profiling: Results from a VAMAS Interlaboratory Study.

PubMed

Shard, Alexander G; Havelund, Rasmus; Spencer, Steve J; Gilmore, Ian S; Alexander, Morgan R; Angerer, Tina B; Aoyagi, Satoka; Barnes, Jean-Paul; Benayad, Anass; Bernasik, Andrzej; Ceccone, Giacomo; Counsell, Jonathan D P; Deeks, Christopher; Fletcher, John S; Graham, Daniel J; Heuser, Christian; Lee, Tae Geol; Marie, Camille; Marzec, Mateusz M; Mishra, Gautam; Rading, Derk; Renault, Olivier; Scurr, David J; Shon, Hyun Kyong; Spampinato, Valentina; Tian, Hua; Wang, Fuyi; Winograd, Nicholas; Wu, Kui; Wucher, Andreas; Zhou, Yufan; Zhu, Zihua; Cristaudo, Vanina; Poleunis, Claude

2015-08-20

We report the results of a VAMAS (Versailles Project on Advanced Materials and Standards) interlaboratory study on the measurement of composition in organic depth profiling. Layered samples with known binary compositions of Irganox 1010 and either Irganox 1098 or Fmoc-pentafluoro-l-phenylalanine in each layer were manufactured in a single batch and distributed to more than 20 participating laboratories. The samples were analyzed using argon cluster ion sputtering and either X-ray photoelectron spectroscopy (XPS) or time-of-flight secondary ion mass spectrometry (ToF-SIMS) to generate depth profiles. Participants were asked to estimate the volume fractions in two of the layers and were provided with the compositions of all other layers. Participants using XPS provided volume fractions within 0.03 of the nominal values. Participants using ToF-SIMS either made no attempt, or used various methods that gave results ranging in error from 0.02 to over 0.10 in volume fraction, the latter representing a 50% relative error for a nominal volume fraction of 0.2. Error was predominantly caused by inadequacy in the ability to compensate for primary ion intensity variations and the matrix effect in SIMS. Matrix effects in these materials appear to be more pronounced as the number of atoms in both the primary analytical ion and the secondary ion increase. Using the participants' data we show that organic SIMS matrix effects can be measured and are remarkably consistent between instruments. We provide recommendations for identifying and compensating for matrix effects. Finally, we demonstrate, using a simple normalization method, that virtually all ToF-SIMS participants could have obtained estimates of volume fraction that were at least as accurate and consistent as XPS.

Measuring Compositions in Organic Depth Profiling: Results from a VAMAS Interlaboratory Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shard, A. G.; Havelund, Rasmus; Spencer, Steve J.

We report the results of a VAMAS (Versailles Project on Advanced Materials and Standards) interlaboratory study on the measurement of composition in organic depth profiling. Layered samples with known binary compositions of Irganox 1010 and either Irganox 1098 or Fmoc-pentafluoro-L-phenylalanine in each layer were manufactured in a single batch and distributed to more than 20 participating laboratories. The samples were analyzed using argon cluster ion sputtering and either X-ray Photoelectron Spectroscopy (XPS) or Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) to generate depth profiles. Participants were asked to estimate the volume fractions in two of the layers and were provided withmore » the compositions of all other layers. Participants using XPS provided volume fractions within 0.03 of the nominal values. Participants using ToF-SIMS either made no attempt, or used various methods that gave results ranging in error from 0.02 to over 0.10 in volume fraction, the latter representing a 50% relative error for a nominal volume fraction of 0.2. Error was predominantly caused by inadequacy in the ability to compensate for primary ion intensity variations and the matrix effect in SIMS. Matrix effects in these materials appear to be more pronounced as the number of atoms in both the primary analytical ion and the secondary ion increase. Using the participants’ data we show that organic SIMS matrix effects can be measured and are remarkably consistent between instruments. We provide recommendations for identifying and compensating for matrix effects. Finally we demonstrate, using a simple normalization method, that virtually all ToF-SIMS participants could have obtained estimates of volume fraction that were at least as accurate and consistent as XPS.« less

Highly efficient removal of heavy metals by polymer-supported nanosized hydrated Fe(III) oxides: behavior and XPS study.

PubMed

Pan, Bingjun; Qiu, Hui; Pan, Bingcai; Nie, Guangze; Xiao, Lili; Lv, Lu; Zhang, Weiming; Zhang, Quanxing; Zheng, Shourong

2010-02-01

The present study developed a polymer-based hybrid sorbent (HFO-001) for highly efficient removal of heavy metals [e.g., Pb(II), Cd(II), and Cu(II)] by irreversibly impregnating hydrated Fe(III) oxide (HFO) nanoparticles within a cation-exchange resin D-001 (R-SO(3)Na), and revealed the underlying mechanism based on X-ray photoelectron spectroscopy (XPS) study. HFO-001 combines the excellent handling, flow characteristics, and attrition resistance of conventional cation-exchange resins with the specific affinity of HFOs toward heavy metal cations. As compared to D-001, sorption selectivity of HFO-001 toward Pb(II), Cu(II), and Cd(II) was greatly improved from the Ca(II) competition at greater concentration. Column sorption results indicated that the working capacity of HFO-001 was about 4-6 times more than D-001 with respect to removal of three heavy metals from simulated electroplating water (pH approximately 4.0). Also, HFO-001 is particularly effective in removing trace Pb(II) and Cd(II) from simulated natural waters to meet the drinking water standard, with treatment volume orders of magnitude higher than D-001. The superior performance of HFO-001 was attributed to the Donnan membrane effect exerted by the host D-001 as well as to the impregnated HFO nanoparticles of specific interaction toward heavy metal cations, as further confirmed by XPS study on lead sorption. More attractively, the exhausted HFO-001 beads can be effectively regenerated by HCl-NaCl solution (pH 3) for repeated use without any significant capacity loss. (c) 2009 Elsevier Ltd. All rights reserved.

Morphological investigation of nanostructured CoMo catalysts

NASA Astrophysics Data System (ADS)

Pawelec, B.; Castaño, P.; Zepeda, T. A.

2008-04-01

This work reports the morphological investigation of nanostructured sulfided CoMo catalysts by means of high-resolution transmission electron microscopy (HRTEM). The catalysts were supported on Ti-modified hexagonal mesoporous silica (HMS-Ti) and P-modified HMS-Ti (P/HMS-Ti) materials. The oxide precursors were characterized by specific surface area (S BET), temperature-programmed reduction (TPR), diffuse reflectance infrared Fourier transform spectroscopy in the OH region (DRIFTS-OH) and X-ray photoelectron spectroscopy (XPS) in order to elucidate the influence of the impregnation sequence (successive vs. simultaneous) and the effect of P-incorporation into HMS-Ti material on the morphology of calcined CoMo catalysts. Both TPR and XPS measurements indicate that the catalysts prepared by successive impregnation possess well-dispersed MoO 3 and CoO phases, whereas their counterparts prepared by simultaneous impregnation additionally possess the CoMoO 4 phase. For all sulfided catalysts, the presence of MoS 2 phase with particle size in the range 3.3-4.4 nm was confirmed by HRTEM. Catalytic activity was evaluated in the reaction of hydrodesulfurization (HDS) of dibenzothiophene (DBT) carried out in a flow reactor at 593 K and hydrogen pressure of 5.5 MPa. P-incorporation into the HMS-Ti material led to an overall increase in HDS activity and the hydrogenation ability of the sulfided catalysts. All catalysts proved to be stable during 10 h time-on-stream (TOS) operation. The activity of sulfide catalysts in the target reaction depends linearly on the surface exposure of Co species in the oxide precursors, as determined by XPS, and on the morphology of the sulfide form of catalysts (surface density of MoS 2 particles and their sizes) as determined by HRTEM.

Physicochemical characterization of point defects in fluorine doped tin oxide films

NASA Astrophysics Data System (ADS)

Akkad, Fikry El; Joseph, Sudeep

2012-07-01

The physical and chemical properties of spray deposited FTO films are studied using FESEM, x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), electrical and optical measurements. The results of XRD measurements showed that the films are polycrystalline (grain size 20-50 nm) with Rutile structure and mixed preferred orientation along the (200) and (110) planes. An angular shift of the XRD peaks after F-doping is observed and interpreted as being due to the formation of substitutional fluorine defects (FO) in presence of high concentration of oxygen vacancies (VO) that are electrically neutral. The electrical neutrality of oxygen vacancies is supported by the observation that the electron concentration n is two orders of magnitude lower than the VO concentration calculated from chemical analyses using XPS measurements. It is shown that an agreement between XPS, XRD, and Hall effect results is possible provided that the degree of deviation from stoichiometry is calculated with the assumption that the major part of the bulk carbon content is involved in O-C bonds. High temperature thermal annealing is found to cause an increase in the FO concentration and a decrease in both n and VO concentrations with the increase of the annealing temperature. These results could be interpreted in terms of a high temperature chemical exchange reaction between the SnO2 matrix and a precipitated fluoride phase. In this reaction, fluorine is released to the matrix and Sn is trapped by the fluoride phase, thus creating substitutional fluorine FO and tin vacancy VSn defects. The enthalpy of this reaction is determined to be approximately 2.4 eV while the energy of formation of a VSn through the migration of SnSn host atom to the fluoride phase is approximately 0.45 eV.

Assessing the oxidation states and structural stability of the Ce analogue of brannerite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aluri, Esther Rani; Bachiu, Lisa M.; Grosvenor, Andrew P.

2017-07-04

The Ce-containing analogue of brannerite (ie, UTi2O6) was previously considered to be stoichiometric (ie, CeTi2O6); however, it has recently been determined that the material is O deficient. This oxygen-deficient material has been suggested to be charged balanced by the presence of a minor concentration of Ce3+ or by the A-site being cation deficient with the Ce oxidation state being 4+. A variety of Ti-containing oxides (including brannerite) have been investigated as potential nuclear wasteforms, and it is necessary to understand the electronic structure of a proposed nuclear wasteform material as well as how the structure responds to radiation from incorporatedmore » waste elements. The radiation resistance of a material can be simulated by ion implantation. The objective of this study was to confirm the Ce oxidation state in the cation- and oxygen-deficient material (ie, Ce0.94Ti2O6 - δ) and to determine how radiation damage affects this material. X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy were used to study Ce0.94Ti2O6 - δ before and after being implanted with 2 MeV Au- ions. Analysis of the Ce 3d XPS spectra from the as-synthesized samples by using a previously developed fitting method has unequivocally shown that Ce adopts both 4+ (major) and 3+ (minor) oxidation states, which was confirmed by examination of magnetic susceptibility data. Analysis of XPS and X-ray absorption near-edge spectroscopy spectra from ion-implanted materials showed that both Ce and Ti were reduced because of radiation damage and that the local coordination environments of the cations are greatly affected by radiation damage.« less

Growth of an Ultrathin Zirconia Film on Pt3Zr Examined by High-Resolution X-ray Photoelectron Spectroscopy, Temperature-Programmed Desorption, Scanning Tunneling Microscopy, and Density Functional Theory.

PubMed

Li, Hao; Choi, Joong-Il Jake; Mayr-Schmölzer, Wernfried; Weilach, Christian; Rameshan, Christoph; Mittendorfer, Florian; Redinger, Josef; Schmid, Michael; Rupprechter, Günther

2015-02-05

Ultrathin (∼3 Å) zirconium oxide films were grown on a single-crystalline Pt 3 Zr(0001) substrate by oxidation in 1 × 10 -7 mbar of O 2 at 673 K, followed by annealing at temperatures up to 1023 K. The ZrO 2 films are intended to serve as model supports for reforming catalysts and fuel cell anodes. The atomic and electronic structure and composition of the ZrO 2 films were determined by synchrotron-based high-resolution X-ray photoelectron spectroscopy (HR-XPS) (including depth profiling), low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. Oxidation mainly leads to ultrathin trilayer (O-Zr-O) films on the alloy; only a small area fraction (10-15%) is covered by ZrO 2 clusters (thickness ∼0.5-10 nm). The amount of clusters decreases with increasing annealing temperature. Temperature-programmed desorption (TPD) of CO was utilized to confirm complete coverage of the Pt 3 Zr substrate by ZrO 2 , that is, formation of a closed oxide overlayer. Experiments and DFT calculations show that the core level shifts of Zr in the trilayer ZrO 2 films are between those of metallic Zr and thick (bulklike) ZrO 2 . Therefore, the assignment of such XPS core level shifts to substoichiometric ZrO x is not necessarily correct, because these XPS signals may equally well arise from ultrathin ZrO 2 films or metal/ZrO 2 interfaces. Furthermore, our results indicate that the common approach of calculating core level shifts by DFT including final-state effects should be taken with care for thicker insulating films, clusters, and bulk insulators.

Sample-morphology effects on x-ray photoelectron peak intensities. II. Estimation of detection limits for thin-film materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Powell, Cedric J., E-mail: cedric.powell@nist.gov; Werner, Wolfgang S. M.; Smekal, Werner

2014-09-01

The authors show that the National Institute of Standards and Technology database for the simulation of electron spectra for surface analysis (SESSA) can be used to determine detection limits for thin-film materials such as a thin film on a substrate or buried at varying depths in another material for common x-ray photoelectron spectroscopy (XPS) measurement conditions. Illustrative simulations were made for a W film on or in a Ru matrix and for a Ru film on or in a W matrix. In the former case, the thickness of a W film at a given depth in the Ru matrix wasmore » varied so that the intensity of the W 4d{sub 5/2} peak was essentially the same as that for a homogeneous RuW{sub 0.001} alloy. Similarly, the thickness of a Ru film at a selected depth in the W matrix was varied so that the intensity of the Ru 3p{sub 3/2} peak matched that from a homogeneous WRu{sub 0.01} alloy. These film thicknesses correspond to the detection limits of each minor component for measurement conditions where the detection limits for a homogeneous sample varied between 0.1 at. % (for the RuW{sub 0.001} alloy) and 1 at. % (for the WRu{sub 0.01} alloy). SESSA can be similarly used to convert estimates of XPS detection limits for a minor species in a homogeneous solid to the corresponding XPS detection limits for that species as a thin film on or buried in the chosen solid.« less

Crystal structure and X-ray photoemission spectroscopic study of A{sub 2}LaMO{sub 6} [A=Ba, Ca; M=Nb, Ta

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutta, Alo, E-mail: alo_dutta@yahoo.com; Saha, Sujoy; Kumari, Premlata

2015-09-15

The X-ray photoemission spectroscopic (XPS) study of the double perovskite oxides A{sub 2}LaMO{sub 6} [A=Ba, Ca; M=Nb, Ta] synthesized by the solid-state reaction technique has been carried out to investigate the nature of the chemical state of the constituent ions and the bonding between them. The Rietveld refinement of the X-ray diffraction patterns suggests the monoclinic crystal structure of all the materials at room temperature. The negative and positive chemical shifts of the core level XPS spectrum of O-1s and Nb-3d{sub 3/2}/Ta-4f{sub 5/2} respectively suggest the covalent bonding between Nb/Ta cations and O ion. The change of the bonding strengthmore » between the anion and the cations from one material to another has been analyzed. The vibrational property of the materials is investigated using the room temperature Raman spectra. A large covalency of Ta-based compound than Nb compound is confirmed from the relative shifting of the Raman modes of the materials. - Graphical abstract: Crystal structure of two perovskite oxides CLN and CLT is investigated. XPS study confirms the two different co-ordination environments of Ca and covalent bonding between B-site cations and O-ion. - Highlights: • Ordered perovskite structure obtained by Rietveld refinement of XRD patterns. • Study of nature of chemical bonding by X-ray photoemission spectroscopy. • Opposite chemical shift of d-states of Nb/Ta with respect to O. • Covalent bonding between d-states of Nb/Ta and O. • Relative Raman shifts of CLN and CLT substantiate the more covalent character of Ta than Nb.« less

Low Temperature Approach to Serpentinization Processes on Ocean Worlds

NASA Astrophysics Data System (ADS)

Neto-Lima, J.; Fernández-Sampedro, M.; Prieto-Ballesteros, O.

2018-05-01

MIR results from laboratory experiments at constant temperature of 90ºC. The monitoring of the mineral alterations is done in the presence of different amounts of a Fe-Ni catalyst (awaruite) and ammonia, using XRPD, IR, SEM-EDS, XPS,RAMAN and ICP-MS.

Research on the Composition and Distribution of Organic Sulfur in Coal.

PubMed

Zhang, Lanjun; Li, Zenghua; Yang, Yongliang; Zhou, Yinbo; Li, Jinhu; Si, Leilei; Kong, Biao

2016-05-13

The structure and distribution of organic sulfur in coals of different rank and different sulfur content were studied by combining mild organic solvent extraction with XPS technology. The XPS results have shown that the distribution of organic sulfur in coal is related to the degree of metamorphism of coal. Namely, thiophenic sulfur content is reduced with decreasing metamorphic degree; sulfonic acid content rises with decreasing metamorphic degree; the contents of sulfate sulfur, sulfoxide and sulfone are rarely related with metamorphic degree. The solvent extraction and GC/MS test results have also shown that the composition and structure of free and soluble organic sulfur small molecules in coal is closely related to the metamorphic degree of coal. The free organic sulfur small molecules in coal of low metamorphic degree are mainly composed of aliphatic sulfides, while those in coal of medium and high metamorphic degree are mainly composed of thiophenes. Besides, the degree of aromatization of organic sulfur small molecules rises with increasing degree of coalification.

Synthesis of High Valence Silver-Loaded Mesoporous Silica with Strong Antibacterial Properties

PubMed Central

Chen, Chun-Chi; Wu, Hsin-Hsien; Huang, Hsin-Yi; Liu, Chen-Wei; Chen, Yi-Ning

2016-01-01

A simple chemical method was developed for preparing high valence silver (Ag)-loaded mesoporous silica (Ag-ethylenediaminetetraacetic acid (EDTA)-SBA-15), which showed strong antibacterial activity. Ag-EDTA-SBA-15 exhibited stronger and more effective antibacterial activity than commercial Ag nanoparticles did, and it offered high stability of high valence silver in the porous matrix and long-lasting antibacterial activity. The synthesized materials were characterized using Fourier transform infrared spectroscopy, powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) analysis, and transmission electron microscopy (TEM). Ag existed in both surface complexation and Ag particles. EDTA anchored within a porous structure chelated Ag ions in higher oxidation states and prevented their agglomeration and oxidation reduction. The XRD results showed that most Ag in the Ag-EDTA-SBA-15 existed in higher oxidation states such as Ag(II) and Ag(III). However, the XPS and TEM results showed that Ag easily reduced in lower oxidation states and agglomerated as Ag particles on the exterior layer of the SBA-15. PMID:26742050

X-ray probe of GaN thin films grown on InGaN compliant substrates

NASA Astrophysics Data System (ADS)

Xu, Xiaoqing; Li, Yang; Liu, Jianming; Wei, Hongyuan; Liu, Xianglin; Yang, Shaoyan; Wang, Zhanguo; Wang, Huanhua

2013-04-01

GaN thin films grown on InGaN compliant substrates were characterized by several X-ray technologies: X-ray reciprocal space mapping (RSM), grazing incidence X-ray diffraction (GIXRD), and X-ray photoemission spectrum (XPS). Narrow Lorentz broadening and stress free state were observed for GaN grown on InGaN compliant substrate, while mosaic structure and large tensile stress were observed at the presence of residual indium atoms. RSM disclosed the mosaicity, and the GIXRD was conducted to investigate the depth dependences of crystal quality and strain states. XPS depth profile of indium contents indicated that residual indium atoms deteriorated the crystal quality of GaN not only by producing lattice mismatch at the interface of InGaN and GaN but also by diffusing into GaN overlayers. Accordingly, two solutions were proposed to improve the efficiency of self-patterned lateral epitaxial overgrowth method. This research goes a further step in resolving the urgent substrate problem in GaN fabrication.

Study on the surface sulfidization behavior of smithsonite at high temperature

NASA Astrophysics Data System (ADS)

Lv, Jin-fang; Tong, Xiong; Zheng, Yong-xing; Xie, Xian; Wang, Cong-bing

2018-04-01

Surface sulfidization behavior of smithsonite at high temperature was investigated by X-ray powder diffractometer (XRD) along with thermodynamic calculation, X-ray photoelectron spectroscopy (XPS) and electron probe microanalysis (EPMA). The XRD and thermodynamic analyses indicated that the smithsonite was decomposed into zincite at high temperatures. After introducing a small amount of pyrite, artificial sulfides were formed at surface of the obtained zincite. The XPS analyses revealed that the sulfide species including zinc sulfide and zinc disulfide were generated at the zincite surface. The EPMA analyses demonstrated that the film of sulfides was unevenly distributed at the zincite surface. The average concentration of elemental sulfur at the sample surface increased with increasing of pyrite dosage. A suitable mole ratio of FeS2 to ZnCO3 for the surface thermal modification was determined to be about 0.3. These findings can provide theoretical support for improving the process during which the zinc recovery from refractory zinc oxide ores is achieved by xanthate flotation.

Investigation of the interfacial reaction between metal and fluorine-contained polyimides

NASA Astrophysics Data System (ADS)

Yang, Ching-Yu; Chen, J. S.; Hsu, S. L. C.

2005-07-01

In this work, thin metal films (Cr and Ta) were deposited on fluorine-contained polyimides, 6FDA-BisAAF, and 6FDA-PPD. The chemical states of the metal/polyimide samples were characterized by using x-ray photoelectron spectroscopy (XPS). XPS analysis reveals that metal-C, C-O, and metal-O bondings are present in metallized 6FDA-BisAAF and 6FDA-PPD. C-F bonds are observed in bare 6FDA-BisAAF and 6FDA-PPD however, they are not seen in the metallized samples. Disappearance of the C-F bonding is attributed to the disruption of CF3 side groups from the main chains of 6FDA-BisAAF and 6FDA-PPD when the chains are exposed to the plasma during the metal deposition. Nevertheless, the disruption of CF3 side groups also creates sites for the formation of metal-C or C-O bondings, which provide a positive adhesion strength at the metal/polyimide interface, as revealed by the tape test.

Examination of U valence states in the brannerite structure by near-infrared diffuse reflectance and X-ray photoelectron spectroscopies

NASA Astrophysics Data System (ADS)

Finnie, Kim S.; Zhang, Zhaoming; Vance, Eric R.; Carter, Melody L.

2003-04-01

The valence state of uranium doped into a f 0 thorium analog of brannerite (i.e., thorutite) has been examined using near-infrared (NIR) diffuse reflectance (DRS) and X-ray photoelectron (XPS) spectroscopies. NIR transitions of U 4+, which are not observed in spectra of brannerite, have been detected in the samples of U xTh 1- xTi 2O 6, and we propose that strong specular reflectance is responsible for the lack of U 4+ features in UTi 2O 6. Characteristic U 5+ bands have been identified in samples in which sufficient Ca 2+ has been added to nominally effect complete oxidation to U 5+. XPS results support the assignments of U 4+ and U 5+ by DRS. The presence of residual U 4+ bands in the spectra of the Ca-doped samples is consistent with segregation of Ca 2+ to the grain boundaries during high temperature sintering.

Improving the oxidation resistance and stability of Ag nanoparticles by coating with multilayered reduced graphene oxide

NASA Astrophysics Data System (ADS)

Li, Yahui; Zhang, Huayu; Wu, Bowen; Guo, Zhuo

2017-12-01

A kind of coating nanostructure, Ag nanoparticles coated with multilayered reduced graphene oxide (RGO), is fabricated by employing a three-step reduction method in an orderly manner, which is significantly different from the conventional structures that are simply depositing or doping with Ag nanoparticles on RGO via chemical reduction. The as-prepared nanostructure is investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected-area electronic diffraction (SEAD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). The results show that the obtained Ag/RGO nanostructure is observed to be a perfect coating structure with well dispersed Ag particles, which is responsible for the remarkable oxidation resistance. The results of XPS spectra indicate the content of metallic Ag is far greater than that of Ag oxides despite of prolonged exposure to the air, which fully demonstrate the excellent stability of thus coating nanostructure.

The electronic characterization of biphenylene—Experimental and theoretical insights from core and valence level spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lüder, Johann; Sanyal, Biplab; Eriksson, Olle

In this paper, we provide detailed insights into the electronic structure of the gas phase biphenylene molecule through core and valence spectroscopy. By comparing results of X-ray Photoelectron Spectroscopy (XPS) measurements with ΔSCF core-hole calculations in the framework of Density Functional Theory (DFT), we could decompose the characteristic contributions to the total spectra and assign them to non-equivalent carbon atoms. As a difference with similar molecules like biphenyl and naphthalene, an influence of the localized orbitals on the relative XPS shifts was found. The valence spectrum probed by photoelectron spectroscopy at a photon energy of 50 eV in conjunction withmore » hybrid DFT calculations revealed the effects of the localization on the electronic states. Using the transition potential approach to simulate the X-ray absorption spectroscopy measurements, similar contributions from the non-equivalent carbon atoms were determined from the total spectrum, for which the slightly shifted individual components can explain the observed asymmetric features.« less

The optical and electrical properties of graphene oxide with water-soluble conjugated polymer composites by radiation.

PubMed

Jungo, Seung Tae; Oh, Seung-Hwan; Kim, Hyun Bin; Jeun, Joon-Pyo; Lee, Bum-Jae; Kang, Phil-Hyun

2013-11-01

In order to overcome the difficulty of dispersion and low conductivity in composite containing graphene, graphene oxide (GO) has been used instead of neat graphene. And the GO treated by radiation, could give improved conductivity of the GO-containing polymer composite. In this study, fluorene based water-soluble conjugated polymer (WPF-6-oxy-F) was introduced in GO solution to investigate the change of optical and electrical properties through radiation process. UV-Vis absorption of irradiated WPF-6-oxy-F-GO composite was red shifted and I(D)/I(G) ratio of Raman spectra decreased. XPS analysis showed that C-N bonds was formed after the irradiation and confirmed the increased bonds between the GO and the water-soluble conjugated polymer matrix. From the AFM and XPS analysis, it was found that the water-soluble conjugated polymer matrix was stacked between the modified GO in the morphology of irradiated WPF-6-oxy-F-GO composite was increased after gamma ray irradiation up to 10(-2) S/cm.

Interfacial microanalysis of rubber tyre-cord adhesion and the influence of cobalt

NASA Astrophysics Data System (ADS)

Fulton, W. Stephen; Smith, Graham C.; Titchener, Keith J.

2004-01-01

The effect of cobalt-containing adhesion promoters on the structure and morphology of rubber-brass and rubber-tyre-cord interfaces before and after ageing has been investigated by X-ray photoelectron spectroscopy (XPS) depth profiling, glancing incidence X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effect the cobalt adhesion promoters had upon the interface morphology as they suppressed the growth of crystalline dendrites normally associated with the ageing process was imaged in TEM using samples prepared by the focused ion beam (FIB) milling technique. XPS depth profiling through the interfaces revealed that different types of adhesion promoter influenced the amount and distribution of cobalt ions in the bonding layer. XRD demonstrated the influence that cobalt had upon the structure of the interface and subsequent crystallinity, with a lesser degree of crystallinity being associated with better adhesion performance. From the results a model for the effect of the Co chemistry of the adhesion promotor has been developed.

Solution chemistry of carbonate minerals and its effects on the flotation of hematite with sodium oleate

NASA Astrophysics Data System (ADS)

Li, Dong; Yin, Wan-zhong; Xue, Ji-wei; Yao, Jin; Fu, Ya-feng; Liu, Qi

2017-07-01

The effects of carbonate minerals (dolomite and siderite) on the flotation of hematite using sodium oleate as a collector were investigated through flotation tests, supplemented by dissolution measurements, solution chemistry calculations, zeta-potential measurements, Fourier transform infrared (FTIR) spectroscopic studies, and X-ray photoelectron spectroscopy (XPS) analyses. The results of flotation tests show that the presence of siderite or dolomite reduced the recovery of hematite and that the inhibiting effects of dolomite were stronger. Dissolution measurements, solution chemistry calculations, and flotation tests confirmed that both the cations (Ca2+ and Mg2+) and CO3 2- ions dissolved from dolomite depressed hematite flotation, whereas only the CO3 2- ions dissolved from siderite were responsible for hematite depression. The zeta-potential, FTIR spectroscopic, and XPS analyses indicated that Ca2+, Mg2+, and CO3 2- (HCO3 -) could adsorb onto the hematite surface, thereby hindering the adsorption of sodium oleate, which was the main reason for the inhibiting effects of carbonate minerals on hematite flotation.

The effects of surface pretreatment and nitrogen tetroxide purification on the corrosion rate of Type 304L stainless steel

NASA Technical Reports Server (NTRS)

Blue, G. D.; Moran, C. M.

1985-01-01

Corrosion rates of 304L stainless steel coupons in MON-1 oxidizer have been measured as a function of cleaning procedures employed, surface layer positions, propellant impurity levels, and short-term exposure durations (14 to 90 days). Of special interest was propellant contamination by buildup of soluble iron, which may cause flow decay. Surface treatments employed were combinations of cleaning, pickling, and passivation procedures. Propellants used were MIL-SPEC MON-1 and several types of purified NTO (i.e., low water, low chloride) which may, at a later time, be specified as spacecraft grade. Pretest coupon surface analysis by X-ray photoelectron spectroscopy (XPS-ESCA) has revealed important differences, for the different cleaning procedures, in the make-up of the surface layer, both in composition and state of chemical combination of the elements involved. Comparisons will be made of XPS/ESCA data, for different cleaning procedures, for specimens before and after propellant exposure.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sarkar, S.; Mondal, A.; Dey, K.

Highlights: • Reduced graphene oxides (RGO) are prepared by two chemical routes. • Defects in RGO are characterized by Raman, FTIR and XPS studies. • Defects tailor colossal dielectricity in RGO. - Abstract: Reduced graphene oxide (RGO) is prepared in two different chemical routes where reduction of graphene oxide is performed by hydrazine hydrate and through high pressure in hydrothermal reactor. Samples are characterized by X-ray powdered diffraction (XRD), thermo gravimetric analysis (TGA), field emission scanning electron microscopy (FESEM) and tunneling electron microscopy (TEM). Types of defects are probed by Raman, FTIR spectroscopy and X-ray photoelectron spectroscopy (XPS). UV–vis absorptionmore » reveals different optical band gaps of the two RGOs. Conductivity mechanism is studied through I–V measurements displaying different characteristic features which are addressed due to the presence of defects appeared in different synthesis. Significantly high value (∼10{sup 4}) of dielectric permittivity at 10 MHz is attractive for technological application which could be tuned by the defects present in RGO.« less

Corrosion behavior and surface structure of orthodontic Ni-Ti alloy wires.

PubMed

Iijima, M; Endo, K; Ohno, H; Yonekura, Y; Mizoguchi, I

2001-03-01

The corrosion behaviors of a commercial Ni-Ti alloy orthodontic wire and a polished plate with same composition in 0.9% NaCl and 1% lactic acid solutions were examined using an electrochemical technique, an analysis of released ions, and a surface analysis by X-ray photoelectron spectroscopy (XPS). The effect of polishing the wire on the corrosion was also examined. The XPS analysis demonstrated the presence of a thick oxide film mainly composed of TiO2 with trace amounts of Ni hydroxide, which had formed on the wire surface during the heat treatment and subsequent pickling processes. This oxide layer contributed to the higher resistance of the as-received wire to both general and localized corrosion in 0.9% NaCl solution, compared with that of the polished plate and the polished wire. The thick oxide layer, however, was not stable and did not protect the orthodontic wire from corrosion in 0.1% lactic acid solution.

Organophosphonate-based PNA-functionalization of silicon nanowires for label-free DNA detection.

PubMed

Cattani-Scholz, Anna; Pedone, Daniel; Dubey, Manish; Neppl, Stefan; Nickel, Bert; Feulner, Peter; Schwartz, Jeffrey; Abstreiter, Gerhard; Tornow, Marc

2008-08-01

We investigated hydroxyalkylphosphonate monolayers as a novel platform for the biofunctionalization of silicon-based field effect sensor devices. This included a detailed study of the thin film properties of organophosphonate films on Si substrates using several surface analysis techniques, including AFM, ellipsometry, contact angle, X-ray photoelectron spectroscopy (XPS), X-ray reflectivity, and current-voltage characteristics in electrolyte solution. Our results indicate the formation of a dense monolayer on the native silicon oxide that has excellent passivation properties. The monolayer was biofunctionalized with 12 mer peptide nucleic acid (PNA) receptor molecules in a two-step procedure using the heterobifunctional linker, 3-maleimidopropionic-acid-N-hydroxysuccinimidester. Successful surface modification with the probe PNA was verified by XPS and contact angle measurements, and hybridization with DNA was determined by fluorescence measurements. Finally, the PNA functionalization protocol was translated to 2 microm long, 100 nm wide Si nanowire field effect devices, which were successfully used for label-free DNA/PNA hybridization detection.

Catalyst-free growth of Al-doped SnO2 zigzag-nanobelts for low ppm detection of organic vapours

NASA Astrophysics Data System (ADS)

Sinha, Sudip Kumar; Ghosh, Saptarshi

2016-10-01

In this effort, we report on development of specific sensors dedicated for detection of two of these volatiles, namely ethanol and acetone, below the prescribed statutory limits. Single crystalline Al-doped SnO2 zigzag nanobelt structures were deposited on Si substrate by a catalyst-free thermal evaporation method. The Al-doped SnO2 zigzag nanostructures exhibit high sensitivity and repeatability together with coveted features like fast response and excellent stability. Structural attributes involving the crystal quality and morphology of Al-doped SnO2 zigzag nanobelts were analyzed using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy and transmission electron microscopy. The microscopic images revealed formation of randomly oriented 'zigzag-like' nanobelts with characteristic width between 60 nm and 200 nm and length of 50-300 μm. The Al-doping was observed to have a discerning effect in enhancing the sensitivity in comparison to the pristine nanowires by creating excess oxygen vacancies in the crystal lattice, confirmed through XPS and PL spectra.

Surface analysis of graphite fiber reinforced polyimide composites

NASA Technical Reports Server (NTRS)

Messick, D. L.; Progar, D. J.; Wightman, J. P.

1983-01-01

Several techniques have been used to establish the effect of different surface pretreatments on graphite-polyimide composites. Composites were prepared from Celion 6000 graphite fibers and the polyimide LARC-160. Pretreatments included mechanical abrasion, chemical etching and light irradiation. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were used in the analysis. Contact angle of five different liquids of varying surface tensions were measured on the composites. SEM results showed polymer-rich peaks and polymer-poor valleys conforming to the pattern of the release cloth used durng fabrication. Mechanically treated and light irradiated samples showed varying degrees of polymer peak removal, with some degradation down to the graphite fibers. Minimal changes in surface topography were observed on concentrations of surface fluorine even after pretreatment. The light irradiation pretreatment was most effective at reducing surface fluorine concentrations whereas chemical pretreatment was the least effective. Critical surface tensions correlated directly with the surface fluorine to carbon ratios as calculated from XPS.

X-ray photoelectron spectroscopic analysis of rice kernels and flours: Measurement of surface chemical composition.

PubMed

Nawaz, Malik A; Gaiani, Claire; Fukai, Shu; Bhandari, Bhesh

2016-12-01

The objectives of this study were to evaluate the ability of X-ray photoelectron spectroscopy (XPS) to differentiate rice macromolecules and to calculate the surface composition of rice kernels and flours. The uncooked kernels and flours surface composition of the two selected rice varieties, Thadokkham-11 (TDK11) and Doongara (DG) demonstrated an over-expression of lipids and proteins and an under-expression of starch compared to the bulk composition. The results of the study showed that XPS was able to differentiate rice polysaccharides (mainly starch), proteins and lipids in uncooked rice kernels and flours. Nevertheless, it was unable to distinguish components in cooked rice samples possibly due to complex interactions between gelatinized starch, denatured proteins and lipids. High resolution imaging methods (Scanning Electron Microscopy and Confocal Laser Scanning Microscopy) were employed to obtain complementary information about the properties and location of starch, proteins and lipids in rice kernels and flours. Copyright © 2016. Published by Elsevier Ltd.

Characterization of pulsed laser deposition grown V2O3 converted VO2

NASA Astrophysics Data System (ADS)

Majid, Suhail; Shukla, D. K.; Rahman, F.; Gautam, Kamini; Sathe, V. G.; Choudhary, R. J.; Phase, D. M.

2016-10-01

Controllable tuning of Metal-insulator transition in VxOy thin film has been a field of extensive research. However controlled synthesis of desired Vanadium oxide phase is a challenging task. We have successfully achieved VO2 phase on Silicon substrate after post deposition annealing treatment to the PLD grown as deposited V2O3 thin films. The annealed thin film was characterized by x-ray diffraction (XRD), resistivity, Raman spectroscopy, X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) measurements. XRD confirms the crystalline nature and growth of VO2 phase in thin film. The characteristic MIT was observed from resistivity measurements and transition temperature appeared at lower value around 336 K, compared to bulk VO2. The structural transition accompanied with MIT from lower temperature monoclinic phase to higher temperature Rutile phase became evident from temperature dependent Raman measurements. Chemical state of vanadium was examined using XAS and XPS measurements which confirm the presence of +4 oxidation state of vanadium in thin film.

The effect of lizardite surface characteristics on pyrite flotation

NASA Astrophysics Data System (ADS)

Feng, Bo; Feng, Qiming; Lu, Yiping

2012-10-01

The effect of lizardite surface characteristics on pyrite flotation has been investigated through flotation tests, adsorption tests, zeta potential measurements, FTIR study, X-ray photoelectron spectroscopy (XPS) and sedimentation tests. The flotation results show that at pH value 9, where flotation of nickel sulfide ores is routinely performed, two kinds of lizardite samples (native lizardite and leached lizardite) have different effects on the flotation of pyrite. The native lizardite adheres to the surface of pyrite and reduces pyrite flotation recovery while the leached lizardite does not interfere with pyrite flotation. Infrared analyses and XPS tests illustrate that acid leaching changed the surface characteristics of lizardite mineral and the leached lizardite has less magnesium on its surface. It has been determined that the electro-kinetic behavior of lizardite aqueous suspensions is mainly a function of the Mg/Si atomic ratio on lizardite surface. So, the low isoelectric point observed in the leached sample has been linked to values of this ratio lower than that of the native lizardite.

Comparative surface studies on wet and dry sacrificial thermal oxidation on silicon carbide

NASA Astrophysics Data System (ADS)

Koh, A.; Kestle, A.; Wright, C.; Wilks, S. P.; Mawby, P. A.; Bowen, W. R.

2001-04-01

A comparative study on the effect of wet and dry thermal oxidation on 4H-silicon carbide (SiC) and on sacrificial silicon (Si) thermal oxidation on 4H-SiC surface has been conducted using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The AFM images show the formation of 'nano-islands' of varying density on the SiC surface after the removal of thermal oxide using hydrofluoric (HF) acid etch. These nano-islands are resistant to HF acid and have been previously linked to residual carbon [1-3] resulting from the oxidation process. This paper presents the use of a sacrificial silicon oxidation (SSO) step as a form of surface preparation that gives a reproducible clean SiC surface. XPS results show a slight electrical shift in binding energy between the wet and dry thermal oxidation on the standard SiC surface, while the surface produced by the SSO technique shows a minimal shift.

MPI implementation of PHOENICS: A general purpose computational fluid dynamics code

NASA Astrophysics Data System (ADS)

Simunovic, S.; Zacharia, T.; Baltas, N.; Spalding, D. B.

1995-03-01

PHOENICS is a suite of computational analysis programs that are used for simulation of fluid flow, heat transfer, and dynamical reaction processes. The parallel version of the solver EARTH for the Computational Fluid Dynamics (CFD) program PHOENICS has been implemented using Message Passing Interface (MPI) standard. Implementation of MPI version of PHOENICS makes this computational tool portable to a wide range of parallel machines and enables the use of high performance computing for large scale computational simulations. MPI libraries are available on several parallel architectures making the program usable across different architectures as well as on heterogeneous computer networks. The Intel Paragon NX and MPI versions of the program have been developed and tested on massively parallel supercomputers Intel Paragon XP/S 5, XP/S 35, and Kendall Square Research, and on the multiprocessor SGI Onyx computer at Oak Ridge National Laboratory. The preliminary testing results of the developed program have shown scalable performance for reasonably sized computational domains.

MPI implementation of PHOENICS: A general purpose computational fluid dynamics code

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simunovic, S.; Zacharia, T.; Baltas, N.

1995-04-01

PHOENICS is a suite of computational analysis programs that are used for simulation of fluid flow, heat transfer, and dynamical reaction processes. The parallel version of the solver EARTH for the Computational Fluid Dynamics (CFD) program PHOENICS has been implemented using Message Passing Interface (MPI) standard. Implementation of MPI version of PHOENICS makes this computational tool portable to a wide range of parallel machines and enables the use of high performance computing for large scale computational simulations. MPI libraries are available on several parallel architectures making the program usable across different architectures as well as on heterogeneous computer networks. Themore » Intel Paragon NX and MPI versions of the program have been developed and tested on massively parallel supercomputers Intel Paragon XP/S 5, XP/S 35, and Kendall Square Research, and on the multiprocessor SGI Onyx computer at Oak Ridge National Laboratory. The preliminary testing results of the developed program have shown scalable performance for reasonably sized computational domains.« less

Wet chemical passivation of YBa2Cu3O(7-x)

NASA Technical Reports Server (NTRS)

Vasquez, R. P.; Hunt, B. D.; Foote, M. C.

1990-01-01

Wet chemical techniques are described for treatment of YBa2Cu3O(7-x) surfaces, which result in the formation of native compounds known to have little or no reactivity to water. Suitable native compounds include CuI, BaSO4, CuS, Cu2S, YF3, and the oxalates. Formation of surface layers in which these nonreactive native compounds are major constituents is verified with X-ray photoelectron spectroscopy (XPS) measurements on YBa2Cu3O(7-x) films treated with dilute solutions of HI, H2SO4, Na2S, HF, or H2C2O4. No significant changes are observed in the XPS spectra when the sulfide, sulfate, or oxalate films are dipped in water, while the iodide and fluoride films show evidence of reaction with water. X-ray diffraction measurements show that the superconducting phase is absent in the sulfide film, but is unaffected by the oxalate and sulfate treatments.

Adsorption behavior of glycidoxypropyl-trimethoxy-silane on titanium alloy Ti-6.5Al-1Mo-1V-2Zr

NASA Astrophysics Data System (ADS)

Liu, Jian-hua; Zhan, Zhong-wei; Yu, Mei; Li, Song-mei

2013-01-01

The adsorption behavior of glycidoxypropyl-trimethoxy-silane (GTMS) on titanium alloy Ti-6.5Al-1Mo-1V-2Zr was investigated by using X-ray photoelectron spectroscopy (XPS), Tafel polarization test, and electrochemical impedance spectroscopy (EIS). From the XPS results, it was found that the silane coverage on the titanium surface generally increased with GTMS concentration, with a slight decrease at concentration of 0.1%. Based on the relationship between isoelectronic point (IEP) of titanium surface and the pH values of silane solutions, adsorption mechanisms at different concentrations were proposed. The surface coverage data of GTMS on titanium surface was also derived from electrochemical measurements. By linear fitting the coverage data, it revealed that the adsorption of GTMS on the titanium alloy surface at 30 °C was of a physisorption-based mechanism, and obeyed Langmuir adsorption isotherm. The adsorption equilibrium constant (Kads) and free energy of adsorption process (ΔGads) were calculated to elaborate the mechanism of GTMS adsorption.

Surface layer formation of LiCoO2 thin film electrodes in non-aqueous electrolyte containing lithium bis(oxalate)borate

NASA Astrophysics Data System (ADS)

Matsui, Masaki; Dokko, Kaoru; Akita, Yasuhiro; Munakata, Hirokazu; Kanamura, Kiyoshi

2012-07-01

Surface layer formation processes on a LiCoO2 thin film electrode in a non-aqueous electrolyte containing lithium bis(oxalate)borate (LiBOB) were investigated using in situ FTIR spectroscopy and X-ray photoelectron spectroscopy (XPS). The in situ FTIR spectra of the electrolyte solution containing LiBOB showed that the adsorption of BOB anions on the electrode surface occurred during the charge process of the LiCoO2 thin film electrode above 4.0 V. XPS analysis for the LiCoO2 thin film electrode charged in an electrolyte containing LiBOB suggested that the adsorbed BOB anions on the electrode surface prevent the continuous decomposition of hexafluorophosphate (PF6) anions resulting in the formation of a very thin surface layer containing organic species, while the LiCoO2 charged in a LiPF6 solution had a relatively thick surface layer containing organic species and inorganic species.

[Characteristics of hydroxyapatite/PMMA nanocomposites for provisional restoration and its biocompatibility with human gingival fibroblasts].

PubMed

Zhang, Jing-chao; Mo, An-chun; Li, Ji-dong; Wang, Xue-jiang; Li, Yu-bao

2014-05-01

To formulate hydroxyapatite (HA)/polymethyl methacrylate (PMMA) composites with improved cytocompatibility for provisional restoration. Nanocomposites with 20 wt%, 30 wt%, 40 wt%, and 50 wt% HA/PMMA (H/P) were developed and examined using X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM). Human gingival fibroblasts were cultured on those HA/PMMA discs and investigated by fluorescent staining on 24 h and MTT assay at 1 d, 3 d, 5 d and 7 d. Chemical integration of HA/PMMA interface was confirmed by XPS. Typical fusiform cells with adhesion spots were detected on 40 wt% and 50 wt% H/P discs. MTT results showed insignificant differences in cell growth between 40 wt% H/P and pure titanium (Ti, P > 0.05), while the other H/P discs showed significantly lower cell growth than pure Ti (P < 0.05). 40 wt% H/P might be a promising candidate for provisional dental implant restoration and for esthetic gingival contour.

Thermal stability of electron-irradiated poly(tetrafluoroethylene) - X-ray photoelectron and mass spectroscopic study

NASA Technical Reports Server (NTRS)

Wheeler, Donald R.; Pepper, Stephen V.

1990-01-01

Polytetrafluoroethylene (PTFE) was subjected to 3 keV electron bombardment and then heated in vacuum to 300 C. The behavior of the material as a function of radiation dose and temperature was studied by X-ray photoelectron spectroscopy (XPS) of the surface and mass spectroscopy of the species evolved. Lightly damaged material heated to 300 C evolved saturated fluorocarbon species, whereas unsaturated fluorocarbon species were evolved from heavily damaged material. After heating the heavily damaged material, those features in the XPS spectrum that were associated with damage diminished, giving the appearance that the radiation damage had annealed. The observations were interpreted by incorporating mass transport of severed chain fragments and thermal decomposition of severely damaged material into the branched and cross-linked network model of irradiated PTFE. The apparent annealing of the radiation damage was due to covering of the network by saturated fragments that easily diffused through the decomposed material to the surface region upon heating.

Impact of water vapour and carbon dioxide on surface composition of C{sub 3}A polymorphs studied by X-ray photoelectron spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dubina, E.; Plank, J.; Black, L., E-mail: l.black@leeds.ac.uk

2015-07-15

The surface specific analytical method, X-ray photoelectron spectroscopy (XPS), has been used to study the effects of water vapour and CO{sub 2} on the cubic and orthorhombic polymorphs of C{sub 3}A. Significant differences between the two polymorphs were observed in the XPS spectra. Upon exposure to water vapour, both polymorphs produced C{sub 4}AH{sub 13} on their surfaces. Additionally, the sodium-doped o-C{sub 3}A developed NaOH and traces of C{sub 3}AH{sub 6} on its surface. Subsequent carbonation yielded mono carboaluminate on both polymorphs. Large amounts of Na{sub 2}CO{sub 3} also formed on the surface of o-C{sub 3}A as a result of carbonationmore » of NaOH. Furthermore, the extent of carbonation was much more pronounced for o-C{sub 3}A{sub o} than for c-C{sub 3}A.« less

Crosslinking of polysaccharides in room temperature ionic liquids by ionizing radiation

NASA Astrophysics Data System (ADS)

Kimura, Atsushi; Nagasawa, Naotsugu; Shimada, Akihiko; Taguchi, Mitsumasa

2016-07-01

Crosslinking of polysaccharides in room temperature ionic liquids (RTILs) by ionizing radiation were investigated by the scavenging method, fluorescent and X-ray photoelectron spectroscopy (XPS) analysis. Radiation chemical yields of hydroxyl radicals inducing the crosslinking of cellulose were estimated with phenol as a scavenger, and increased with water content in 1-ethyl-3-methylimidazolium acetate (EMI-acetate). Cellulose gel was also produced in fluorescent carboxylate-based RTILs, 1,3-dibutylimidazolium acetate (DBI-acetate). Light emission from DBI-acetate in cellulose gel was observed and 20-nm red shifted at a maximum wavelength of 415 nm when excited at 323 nm. Expected elements of carbon and oxygen were detected in neat cellulose by XPS, while additional nitrogen was detected in radiation-crosslinked cellulose gel produced in EMI-acetate. These results indicate that RTILs is incorporated in the cellulose gel. Chitin gel was first obtained in 1-butyl-3-methyimidazolium chloride by γ-ray irradiations, and its gel fraction increased with the dose and reached 86% at 60 kGy.

The effect of Cr substitution on the structural, electronic and magnetic properties of pulsed laser deposited NiFe2O4 thin films

NASA Astrophysics Data System (ADS)

Panwar, Kalpana; Tiwari, Shailja; Bapna, Komal; Heda, N. L.; Choudhary, R. J.; Phase, D. M.; Ahuja, B. L.

2017-01-01

We have studied the structural, electronic and magnetic properties of pulsed laser deposited thin films of Ni1-xCrxFe2O4 (x=0.02 and 0.05) on Si (111) and Si (100) substrates. The films reveal single phase, polycrystalline structure with larger grain size on Si (111) substrate than that on Si (100) substrate. Contrary to the expected inverse spinel structure, x-ray photoemission (XPS) studies reveal the mixed spinel structure. XPS results suggest that Ni and Fe ions exist in 2+ and 3+ states, respectively, and they exist in tetrahedral as well as octahedral sites. The deviation from the inverse spinel leads to modified magnetic properties. It is observed that saturation magnetization drastically drops compared to the expected saturation value for inverse spinel structure. Strain in the films and lattice distortion produced by the Cr doping also appear to influence the magnetic properties.

SeO2 adsorption on CaO surface: DFT and experimental study on the adsorption of multiple SeO2 molecules

NASA Astrophysics Data System (ADS)

Fan, Yaming; Zhuo, Yuqun; Li, Liangliang

2017-10-01

SeO2 adsorption mechanisms on CaO surface were firstly investigated by both density functional theory (DFT) calculations and adsorption experiments. Adsorption of multiple SeO2 on the CaO (001) surface was investigated using slab model. Based on the results of adsorption energy and surface property, a double-layer adsorption mechanisms were proposed. In experiments, the SeO2 adsorption products were prepared in a U-shaped quartz reactor at 200 °C. The surface morphology was investigated by field emission scanning electron microscopy (FE-SEM). The superficial and total SeO2 mass fractions were measured by X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES), respectively. The surface valence state and bulk structure are determined by XPS and X-Ray Diffraction (XRD). The experimental results are in good agreement with the DFT results. In conclusion, the fundamental SeO2 chemisorption mechanisms on CaO surface were suggested.

Corrosion behavior of ion implanted nickel-titanium orthodontic wire in fluoride mouth rinse solutions.

PubMed

Iijima, Masahiro; Yuasa, Toshihiro; Endo, Kazuhiko; Muguruma, Takeshi; Ohno, Hiroki; Mizoguchi, Itaru

2010-01-01

This study investigated the corrosion properties of ion implanted nickel-titanium wire (Neo Sentalloy Ionguard) in artificial saliva and fluoride mouth rinse solutions (Butler F Mouthrinse, Ora-Bliss). Non ion implanted nickel-titanium wire (Neo Sentalloy) was used as control. The anodic corrosion behavior was examined by potentiodynamic polarization measurement. The surfaces of the specimens were examined with SEM. The elemental depth profiles were characterized by XPS. Neo Sentalloy Ionguard in artificial saliva and Butler F Mouthrinse (500 ppm) had a lower current density than Neo Sentalloy. In addition, breakdown potential of Neo Sentalloy Ionguard in Ora-Bliss (900 ppm) was much higher than that of Neo Sentalloy although both wires had similar corrosion potential in Ora-Bliss (450 and 900 ppm). The XPS results for Neo Sentalloy Ionguard suggested that the layers consisted of TiO(2) and TiN were present on the surface and the layers may improve the corrosion properties.

Facile fabrication of BiVO4 nanofilms with controlled pore size and their photoelectrochemical performances

NASA Astrophysics Data System (ADS)

Feng, Chenchen; Jiao, Zhengbo; Li, Shaopeng; Zhang, Yan; Bi, Yingpu

2015-12-01

We demonstrate a facile method for the rational fabrication of pore-size controlled nanoporous BiVO4 photoanodes, and confirmed that the optimum pore-size distributions could effectively absorb visible light through light diffraction and confinement functions. Furthermore, in situ X-ray photoelectron spectroscopy (XPS) reveals more efficient photoexcited electron-hole separation than conventional particle films, induced by light confinement and rapid charge transfer in the inter-crossed worm-like structures.We demonstrate a facile method for the rational fabrication of pore-size controlled nanoporous BiVO4 photoanodes, and confirmed that the optimum pore-size distributions could effectively absorb visible light through light diffraction and confinement functions. Furthermore, in situ X-ray photoelectron spectroscopy (XPS) reveals more efficient photoexcited electron-hole separation than conventional particle films, induced by light confinement and rapid charge transfer in the inter-crossed worm-like structures. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06584d

An X-ray photoelectron spectroscopy study of the thermal nitridation of SiO2/Si

NASA Technical Reports Server (NTRS)

Vasquez, R. P.; Madhukar, A.; Grunthaner, F. J.; Naiman, M. L.

1986-01-01

The dependence of the nitrogen distribution in thermally nitrided SiO2 films on the nitridation time and temperature has been studied by means of X-ray photoelectron spectroscopy (XPS). The photoelectron peak intensities were measured by fitting Voigt profiles to the XPS spectra and were used to calculate the film composition as a function of film depth, applying an analytical method described in detail. The times of appearance of the maxima in interfacial nitrogen concentration are shown for 800, 1000, and 1150 C, and the data are related to a kinetic model of Vasquez and Madhukar (1985), which considers the effect of interfacial strain on the nitridation kinetics. In addition, the intensity of a fluorine marker (from the HF used in the etching step) was found to correlate with the nitrogen concentration. It is postulated that the F bonds preferentially to defects. This hypothesis and the measured F intensities are consistent with the proposed strain-dependent energy of defect formation.

Portable total reflection x-ray fluorescence analysis in the identification of unknown laboratory hazards

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Ying, E-mail: liu.ying.48r@st.kyoto-u.ac.jp; Imashuku, Susumu; Sasaki, Nobuharu

In this study, a portable total reflection x-ray fluorescence (TXRF) spectrometer was used to analyze unknown laboratory hazards that precipitated on exterior surfaces of cooling pipes and fume hood pipes in chemical laboratories. With the aim to examine the accuracy of TXRF analysis for the determination of elemental composition, analytical results were compared with those of wavelength-dispersive x-ray fluorescence spectrometry, scanning electron microscope and energy-dispersive x-ray spectrometry, energy-dispersive x-ray fluorescence spectrometry, inductively coupled plasma atomic emission spectrometry, x-ray diffraction spectrometry (XRD), and x-ray photoelectron spectroscopy (XPS). Detailed comparison of data confirmed that the TXRF method itself was not sufficient tomore » determine all the elements (Z > 11) contained in the samples. In addition, results suggest that XRD should be combined with XPS in order to accurately determine compound composition. This study demonstrates that at least two analytical methods should be used in order to analyze the composition of unknown real samples.« less

Improved flotation performance of hematite fines using citric acid as a dispersant

NASA Astrophysics Data System (ADS)

Luo, Xi-mei; Yin, Wan-zhong; Sun, Chuan-yao; Wang, Nai-ling; Ma, Ying-qiang; Wang, Yun-fan

2016-10-01

In this study, citric acid was used as a dispersant to improve the flotation performance of hematite fines. The effect and mechanism of citric acid on the reverse flotation of hematite fines were investigated by flotation tests, sedimentation experiments, scanning electron microscopy (SEM), zeta-potential measurements, and X-ray photoelectron spectroscopy (XPS). The results of SEM analysis and flotation tests reveal that a strong heterocoagulation in the form of slime coating or coagulation in hematite fine slurry affects the beneficiation of hematite ores by froth flotation. The addition of a small amount of citric acid (less than 300 g/t) favorably affects the reverse flotation of hematite fines by improving particle dispersion. The results of sedimentation experiments, zeta-potential measurements, and XPS measurements demonstrate that citric acid adsorbs onto hematite and quartz surfaces via hydrogen bonding, thereby reducing the zeta potentials of mineral surfaces, strengthening the electrical double-layer repulsion between mineral particles, and dispersing the pulp particles.

Friction and Wear of Iron in Corrosive Media

NASA Technical Reports Server (NTRS)

Rengstorff, G. W. P.; Miyoshi, K.; Buckley, D. H.

1982-01-01

Friction and wear experiments were conducted with elemental iron exposed to various corrosive media including two acids, base, and a salt. Studies involved various concentrations of nitric and sulfuric acids, sodium hydroxide, and sodium chloride. Load and reciprocating sliding speed were kept constant. With the base NaOH an increase in normality beyond 0.01 N resulted in a decrease in both friction and wear. X-ray photoelectron spectroscopy (XPS) analysis of the surface showed a decreasing concentration of ferric oxide (Fe2O3) on the iron surface with increasing NaOH concentration. With nitric acid (HNO3) friction decreased in solutions to 0.05 N, beyond which no further change in friction was observed. The concentration of Fe2O3 on the surface continued to increase with increasing normality. XPS analysis revealed the presence of sulfates in addition of Fe2O3 on surfaces exposed to sulfuric acid and iron chlorides but no sodium on surfaces exposed to NaCl.

Effect of Electron Beam Irradiation on Structural and Optical Properties of Cu-Doped In2O3 Films Prepared by RF Magnetron Sputtering

NASA Astrophysics Data System (ADS)

Krishnan, R. Reshmi; Sanjeev, Ganesh; Prabhu, Radhakrishna; Pillai, V. P. Mahadevan

2018-02-01

Undoped and Cu-doped In2O3 films were prepared by radiofrequency magnetron sputtering technique. The effects of Cu doping and high-energy electron beam irradiation on the structural and optical properties of as-prepared films were investigated using techniques such as x-ray diffraction, x-ray photoelectron spectroscopy (XPS), lateral scanning electron microscopic image analysis, energy-dispersive x-ray (EDX) spectroscopy, micro-Raman, and ultraviolet-visible (UV-vis) spectroscopy. Moderate doping of Cu in In2O3 enhanced the intensity of (222) peak, indicating alignment of crystalline grains along <111>. Electron beam irradiation promoted orientation of crystalline grains along <111> in undoped and moderately Cu-doped films. EDX spectroscopic and XPS analyses revealed incorporation of Cu2+ ions in the lattice. The transmittance of Cu-doped films decreased with e-beam irradiation. Systematic reduction of the bandgap energy with increase in Cu doping concentration was seen in unirradiated and electron-beam-irradiated films.

Hydrothermal-reduction synthesis of manganese oxide nanomaterials for electrochemical supercapacitors.

PubMed

Zhang, Xiong; Chen, Yao; Yu, Peng; Ma, Yanwei

2010-11-01

In the present work, amorphous manganese oxide nanomaterials have been synthesized by a common hydrothermal method based on the redox reaction between MnO4(-) and Fe(2+) under an acidic condition. The synthesized MnO2 samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and electrochemical studies. XRD results showed that amorphous manganese oxide phase was obtained. XPS quantitative analysis revealed that the atomic ratio of Mn to Fe was 3.5 in the MnO2 samples. TEM images showed the porous structure of the samples. Electrochemical properties of the MnO2 electrodes were studied using cyclic voltammetry and galvanostatic charge-discharge cycling in 1 M Na2SO4 aqueous electrolyte, which showed excellent pseudocapacitance properties. A specific capacitance of 192 Fg(-1) at a current density of 0.5 Ag(-1) was obtained at the potential window from -0.1 to 0.9 V (vs. SCE).

Compositional depth profile of a native oxide LPCVD MNOS structure using X-ray photoelectron spectroscopy and chemical etching

NASA Technical Reports Server (NTRS)

Wurzbach, J. A.; Grunthaner, F. J.

1983-01-01

It is pointed out that there is no report of an unambiguous analysis of the composition and interfacial structure of MNOS (metal-nitride oxide semiconductor) systems, despite the technological importance of these systems. The present investigation is concerned with a study of an MNOS structure on the basis of a technique involving the use of X-ray photoelectron spectroscopy (XPS) with a controlled stopped-flow chemical-etching procedure. XPS is sensitive to the structure of surface layers, while stopped-flow etching permits the controlled removal of overlying material on a scale of atomic layers, to expose new surface layers as a function of thickness. Therefore, with careful analysis of observed intensities at measured depths, this combination of techniques provides depth resolution between 5 and 10 A. According to the obtained data there is intact SiO2 at the substrate interface. There appears to be a thin layer containing excess bonds to silicon on top of the SiO2.

Reactivity assay of surface carboxyl chain-ends of poly(ethylene terephthalate) (PET) film and track-etched microporous membranes using fluorine labelled- and/or 3H-labelled derivatization reagents: tandem analysis by X-ray photoelectron spectroscopy (XPS) and liquid scintillation counting (LSC)

NASA Astrophysics Data System (ADS)

Deldime, Michèle; Dewez, Jean-Luc; Schneider, Yves-Jacques; Marchand-Brynaert, Jacqueline

1995-09-01

Poly(ethylene terephthalate) (PET) films and track-etched microporous membranes of two different porosities were pretreated by hydrolysis and/or oxidation in order to enhance the amount of carboxyl chain-ends displayed on their surface. The reactivity of these carboxyl functions was determined by derivatization assays in which the reactions were carried out under conditions likely to be encountered in the coupling of water-soluble biochemical signals on the surface of biomaterials. Original reagents, fluorine-labelled and/or 3H-labelled aminoacid compounds, were used. The derivatized PET samples were examined by X-ray photoelectron spectroscopy (XPS) to characterize their apparent surfaces, and by liquid scintillation counting (LSC) to quantify the amount of tags fixed on their open surfaces. Using this dual assay technique, we analyzed the surface of microporous membranes which are currently used as substrates for cell culture systems.

Ferromagnetic mechanism of (Co, Cu)-codoped ZnO films with different Co concentrations investigated by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Yuan, Huan; Du, Xiaosong; Xu, Ming

2016-05-01

Cobalt/copper-codoped ZnO nanoparticles, synthesized with different Co concentrations by a sol-gel method using ethanol as solvent, were studied via XPS. Hexagonal wurtzite structure was found in all samples, with no evidence of any secondary phase. The average crystallite size of the samples was around 20-30 nm, altered significantly with increasing Co concentration. Copper ions and Cobalt ions are indeed substituted into the ZnO lattice at the Zn2+ site, as shown by XRD and XPS. Further studies showed dramatic changes of Cu valence from +2 to +1 as the Co concentration level exceeds 1%, accompanied by a blue-shift of the optical bandgap from 3.01 to 3.13 eV. Ferromagnetism of the Co-doped Zn0.95Cu0.05O thin films was observed and found to be tunable - a phenomenon associated with the valence state of the Cu ions and the existence of some defects like oxygen vacancies in the films.

Band offsets and growth mode of molecular beam epitaxy grown MgO (111) on GaN (0002) by x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Craft, H. S.; Collazo, R.; Losego, M. D.; Mita, S.; Sitar, Z.; Maria, J.-P.

2007-10-01

MgO is a proposed dielectric for use as a tunneling barrier in devices integrating GaN and ferroelectric oxides. In this study, we present data regarding the growth mode and band offsets of MgO grown epitaxially on GaN (0002) surfaces using molecular beam epitaxy. Using in situ x-ray photoelectron spectroscopy (XPS) and molecular beam epitaxy, we determine, from sequential growth experiments, that the growth of MgO proceeds via the Volmer-Weber (three-dimensional) mode, and full coalescence of the film does not occur until approximately 12nm of MgO has been deposited. The observation of a three-dimensional growth mode is in agreement with previously published data. For the valence band offset, we find a value of 1.2±0.2eV, which corresponds to a 3.2eV conduction band offset. XPS measurements suggest a chemically abrupt interface and no effect on band lineup due to the slow coalescence behavior.

High performance SONOS flash memory with in-situ silicon nanocrystals embedded in silicon nitride charge trapping layer

NASA Astrophysics Data System (ADS)

Lim, Jae-Gab; Yang, Seung-Dong; Yun, Ho-Jin; Jung, Jun-Kyo; Park, Jung-Hyun; Lim, Chan; Cho, Gyu-seok; Park, Seong-gye; Huh, Chul; Lee, Hi-Deok; Lee, Ga-Won

2018-02-01

In this paper, SONOS-type flash memory device with highly improved charge-trapping efficiency is suggested by using silicon nanocrystals (Si-NCs) embedded in silicon nitride (SiNX) charge trapping layer. The Si-NCs were in-situ grown by PECVD without additional post annealing process. The fabricated device shows high program/erase speed and retention property which is suitable for multi-level cell (MLC) application. Excellent performance and reliability for MLC are demonstrated with large memory window of ∼8.5 V and superior retention characteristics of 7% charge loss for 10 years. High resolution transmission electron microscopy image confirms the Si-NC formation and the size is around 1-2 nm which can be verified again in X-ray photoelectron spectroscopy (XPS) where pure Si bonds increase. Besides, XPS analysis implies that more nitrogen atoms make stable bonds at the regular lattice point. Photoluminescence spectra results also illustrate that Si-NCs formation in SiNx is an effective method to form deep trap states.

Density control of dodecamanganese clusters anchored on silicon(100).

PubMed

Condorelli, Guglielmo G; Motta, Alessandro; Favazza, Maria; Nativo, Paola; Fragalà, Ignazio L; Gatteschi, Dante

2006-04-24

A synthetic strategy to control the density of Mn12 clusters anchored on silicon(100) was investigated. Diluted monolayers suitable for Mn12 anchoring were prepared by Si-grafting mixtures of the methyl 10-undecylenoate precursor ligand with 1-decene spectator spacers. Different ratios of these mixtures were tested. The grafted surfaces were hydrolyzed to reveal the carboxylic groups available for the subsequent exchange with the [Mn12O12(OAc)16(H2O)4]4 H2O2 AcOH cluster. Modified surfaces were analyzed by attenuated total reflection (ATR)-FTIR spectroscopy, X-ray photoemission spectroscopy (XPS), and AFM imaging. Results of XPS and ATR-FTIR spectroscopy show that the surface mole ratio between grafted ester and decene is higher than in the source solution. The surface density of the Mn12 cluster is, in turn, strictly proportional to the ester mole fraction. Well-resolved and isolated clusters were observed by AFM, using a diluted ester/decene 1:1 solution.

A novel approach of chemical mechanical polishing for cadmium zinc telluride wafers.

PubMed

Zhang, Zhenyu; Wang, Bo; Zhou, Ping; Kang, Renke; Zhang, Bi; Guo, Dongming

2016-05-26

A novel approach of chemical mechanical polishing (CMP) is developed for cadmium zinc telluride (CdZnTe or CZT) wafers. The approach uses environment-friendly slurry that consists of mainly silica, hydrogen peroxide, and citric acid. This is different from the previously reported slurries that are usually composed of strong acid, alkali, and bromine methanol, and are detrimental to the environment and operators. Surface roughness 0.5 nm and 4.7 nm are achieved for Ra and peak-to-valley (PV) values respectively in a measurement area of 70 × 50 μm(2), using the developed novel approach. Fundamental polishing mechanisms are also investigated in terms of X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. Hydrogen peroxide dominates the passivating process during the CMP of CZT wafers, indicating by the lowest passivation current density among silica, citric acid and hydrogen peroxide solution. Chemical reaction equations are proposed during CMP according to the XPS and electrochemical measurements.

A novel approach of chemical mechanical polishing for cadmium zinc telluride wafers

PubMed Central

Zhang, Zhenyu; Wang, Bo; Zhou, Ping; Kang, Renke; Zhang, Bi; Guo, Dongming

2016-01-01

A novel approach of chemical mechanical polishing (CMP) is developed for cadmium zinc telluride (CdZnTe or CZT) wafers. The approach uses environment-friendly slurry that consists of mainly silica, hydrogen peroxide, and citric acid. This is different from the previously reported slurries that are usually composed of strong acid, alkali, and bromine methanol, and are detrimental to the environment and operators. Surface roughness 0.5 nm and 4.7 nm are achieved for Ra and peak-to-valley (PV) values respectively in a measurement area of 70 × 50 μm2, using the developed novel approach. Fundamental polishing mechanisms are also investigated in terms of X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. Hydrogen peroxide dominates the passivating process during the CMP of CZT wafers, indicating by the lowest passivation current density among silica, citric acid and hydrogen peroxide solution. Chemical reaction equations are proposed during CMP according to the XPS and electrochemical measurements. PMID:27225310

Synthesis of Ternary Borocarbonitrides by High Temperature Pyrolysis of Ethane 1,2-Diamineborane

PubMed Central

Leardini, Fabrice; Massimi, Lorenzo; Flores-Cuevas, Eduardo; Fernández, Jose Francisco; Ares, Jose Ramon; Betti, Maria Grazia; Mariani, Carlo

2015-01-01

Ethane 1,2-diamineborane (EDAB) is an alkyl-containing amine-borane adduct with improved hydrogen desorption properties as compared to ammonia borane. In this work, it is reported the high temperature thermolytic decomposition of EDAB. Thermolysis of EDAB has been investigated by concomitant thermogravimetry-differential thermal analysis-mass spectrometry experiments. EDAB shows up to four H2 desorption events below 1000 °C. Small fractions of CH4, C2H4 and CO/CO2 are also observed at moderate-high temperatures. The solid-state thermolysis product has been characterized by means of different structural and chemical methods, such as X-ray diffraction, Raman spectroscopy, Scanning electron microscopy, Elemental analysis, and X-ray photoelectron spectroscopy (XPS). The obtained results indicate the formation of a ternary borocarbonitride compound with a poorly-crystalline graphitic-like structure. By contrast, XPS measurements show that the surface is rich in carbon and nitrogen oxides, which is quite different to the bulk of the material. PMID:28793545

Preparation, Characterization and Intracellular Imaging of 2,4-Dichlorophenoxyacetic Acid Conjugated Gold Nanorods.

PubMed

Jia, Jin-Liang; Jin, Xiao-Yong; Liu, Qing-Le; Liang, Wen-Long; Lin, Miao-Shan; Xu, Han-Hong

2016-05-01

Visualizing the biodistribution of pesticides inside living cells is great importance for enhancing targeting of pesticides. Here we reported for the first time that gold nanorods (Au NRs) with size of 39.4 nm x 11.3 nm could be used as a fluorescent tracer to examine the distribution of a typical herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D), in tobacco bright yellow 2 (BY-2) cells. The nanostructures of hybrid materials were analyzed by using Raman spectra and X-ray photoelectron spectroscopy (XPS), including spectra assignments and electronic property. These data revealed 2,4-D has successfully conjugated MP-Au NRs according to Raman and XPS. The biodistribution of the conjugates inside BY-2 cells was directly examined at 12 and 24 h by the two-photon microscopy. The intensity of two-photon luminescence (TPL) inside cells demonstrated that the conjugates could be localized and excluded by BY-2 cells. Thus, this labeling approach opens up new avenues to the facile and efficient labeling of pesticides.

Synthesis of Ag metallic nanoparticles by 120 keV Ag- ion implantation in TiO2 matrix

NASA Astrophysics Data System (ADS)

Sharma, Himanshu; Singhal, Rahul

2017-12-01

TiO2 thin film synthesized by the RF sputtering method has been implanted by 120 keV Ag- ion with different doses (3 × 1014, 1 × 1015, 3 × 1015, 1 × 1016 and 3 × 1016 ions/cm2). Further, these were characterized by Rutherford back Scattering, XRD, X-ray photoelectron spectroscopy (XPS), UV-visible and fluorescence spectroscopy. Here we reported that after implantation, localized surface Plasmon resonance has been observed for the fluence 3 × 1016 ions/cm2, which was due to the formation of silver nanoparticles. Ag is in metallic form in the matrix of TiO2, which is very interestingly as oxidation of Ag was reported after implantation. Also, we have observed the interaction between nanoparticles of Ag and TiO2, which results in an increasing intensity in lower charge states (Ti3+) of Ti. This interaction is supported by XPS and fluorescence spectroscopy, which can help improve photo catalysis and antibacterial properties.

High-throughput characterization for solar fuels materials discovery

NASA Astrophysics Data System (ADS)

Mitrovic, Slobodan; Becerra, Natalie; Cornell, Earl; Guevarra, Dan; Haber, Joel; Jin, Jian; Jones, Ryan; Kan, Kevin; Marcin, Martin; Newhouse, Paul; Soedarmadji, Edwin; Suram, Santosh; Xiang, Chengxiang; Gregoire, John; High-Throughput Experimentation Team

2014-03-01

In this talk I will present the status of the High-Throughput Experimentation (HTE) project of the Joint Center for Artificial Photosynthesis (JCAP). JCAP is an Energy Innovation Hub of the U.S. Department of Energy with a mandate to deliver a solar fuel generator based on an integrated photoelectrochemical cell (PEC). However, efficient and commercially viable catalysts or light absorbers for the PEC do not exist. The mission of HTE is to provide the accelerated discovery through combinatorial synthesis and rapid screening of material properties. The HTE pipeline also features high-throughput material characterization using x-ray diffraction and x-ray photoemission spectroscopy (XPS). In this talk I present the currently operating pipeline and focus on our combinatorial XPS efforts to build the largest free database of spectra from mixed-metal oxides, nitrides, sulfides and alloys. This work was performed at Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award No. DE-SC0004993.

Effect of surface charge density on the affinity of oxide nanoparticles for the vapor-water interface.

PubMed

Brown, Matthew A; Duyckaerts, Nicolas; Redondo, Amaia Beloqui; Jordan, Inga; Nolting, Frithjof; Kleibert, Armin; Ammann, Markus; Wörner, Hans Jakob; van Bokhoven, Jeroen A; Abbas, Zareen

2013-04-23

Using in-situ X-ray photoelectron spectroscopy at the vapor-water interface, the affinity of nanometer-sized silica colloids to adsorb at the interface is shown to depend on colloid surface charge density. In aqueous suspensions at pH 10 corrected Debye-Hückel theory for surface complexation calculations predict that smaller silica colloids have increased negative surface charge density that originates from enhanced screening of deprotonated silanol groups (≡Si-O(-)) by counterions in the condensed ion layer. The increased negative surface charge density results in an electrostatic repulsion from the vapor-water interface that is seen to a lesser extent for larger particles that have a reduced charge density in the XPS measurements. We compare the results and interpretation of the in-situ XPS and corrected Debye-Hückel theory for surface complexation calculations with traditional surface tension measurements. Our results show that controlling the surface charge density of colloid particles can regulate their adsorption to the interface between two dielectrics.

Electrochemically Controlled Ion-exchange Property of Carbon Nanotubes/Polypyrrole Nanocomposite in Various Electrolyte Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Daiwon; Zhu, Chengzhou; Fu, Shaofang

2016-09-15

The electrochemically controlled ion-exchange properties of multi-wall carbon nanotube (MWNT)/electronically conductive polypyrrole (PPy) polymer composite in the various electrolyte solutions have been investigated. The ion-exchange behavior, rate and capacity of the electrochemically deposited polypyrrole with and without carbon nanotube (CNT) were compared and characterized using cyclic voltammetry (CV), chronoamperometry (CA), electrochemical quartz crystal microbalance (EQCM), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). It has been found that the presence of carbon nanotube backbone resulted in improvement in ion-exchange rate, stability of polypyrrole, and higher anion loading capacity per PPy due to higher surface area, electronic conductivity, porous structuremore » of thin film, and thinner film thickness providing shorter diffusion path. Chronoamperometric studies show that electrically switched anion exchange could be completed more than 10 times faster than pure PPy thin film. The anion selectivity of CNT/PPy film is demonstrated using X-ray photoelectron spectroscopy (XPS).« less

Electron-beam-induced post-grafting polymerization of acrylic acid onto the surface of Kevlar fibers

NASA Astrophysics Data System (ADS)

Xu, Lu; Hu, Jiangtao; Ma, Hongjuan; Wu, Guozhong

2018-04-01

The surface of Kevlar fibers was successfully modified by electron beam (EB)-induced post-grafting of acrylic acid (AA). The generation of radicals in the fibers was confirmed by electron spin resonance (ESR) measurements, and the concentration of radicals was shown to increase as the absorbed dose increased, but decrease with increasing temperature. The influence of the synthesis conditions on the degree of grafting was also investigated. The surface microstructure and chemical composition of the modified Kevlar fibers were characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The SEM images revealed that the surface of the grafted fibers was rougher than those of the pristine and irradiated fibers. XPS analysis confirmed an increase in C(O)OH groups on the surface of the Kevlar fibers, suggesting successful grafting of AA. These results indicate that EB-induced post-grafting polymerization is effective for modifying the surface properties of Kevlar fibers.

Summary: Update to ASTM guide E 1523 to charge control and charge referencing techniques in x-ray photoelectron spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baer, D.R.

2005-05-01

An updated version of the American Society for Testing and Materials (ASTM) guide E 1523 to the methods to charge control and charge referencing techniques in x-ray photoelectron spectroscopy has been released by ASTM [Annual Book of ASTM Standards Surface Analysis (American Society for Testing and Materials, West Conshohocken, PA, 2004), Vol. 03.06]. The guide is meant to acquaint x-ray photoelectron spectroscopy (XPS) users with the various charge control and charge referencing techniques that are and have been used in the acquisition and interpretation of XPS data from surfaces of insulating specimens. The current guide has been expanded to includemore » new references as well as recommendations for reporting information on charge control and charge referencing. The previous version of the document had been published in 1997 [D. R. Baer and K. D. Bomben, J. Vac. Sci. Technol. A 16, 754 (1998)].« less

Effect of doping on the modification of polycrystalline silicon by spontaneous reduction of diazonium salts

NASA Astrophysics Data System (ADS)

Girard, A.; Coulon, N.; Cardinaud, C.; Mohammed-Brahim, T.; Geneste, F.

2014-09-01

The chemical modification of doped polycrystalline silicon materials (N+, N++ and P++) and silicon (1 0 0) and (1 1 1) used as references is investigated by spontaneous reduction of diazonium salts. The effectiveness of the grafting process on all polySi surfaces is shown by AFM and XPS analyses. The effect of substrate doping on the efficiency of the electrografting process is compared by using the thicknesses of the deposited organic films. For a better accuracy, two methods are used to estimate the thicknesses: XPS and the coupling of a O2 plasma etching with AFM measurement. Structural characteristics of the poly-Si films were investigated by Scanning Electron Microscopy and X-ray diffraction to find a correlation between the structure of the material and its reactivity. Different parameters that could have an impact on the efficiency of the grafting procedure are discussed. The observed differences between differently doped silicon surfaces is rather limited, this is in agreement with the radical character of the reacting species.