Combination Of X-ray Photoelectron Spectroscopy Research Articles

A non-platinum counter electrode, MnNx/C, for dye-sensitized solar cell applications

A non-platinum metal catalyst, MnNx/C was synthesized via the high-pressure pyrolysis route. The combination of X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) studies indicated the presence of Mn in +2 oxidation state surrounded by four N atoms. The peak-to-peak separation (ΔEp) of the more negative peak pair observed for I3−/I− redox couple over MnNx/C catalyst was 20mV lower than that of the Pt catalyst, indicating high reversibility of the redox couple over MnNx/C catalyst. The charge transfer resistance of the MnNx/C electrode, as measured by the impedance spectroscopy, is∼2Ω higher than that of Pt, which resulted slightly lower short circuit current (Jsc) value for MnNx/C over Pt, however the fill factor (FF) and power conversion efficiency (PCE) values of MnNx/C was slightly higher and comparable to that of Pt respectively. Hence; replacing Pt with MnNx/C would decrease the cost of DSSCs.

Heteroepitaxy of Fe3O4/Muscovite: A New Perspective for Flexible Spintronics.

Spintronics has captured a lot of attention since it was proposed. It has been triggering numerous research groups to make their efforts on pursuing spin-related electronic devices. Recently, flexible and wearable devices are in a high demand due to their outstanding potential in practical applications. In order to introduce spintronics into the realm of flexible devices, we demonstrate that it is feasible to grow epitaxial Fe3O4 film, a promising candidate for realizing spintronic devices based on tunneling magnetoresistance, on flexible muscovite. In this study, the heteroepitaxy of Fe3O4/muscovite is characterized by X-ray diffraction, high-resolution transmission electron microscopy, and Raman spectroscopy. The chemical composition and magnetic feature are investigated by a combination of X-ray photoelectron spectroscopy and X-ray magnetic circular dichroism. The electrical and magnetic properties are examined to show the preservation of the primitive properties of Fe3O4. Furthermore, various bending tests are performed to show the tunability of functionalities and to confirm that the heterostructures retain the physical properties under repeated cycles. These results illustrate that the Fe3O4/muscovite heterostructure can be a potential candidate for the applications in flexible spintronics.

Complex XPS and Raman Study of Graphene on Copper and Si/SiO<sub>2</sub> Subjected to Ar Ion Treatment

Graphene grown by chemical vapor deposition on copper and the one transferred to Si/SiO2 substrate were subjected to Ar ion treatment. A combination of X-ray photoelectron spectroscopy and Raman spectroscopy were used for characterization. According to XPS data sample on Si/SiO2 appears less susceptible to sputtering under bombardment. However, the defect concentrations introduced to the transferred graphene reach up the value two orders of magnitude higher than that in as grown graphene on Cu. We attribute this difference to the influence of the non-compensated charge formed on the insulating SiO2 layer under bombardment.

Chromium functionalized diglyme plasma polymer coating enhances enzyme-linked immunosorbent assay performance.

Ensuring the optimum orientation, conformation, and density of substrate-bound antibodies is critical for the success of sandwich enzyme-linked immunosorbent assays (ELISAs). In this work, the authors utilize a diethylene glycol dimethyl ether plasma polymer (DGpp) coating, functionalized with chromium within a 96 well plate for the enhanced immobilization of a capture antibody. For an equivalent amount of bound antibody, a tenfold improvement in the ELISA signal intensity is obtained on the DGpp after incubation with chromium, indicative of improved orientation on this surface. Time-of-flight secondary-ion-mass-spectrometry (ToF-SIMS) and principal component analysis were used to probe the molecular species at the surface and showed ion fragments related to lysine, methionine, histidine, and arginine coupled to chromium indicating candidate antibody binding sites. A combined x-ray photoelectron spectroscopy and ToF-SIMS analysis provided a surface molecular characterization that demonstrates antibody binding via the chromium complex. The DGpp+Cr surface treatment holds great promise for improving the efficacy of ELISAs.

Investigation of the thermal stability of Mo-In0.45Ga0.47As for applications as source/drain contacts

The electrical and chemical stability of Mo-InGaAs films for source-drain applications in transistor structures has been investigated. It was found that for 5 nm thick Mo films, the sheet resistance remains approximately constant with increasing anneal temperatures up to 500 °C. A combined hard x-ray photoelectron spectroscopy and x-ray absorption spectroscopy analysis of the chemical structure of the Mo-InGaAs alloy system as a function of annealing temperature showed that the interface is chemically abrupt with no evidence of inter-diffusion between the Mo and InGaAs layers. These results indicate the suitability of Mo as a thermally stable, low resistance source-drain contact metal for InGaAs-channel devices.

An Aqueous Metal-Ion Capacitor with Oxidized Carbon Nanotubes and Metallic Zinc Electrodes

An aqueous metal ion capacitor comprising of a zinc anode, an oxidized carbon nanotubes (oCNTs) cathode and a zinc sulfate electrolyte is reported. Since the shuttling cation is Zn2+, this typical metal ion capacitor is named as zinc-ion capacitor (ZIC). The ZIC integrates the divalent zinc stripping/plating chemistry with the surface-enabled pseudocapacitive cation adsorption/desorption on oCNTs. The surface chemistry and crystallographic structure of oCNTs were extensively characterized by combining X-ray photoelectron spectroscopy, Fourier-transformed infrared spectroscopy, Raman spectroscopy and X-ray powder diffraction. The function of the surface oxygen groups in surface cation storage was elucidated by a series of electrochemical measurement and the surface-enabled ZIC showed better performance than the ZIC with an un-oxidized CNT cathode. The reaction mechanism at the oCNT cathode involves the additional reversible Faradaic process, while the CNTs merely show electric double layer capacitive behavior involving a non-Faradaic process. The aqueous hybrid ZIC comprising the oCNT cathode exhibited a specific capacitance of 20 mF cm-2 (corresponding to 53 F g-1) in the range of 0-1.8 V at 10 mV s-1 and a stable cycling performance up to 5000 cycles.

XPS and SIMS study of the surface and interface of aged C+ implanted uranium

X-ray photoelectron spectroscopy in combination with secondary ion mass spectrometry depth profiling were used to investigate the surface and interfacial chemistry of C+ ion implanted polycrystalline uranium subsequently oxidized in air for over 10 years at ambient temperature. The original implantation of 33 keV C+ ions into U238 with a dose of 4.3 × 1017 cm−3 produced a physically and chemically modified surface layer that was characterized and shown to initially prevent air oxidation and corrosion of the uranium after 1 year in air at ambient temperature. The aging of the surface and interfacial layers were examined by using the chemical shift of the U 4f, C 1s, and O 1s photoelectron lines. In addition, valence band spectra were used to explore the electronic structure of the aged carbide surface and interface layer. Furthermore, the time-of-flight secondary ion mass spectrometry depth profiling results for the aged sample confirmed an oxidized uranium carbide layer over the carbide layer/U metal interface.

Degradation and Stabilization of Lithium Cobalt Oxide in Aqueous Electrolytes

Lithium cobalt oxide (LCO) has long been proven to be an excellent material for cathodes in organic electrolytes [1]. It has shown high volumetric capacity and good stability in non-aqueous environments of commercial lithium-ion (Li-ion) batteries. Unfortunately, the flammability of organic electrolytes in combination with a special propensity for batteries constructed with LCO to experience thermal runaway creates safety concerns [2]. Here we discuss the exceptional electrochemical performance characteristics and stability of LCO in aqueous electrolytes. Aqueous electrolytes offer greatly improved safety and lower cost. In addition, they exhibit higher ionic motilities for the Li+ions and thus can be potentially used for faster charging batteries [3] or batteries with thicker electrodes. While LCO has been demonstrated to cycle for 20-100 cycles in aqueous environments [4, 5], the causes of its degradation have not been investigated in detail. In our previous work we have demonstrated promising characteristics of lithium iron phosphate (LFP) cathodes in aqueous electrolytes [6]. Here we further expanded our studies and demonstrated LCO cathodes with remarkably stable performance showing only 13 % fading after over 1500 cycles. Post mortem analysis of the electrodes was conducted to understand the effect of cycling and the causes of degradation. A powerful combination of X-ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscopy (TEM) Scanning Electron Microscopy (SEM), and X-ray Diffraction (XRD) have been utilized. Our systematic studies and post-mortem analyses of LCO cells reveal that the primary mechanism of LCO degradation in aqueous electrolytes is the formation of a resistive layer of cobalt (II) oxide on the particles’ surfaces. Electrolyte composition was found to have a dramatic impact on the electrochemical performance and stability of LCO in aqueous environments. These results were recently accepted for publication in the Energy and Environmental Science Journal [7]. This talk will provide an overview of our findings and provide guidance for the future designs of aqueous electrochemical cells with stable cathodes.

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.