Combination Of X-ray Photoelectron Spectroscopy Research Articles

Aluminum Nanoparticle Production by Acetonitrile-Assisted Milling: Effects of Liquid- vs Vapor-Phase Milling and of Milling Method on Particle Size and Surface Chemistry

Milling aluminum balls together with either vapor- or liquid-phase acetonitrile (ACN) leads to production of nanoparticles by mechanical attrition; however, vapor-phase ACN is far more efficient at inducing size reduction, leading to more, smaller, and more uniform particles. The attrition process is also more efficient than traditional milling of particulate starting material and produces nanoparticles with substantially lower contamination levels. This paper is aimed at better understanding the nature of the size reduction process, the chemistry driving it, and the particles it produces. Mass spectrometry was used to probe gases generated during milling, and a combination of X-ray photoelectron spectroscopy, infrared spectroscopy, dynamic light scattering, helium ion microscopy, scanning electron microscopy, and thermogravimetric analysis/mass spectrometry was used to probe the particles and their surface layer. To provide further insight into the chemistry occurring between ACN and aluminum under milli...

Combined DFT and XPS investigation of iodine anions adsorption on the sulfur terminated (001) chalcopyrite surface

The adsorption of iodine anions (iodide and iodate) on the sulfur terminated (001) chalcopyrite surface has been systematically investigated combining first-principles calculations based on density functional theory (DFT) with X-ray photoelectron spectroscopy (XPS) measurements. Based on the total energy calculations and geometric optimization, the thermodynamically preferred site was copper atom for iodide adsorption and iron atom for iodate adsorption, respectively. In the case of Cu site mode, the iodate underwent a dissociative adsorption, where one IO bond of iodate ion was broken and the dissociative oxygen atom adsorbed on the adjacent sulphur site. Projected density of states (PDOS) analysis further clarified the interaction mechanism between active sites of chalcopyrite surface and adsorbates. In addition, full-range XPS spectra qualitatively revealed the presence of iodine on chalcopyrite surface. High resolution XPS spectra of the I 3d peaks after adsorption verified the chemical environment of iodine. The binding energies of 618.8eV and 623.5eV for I 3d5/2 peaks unveiled that the adsorption of iodide and iodate ions on copper-iron sulfide minerals was the result of formation of low solubility metal iodides precipitate. Also two I 3d peaks with low intensity around 618eV and 630eV might be related to the inorganic reduction of iodate to iodide by reducing S2− ion of chalcopyrite.

Instability of NiMoS2 and CoMoS2 Hydrodesulfurization Catalysts at Ambient Conditions: A Quasi in Situ High-Resolution Transmission Electron Microscopy and X-ray Photoelectron Spectroscopy Study

The effect of exposure to ambient air of MoS2-based, γ-Al2O3-supported, hydrodesulfurization (HDS) catalysts has been studied using high-resolution transmission electron microscopy (HRTEM). Analysis of unpromoted as well as Ni- and Co-promoted MoS2 samples showed that the number of MoS2 slabs and the average slab length decreased as a function of air exposure time. A parallel X-ray photoelectron spectroscopy (XPS) study showed this effect to be due to oxidation. During the first 24 h of exposure to air, all 1 bar sulfided (Ni/Co)MoS2 samples showed an initial slab length decrease of approximately 20%. After an additional month in air, the slabs had deteriorated significantly further. A sample of CoMoS2 sulfided at 30 bar showed a slightly enhanced effect of oxidation, particularly after the first 5 min in air. The combined HRTEM and XPS results lead to the proposal of the formation of a protective oxide ring around the remaining sulfidic species inside the MoS2 slabs to explain the mechanism of this oxida...

Growth Instabilities as a Source of Surface Chemical Structuration in Functional Perovskite Thin Films

The spontaneous formation of double chemical terminated surfaces of La0.7Sr0.3MnO3 due to deviations from ideal epitaxial growth during its deposition on SrTiO3(001) is presented. The development of surface regions with differentiated topmost composition leads to outstanding surface nanostructuration presenting notably distinct local properties, particularly in terms of electric transport and local work function. Correlation between combined atomic force microscopy and X-ray photoelectron spectroscopy data allows the chemical identification of the two terminations as corresponding to La0.7Sr0.3O and MnO2. The most likely atomistic process at the origin of the surface organization has been interpreted by Monte Carlo simulations that reveal the importance of stacking fault formation as growth proceeds. We present a physical understanding of the experimental results for surfaces in which different electronic responses coexist. The conclusions of the present work can be extended to the growth of other perovskite thin films, therefore broadening the field of functional materials nanostructuration.

BSA adsorption on a plasma-deposited silver nanocomposite film controls silver release: A QCM and XPS-based modelling

Abstract The adsorption of a model protein, the bovine serum albumin (BSA), on plasma-deposited silver nanocomposite thin films was investigated in situ by quartz crystal microbalance (QCM) and ex situ by X-ray photoelectron spectroscopy (XPS). For comparison, BSA adsorption was also studied on pure silver sample and on the polymeric matrix without silver nanoparticles. Both techniques showed that BSA adsorption systematically occurred, regardless of the chemical composition of the solid surface. BSA adsorption was found to be a fast and irreversible process. For the adsorbed BSA layer characterization, a general island model was considered. The height of the protein islands ( h ) and their surface coverage ( γ ) were estimated from combined QCM and XPS data. On the polymeric matrix, the surface coverage was low whereas on pure silver sample and on the nanocomposite film, it was significantly increased. From QCM measurements, mass loss at a constant rate, ascribed to the release and dissolution of Ag particles from the nanocomposite film into the surrounding solution, was observed before and after BSA adsorption, with two different associated rates. The decrease of the silver release rate after BSA adsorption is explained by silver particles coverage by protein islands. BSA molecules adsorbed on silver nanoparticles have a “blocking” effect, decreased the rate of silver nanoparticle release. However, silver dissolution as Ag + ions may still occur.

Selective Growth of Titanium Nitride on HfO2 across Nanolines and Nanopillars

This work targets the area selective atomic layer deposition (AS-ALD) of TiN onto HfO2 for use as the word line in a memory device. Unlike other patterning processes, AS-ALD eliminates etching steps and also allows for growth of patterned films with precise thickness control. This study investigates how AS-ALD differs on planar and nonplanar surfaces. Using a combination of X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy, we demonstrate a way to confer selectivity to a substrate using surface features. Self-assembled monolayers form defects at regions of high curvature, allowing nucleation of TiN films in ALD. This is in contrast to a treated planar surface with no features, which exhibits complete blocking of TiN up to a certain limit of ALD cycles.

Characterization and antibacterial properties of porous fibers containing silver ions

Materials prepared on the base of bioactive silver compounds have become more and more popular. In the present work, the surface morphology, structure and properties, of electrospun Polylactide Polylactic acid (PLA) porous fibers containing various ratios of silver ions were investigated by a combination of X-ray photoelectron spectroscopy (XPS), universal testing machine, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and et al. The biological activities of the proposed porous fibers were discussed in view of the released silver ions concentration. Antibacterial properties of these porous fibers were studied using two bacterial strains: Escherichia coli (E. coli) and Methicillin-resistant Staphylococcus aureus (MRSA). Results of the antibacterial testing suggested that PLA porous fibers containing silver ions could be used as potent antibacterial wound dressing materials in the biomedical field.

Surface Partitioning in Organic-Inorganic Mixtures Contributes to the Size-Dependence of the Phase-State of Atmospheric Nanoparticles.

Atmospheric particulate matter is one of the main factors governing the Earth's radiative budget, but its exact effects on the global climate are still uncertain. Knowledge on the molecular-scale surface phenomena as well as interactions between atmospheric organic and inorganic compounds is necessary for understanding the role of airborne nanoparticles in the Earth system. In this work, surface composition of aqueous model systems containing succinic acid and sodium chloride or ammonium sulfate is determined using a novel approach combining X-ray photoelectron spectroscopy, surface tension measurements and thermodynamic modeling. It is shown that succinic acid molecules are accumulated in the surface, yielding a 10-fold surface concentration as compared with the bulk for saturated succinic acid solutions. Inorganic salts further enhance this enrichment due to competition for hydration in the bulk. The surface compositions for various mixtures are parametrized to yield generalizable results and used to explain changes in surface tension. The enhanced surface partitioning implies an increased maximum solubility of organic compounds in atmospheric nanoparticles. The results can explain observations of size-dependent phase-state of atmospheric nanoparticles, suggesting that these particles can display drastically different behavior than predicted by bulk properties only.

When the Grafting of Double Decker Phthalocyanines on Si(100)-2 × 1 Partly Affects the Molecular Electronic Structure

A combined X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and density functional theory (DFT) study has been performed to characterize the adsorbate interaction of lutetium biphthalocyanine (LuPc2) molecules on the Si(100)-2 × 1 surface. Large molecule–substrate adsorption energies are computed and are found to compete with the molecule–molecule interactions of the double decker molecules. A particularly good matching between STM images and computed ones confirms the deformation of the molecule upon the absorption process. The comparison between DFT calculations and XP spectra reveals that the electronic distribution in the two plateaus of the biphthalocyanine are not affected in the same manner upon the adsorption onto the silicon surface. This finding can be of particular importance in the implementation of organic molecules in hybrid devices.

Understanding the Roles of Electrolyte Additives on the Surface Modification Mechanism of Silicon-Based Anodes in Lithium-Ion Batteries

Silicon is considered as a promising candidate of the anode material for the next generation lithium-ion batteries, due to its substantially higher gravimetric and volumetric capacity compared to conventionally used graphite. Electrolyte additives, fluoroethylene carbonate (FEC) and vinylene carbonate (VC) particularly, are usually applied for silicon-based lithium-ion batteries to tackle the problems such as poor capacity retention and low coulombic efficiency.1-3 In the present work, the decomposition mechanism of FEC as well as the surface modification of Si electrodes were investigated.4 It was observed that the FEC additive degrades at a higher reduction potential prior to the other carbonate solvents. A conformal solid electrolyte interphase (SEI), which consists of the decomposition products of FEC, is instantaneously formed on the silicon electrode as a result. This stable SEI layer sufficiently limits the emergence of cracks and suppresses the additional SEI formation from the decomposition of other electrolyte components. Both of these effects lead to a slower increase in polarization, thus a slower capacity fading, for the FEC containing cell. The differences in the SEI layer, formed with or without the presence of FEC, are schematically demonstrated in Fig 1. Besides, it was also observed that the LiPF6 decomposition can be influenced with the presence of FEC, and this was further studied with a combination of X-ray photoelectron spectroscopy (XPS) and solid-state nuclear magnetic resonance (NMR) techniques. We also demonstrated that by forming an effective SEI layer with the FEC and VC electrolyte additives, the silicon electrodes can be equally well functioning with a novel lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide (LiTDI)-based electrolyte as with the state-of-art LiPF6-based electrolyte.5 Figure 1

External surface structure of organoclays analyzed by transmission electron microscopy and X-ray photoelectron spectroscopy in combination with molecular dynamics simulations

HypothesisInterface properties of organoclay particles can be related directly to type of organic cation, and density and arrangement of organic coating at clay surfaces. ExperimentsThis study provides detailed nanoscale insights on surface structure of hexadecyltrimethylammonium/hexadecylpyridinium-montmorillonite (HDTMA+/HDPy+-M) organoclays by combining several experimental methods (e.g. transmission electron microscopy, TEM, and X-ray photoelectron spectroscopy, XPS) with molecular simulations. FindingsTEM showed a relation between the thickness of the organic coating and the amount of organic cation loading. Furthermore, coating thickness varied for the same sample indicating a heterogeneous surface of clay particles. The changes in elemental composition determined by XPS were correlated with the thickness of the organic coating. High resolution XPS showed changes in binding energies of CN bonds, which were attributed to varying local environment of head groups of organic cations. Classical molecular dynamics (MD) simulations showed a successive transformation of the organic cation coating of the montmorillonite surface from thin disordered monolayers at low up to disordered bilayer or quasi paraffin-type arrangements at high surfactant coverages. For organoclays with low cation loading no significant difference was observed between HDTMA+ and HDPy+. However, at high cation loading, surface packing density was higher for HDTMA+ than for HDPy+.

Characterization of oxygenated species at water/Pt(111) interfaces from DFT energetics and XPS simulations

Determining the atomic-scale structure of oxygenated species at water/Pt(111) interfaces under electrochemical oxygen reduction reaction (ORR) conditions has been a significant, long-term challenge for both experimentalists and theorists. Numerous techniques have elucidated important information about this system, but significant uncertainties relating to the structure and hydration state of adsorbed oxygenated species remain. To resolve some of these questions, an approach based on careful calibration of Density Functional Theory (DFT)-determined energetics, as well as detailed simulation of X-ray Photoelectron Spectroscopy (XPS) signatures, is developed. The combined energetic and XPS analysis of various oxygenated species demonstrates that non-hydrated OH, which has been suggested, by analysis of O 1s core-level binding data from state-of-the-art XPS studies, to be an abundant surface species at water/Pt(111) interfaces during ORR, is in fact unlikely to exist at potentials relevant to ORR, although it might be found in other conditions. The OH is more likely to be present in a fully hydrated state, and the experimentally observed features can be assigned to other oxygen arrangements. This insight about the nature of OH binding at water-Pt interfaces has implications not only for the general understanding of electrified water/Pt interfaces, but also for the design of ORR catalysts with improved performance on the basis of first principles calculations.

CO-Terminated Platinum Electrodeposition on Nb-Doped Bulk Rutile TiO2

Nanoparticulate platinum on carbon as oxygen reduction electrocatalyst suffers from two major drawbacks, namely, low specific activity of the Pt particles and corrosion instability of the carbon support under hydrogen starvation conditions (reverse current degradation). Both issues can be tackled by Pt thin films on TiO2 support. Platinum films were synthesized on commercially available Nb-doped bulk TiO2 electrodes via electrodeposition from Ar- (bulk amounts) and CO-saturated solutions (monolayer amounts). The platinized electrodes were tested for ORR activity in a voltammetric fashion, and the field-free semiconductor properties were evaluated by a combination of X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry (SE), photoelectron yield spectroscopy (PYS), electrochemical impedance spectroscopy (EIS), and bulk conductivity measurements. The deposition of bulk amounts of Pt leads to a situation where the catalytic activity is directly correlated to the conductivity of the electrode. Raising the majority carrier density in the Nb-doped TiO2, via proton intercalation in aqueous HClO4 or glycol, drastically increased the activity. In case of monolayer deposits (CO-terminated deposition), intercalation has practically no effect on activity. Thus, the hypothesis is formed that unfavorable electronic interaction of the TiO2 support with small amounts of platinum drastically reduces ORR activity, an effect which is not observed for monolayer amounts of Pt deposited on gold.

Band diagram for low-k/Cu interconnects: The starting point for understanding back-end-of-line (BEOL) electrical reliability

The starting point for describing the electrostatic operation of any semiconductor device begins with a band diagram illustrating changes in the semiconductor Fermi level and the alignment of the valence and conduction bands with other interfacing semiconductors, insulating dielectrics and metal contacts. Such diagrams are essential for understanding the behavior and reliability of any semiconductor device. For metal interconnects, the band alignment between the metal conductor and the insulating intermetal and interlayer dielectric (ILD) is equally important. However, relatively few investigations have been made. In this regard, we have investigated the band alignment at the most common interfaces present in traditional single and dual damascene low-k/Cu interconnect structures. We specifically report combined X-ray photoelectron spectroscopy and reflection electron energy loss spectroscopy (REELS) measurements of the Schottky barrier present at the ILD and dielectric Cu capping layer (CCL) interfaces with the Ta(N) via/trench Cu diffusion barrier. We also report similar measurements of the valence and conduction band offsets present at the interface between a-SiN(C):H dielectric CCLs and low-k a-SiOC:H ILDs (porous and non-porous). The combined results point to metal interfaces with the CCL having the lowest interfacial barrier for electron transport. As trap and defect states in low-k dielectrics are also important to understanding low-k/Cu interconnect reliability, we additionally present combined electron paramagnetic resonance (EPR) and electrically detected magnetic resonance (EDMR) measurements to determine the chemical identity and energy level of some electrically active trap/defect states in low-k dielectrics. Combined with the photoemission derived band diagrams, the EPR/EDMR measurements point to mid-gap carbon and silicon dangling bond defects in the low-k ILD and CCL, respectively, playing a role in electronic transport in these materials. We show that in many cases the combined band and defect state diagrams can explain and predict some of the observed reliability issues reported for low-k/Cu interconnects.

Impact of the salts and solvents on the SEI formation in Sb/Na batteries: An XPS analysis

A thorough X-ray photoelectron spectroscopy (XPS) is carried out on the Sb/Na electrochemical cell to rationalize the different electrochemical performances in terms of irreversible capacity on first cycle, cumulated capacity losses, reversible capacity and capacity retention. Surface analysis of Sb electrode cycled versus sodium using three different electrolyte formulations by changing the nature of the salt (NaClO4 or NaPF6) and the nature of the solvents (PC or EC/DMC mixture) was performed by a combined XPS core peaks and quantification data analysis to establish the main components of the solid electrolyte interphase film (SEI) and its evolution on cycling. The passivation layer formed during cycling is mainly constituted of carbonates, Na2CO3 and alkylcarbonates, that appear during the discharge after the preferential deposition of NaF from the degradation of FEC. The solvent appears to have a key role, and the NaClO4/PC electrolyte, despite the high viscosity of its solvent gives the best compromise in terms of performances by forming a stable and thick SEI at the surface of all components of the composite electrode.

Synthesis of nanoscale silicon oxide oxidation state distributions: The transformation from hydrophilicity to hydrophobicity

Silicon oxide nanostructures which span the range from hydrophilic to hydrophobic have been synthesized. The surface chemistry of these silicon-based nanostructures was analyzed using a combination of X-ray photoelectron spectroscopy, reflectance infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. The dominant oxidation state for the nanostructured oxides shifts from an average oxidation state of +III to a combination of +II and +III oxidation states. A correlation of the ability to adsorb water with variations in the surface Si:O ratios was observed showing a transition from hydrophilic to hydrophobic character.

Pleomorphic structural imperfections caused by pulsed Bi-implantation in the bulk and thin-film morphologies of TiO2

The results of combined experimental and theoretical study of pleomorphic substitutional and clustering effects in Bi-doped TiO2 hosts (bulk and thin-film morphologies) are presented. Bi-doping of the bulk and thin-film titanium dioxide was made with help of pulsed ion-implantation (EBi+=30 keV, D=1×1017cm−2) without posterior tempering. The X-ray photoelectron spectroscopy (XPS) qualification (core-levels and valence bands) and Density-Functional Theory (DFT) calculations were employed in order to study the electronic structure of Bi-ion implanted TiO2 samples. According to XPS data obtained and DFT calculations, the Bi→Ti cation substitution occurs in Bi-implanted bulk TiO2, whereas in the thin-film morphology of TiO2:Bi the Bi-atoms have metal-like clusters segregation tendency. Based on the combined XPS and DFT considerations the possible reasons and mechanism for the observed effects are discussed. It is believed that established peculiarities of bismuth embedding into employed TiO2 hosts are mostly the sequence of pleomorphic origin for the formed “bismuth–oxygen” chemical bonding.

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

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 (1keV) 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.

Surface complexation modeling of U(VI) adsorption on granite at ambient/elevated temperature: Experimental and XPS study

The Beishan granitic formation is being investigated as a potential host rock for a high-level radioactive waste repository in China. It is important to understand the retention processes, including influential parameters such as the metal ion concentration, pH, ionic strength (I) and temperature. The present study deals with U(VI) adsorption on Beishan granite using batch-type experiments in a CO2-free atmosphere. U(VI) adsorption on granite is shown to be insensitive to ionic strength. Temperature has a positive effect on U(VI) adsorption indicating that surface reactions are endothermic. Combining X-ray photoelectron spectroscopy (XPS) analysis and adsorption data at 25°C, a Generalized Composite (GC) model with three surface complexes, SOUO2+, SO(UO2)2(OH)2+ and SO(UO2)3(OH)5, was constructed. The experimental data at 40°C and 60°C were fitted by the proposed model to obtain the equilibrium constants (K) of the surface reactions at these two temperatures. The enthalpy changes (ΔH) of the surface reactions were evaluated from the equilibrium constants obtained at three temperatures via the van't Hoff equation. Finally, blind modeling predictions were performed to test the robustness of the proposed model and ΔH. Satisfactory agreement with the literature data confirmed that this GC model with ΔH proving a useful tool to predict U(VI) adsorption on granite samples, especially on Beishan granite at ambient/high temperature.

Peptide Conjugation to a Polymer Coating via Native Chemical Ligation of Azlactones for Cell Culture.

Conjugation of biomolecules for stable presentation is an essential step toward reliable chemically defined platforms for cell culture studies. In this work, we describe the formation of a stable and site-specific amide bond via the coupling of a cysteine terminated peptide at low concentration to an azlactone containing copolymer coating. A copolymer of polyethylene glycol methyl ether methacrylate-ran-vinyl azlactone-ran-glycidyl methacrylate P(PEGMEMA-r-VDM-r-GMA) was used to form a thin coating (20-30 nm) on silicon and polycarbonate substrates. The formation and stability of coating-peptide bonds for peptides containing free thiols and amines were quantified by X-ray photoelectron spectroscopy (XPS) after exposure to cell culture conditions. Peptides containing a thiol as the only nucleophile coupled via a thioester bond; however, the bond was labile under cell culture conditions and almost all the bound peptides were displaced from the surface over a period of 2 days. Coupling with N-terminal primary amine peptides resulted in the formation of an amide bond with low efficiency (<20%). In contrast, peptides containing an N-terminal cysteine, which contain both nucleophiles (free thiol and amine) in close proximity, bound with 67% efficiency under neutral pH, and were stable under the same conditions for 2 weeks. Control studies confirm that the stable amide formation was a result of an intramolecular rearrangement through a N-acyl intermediate that resembles native chemical ligation. Through a combination of XPS and cell culture studies, we show that the cysteine terminated peptides undergo a native chemical ligation process at low peptide concentration in aqueous media, short reaction time, and at room temperature resulting in the stable presentation of peptides beyond 2 weeks for cell culture studies.