ToF‐SIMS studies of the oxidation of Fe by D2O vapour: comparison with XPS

The oxidation of iron (Fe) by water (D₂O) vapour at low pressures and room temperature was investigated using time‐of‐flight (ToF) SIMS. The results supported those found previously using XPS and the QUASES^? program in that a duplex oxide structure was found containing a thin outer surface hydroxide (Fe(OD)₂) layer over an inner oxide (FeO) layer. The extraordinary depth resolution of the ToF‐SIMS profiles assisted in identifying the two phases; this resolution was achieved by compensation for surface roughness. A substantial concentration of deuterium was found in the subsurface oxide layer. This observation confirmed previous assessments that the formation of FeO was from the reaction of Fe(OD)₂ with outward‐diffusing Fe, leaving deuterium as a reaction product. Copyright © 2005 John Wiley & Sons, Ltd.     

Study of the degradation of plasma‐oxidized polystyrene by time‐ and angle‐resolved x‐ray photoelectron spectroscopy

Angle‐resolved x‐ray photoelectron spectroscopy (ARXPS) measurements were made, in repeated sequences employing Al and Mg x‐ray sources alternately, on a polystyrene sample that had been exposed to an oxygen plasma. It was observed that oxygen was lost from the sample over a period of 5 h and 40 min. The ARXPS data sets were corrected for the time displacement between consecutive measurements at different photoemission angles and fitted with three simple models in order to extract oxygen concentration–depth profiles, consistent with the data, as a function of time. The oxygen depth profiles were found to evolve in a consistent manner, indicating both a loss of average oxygen content and thickness in the ‘oxidized polymer layer’. Copyright © 2003 John Wiley & Sons, Ltd.     

Nondestructive in‐depth composition profile of oxy‐hydroxide nanolayers on iron surfaces from ARXPS measurement

In this work the maximum entropy method (MEM) is applied, for the first time, to angle‐resolved X‐ray photoelectron spectroscopy (ARXPS) data from oxy‐hydroxide films on iron surfaces. This nondestructively derives information on the in‐depth distribution of the composition and chemical state. An MEM algorithm was created and first tested on the simulated data. The reconstructed composition depth profiles agreed very well with the theoretical ones up to 5% Gaussian noise added to the data. The same algorithm was then applied to ARXPS data from iron samples to investigate the in‐depth variations in the composition and chemical state of the nanosized oxy‐hydroxide film naturally grown on the iron surface. The resulting surface film presents a complex multilayer structure with concentration gradients. The effect of air exposure on the structure was also investigated. Copyright © 2006 John Wiley & Sons, Ltd.     

Investigation into the surface selective oxidation of dual‐phase steels by XPS,SAM and SIMS

Surface selective oxides created during continuous annealing (MnO, SiO₂, etc.) can have a deleterious effect on coating adhesion after hot‐dip galvanizing. Earlier research works have made it clear that increasing the annealing atmosphere oxidizing potential can alleviate the problem by reducing external surface selective oxidation. In the present study, increasing the water vapour content of the nitrogen–hydrogen protective gas mixture was used to raise its oxidizing potential. The technique was applied to a classical dual‐phase steel (0.15% C, 1.5% Mn, 0.45% Si, 0.05% Al…) that was annealed for 60 s at 800–810°C in protective atmospheres of nitrogen and 5% hydrogen with water vapour contents ranging from 10 to 6000 ppm. Post‐annealing surfaces were characterized by x‐ray photoelectron spectroscopy (XPS), secondary ion mass spectroscopy (SIMS) and scanning Auger microscopy (SAM). In situ XPS analyses were carried out right after simulation annealing in the preparation chamber connected to the spectrometer, never returning the specimens to air. This made it possible to identify in a reliable way the elements that segregated to the surface during the treatment, and to determine their corresponding oxidation states. On the other hand, the high sensitivity of SIMS was taken advantage of to assess oxide in‐depth concentration profiles (SiO₂, Al₂O₃, FeO) as a function of the annealing conditions, and SAM was used to characterize the corresponding oxide particle morphology. External selective oxidation was thus shown to decrease with increasing water vapour contents in the atmosphere (from 80 to 6000 ppm), whereas internal oxidation increases drastically to ～4 μm below the free surface. At 10 ppm of H₂O the oxygen partial pressure is very low and the external selective oxidation results in a thin, but almost complete, coverage of the steel surface. Consequently, metallic iron cannot be observed at the surface, thus hampering hot‐dip galvanizability, unless the water vapour content is raised to 6000 ppm. Various surface morphologies were observed and discussed. In the authors' opinion, basic investigations of this type are an indispensable first step to improving the response of highly alloyed steels (dual‐phase, TRIP) to hot‐dip galvanizing. Copyright © 2003 John Wiley & Sons, Ltd.     

Fe(CN)64−‐Doped‐Glutaraldehyde‐Cross‐Linked Poly‐L‐Lysine Film Electrode. Part 2: Stability Improvement and Selective Detection of Dopamine in the Presence of Ascorbic Acid

Highly stable Nafion‐covered hexacyanoferrate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐Fe(CN)₆^4?/Naf) film modified glassy carbon electrode (GCE), for the selective detection of dopamine (DA) in the presence of ascorbic acid (AA), was prepared by first ion‐exchanging Fe(CN)₆^4? into PLL‐GA coating on GCE then sealing it with a Nafion outer layer. The Nafion over layer is crucial in preventing leaching of Fe(CN)₆^4? ions from the inner layer. The first layer was acting as electrocatalyst for DA oxidation and the outer coating acted as discriminating layer for selective permeation of DA in the presence of interfering anionic species. More than 90% of the initial response was retained after coating with the Nafion protecting layer compared to a huge loss (>60%) without Nafion outer layer. 5% Nafion coating was identified as optimum thickness for the selective detection of DA in the presence of AA.     

Fick's law of diffusion depth profiles applied to the degradation of oxidized polystyrene during ARXPS analysis

Angle‐resolved x‐ray photoelectron spectroscopy (ARXPS) measurements were made, using Al Kα and Mg Kα radiation alternately, on a polystyrene sample that had been exposed to a helium plasma. It was observed that oxygen was introduced into the sample surface by the plasma treatment, and that some of it was lost over a period of 5 h under x‐ray irradiation in the vacuum of the spectrometer. Laplace transforms of Fick's law of diffusion profiles were derived and applied to the data. The ARXPS results obtained in this study are consistent with a sample history in which the oxidation of the polymer surface resulting from exposure to plasma is controlled by a diffusion process, whereas the loss of oxygen during exposure to x‐rays is principally controlled by a first‐order reaction such as the liberation of oxygen (presumably as CO₂) from carbon–oxygen groups by the action of radicals created by the ionizing radiation. Copyright © 2005 John Wiley & Sons, Ltd.     

Self‐Recovery of Pd Nanoparticles That Were Dispersed over La(Sr)Fe(Mn)O3 for Intelligent Oxide Anodes of Solid‐Oxide Fuel Cells

Self‐recovery is one of the most‐desirable properties for functional materials. Recently, oxide anodes have attracted significant attention as alternative anode materials for solid‐oxide fuel cells (SOFCs) that can overcome reoxidation, deactivation, and coke‐deposition. However, the electrical conductivity and surface activity of the most‐widely used oxide anodes remain unsatisfactory. Herein, we report the synthesis of an “intelligent oxide anode” that exhibits self‐recovery from power‐density degradation in the redox cycle by using a Pd‐doped La(Sr)Fe‐ (Mn)O₃ cell as an oxide anode for the SOFCs. We investigated the anodic performance and oxidation‐tolerance of the cell by using Pd‐doped perovskite as an anode and fairly high maximum power densities of 0.5 and 0.1 W cm^?2 were achieved at 1073 and 873 K, respectively, despite using a 0.3 mm‐thick electrolyte. Long‐term stability was also examined and the power density was recovered upon exposure of the anode to air. This recovery of the power density can be explained by the formation of Pd nanoparticles, which were self‐recovered through reoxidation and reduction. In addition, the self‐recovery of the anode by oxidation was confirmed by XRD and SEM and this process was effective for improving the durability of SOFC systems when they were exposed to severe operating conditions.     

Quantitative ARXPS investigation of systems with ultrathin aluminium oxide layers

Angle‐resolved x‐ray photoelectron spectroscopy (ARXPS) is a non‐destructive method to investigate the near‐surface structure of specimens with a flat surface. For interpretation of the electron intensities emitted from different depth regions, model calculations are necessary. Based on an earlier algorithm we have developed a program for ARXPS studies of thin multilayers. In our model calculation the sample structure is treated as consisting of several layers (one to three) on the substrate, whereas the top layer can be incomplete. Emitted electrons are assumed to be attenuated exponentially in the layers. Different atomic volumes, electron attenuation lengths (including consideration of elastic scattering) and assumptions on stoichiometry are taken into account for the particular layers. As an application of our model calculations we present a study of a set of Al samples that were oxidized by different methods, i.e. natural and plasma oxidation (plasma obtained by electron cyclotron resonance). The oxide layers produced by plasma oxidation were protected by a 2 nm thick Co film, before exposing the samples to the air. Additionally, in order to check our results of the ARXPS model calculation, x‐ray reflectometry (XRR) analysis was used. Copyright © 2004 John Wiley & Sons, Ltd.     

Gold/Wüstite Core–shell Nanoparticles: Suppression of Iron Oxidation through the Electron‐Transfer Phenomenon

Plasmonic Au and magnetic Fe are coupled into uniform Au@Fe core–shell nanoparticles (NPs) to confirm that electron transfer occurred from the Au core to the Fe shell. Au NPs synthesized in aqueous medium are used as seeds and coated with an Fe shell. The resulting Au@Fe NPs are characterized by using various analytical techniques. X‐ray photoelectron spectroscopy and superconducting quantum interference device measurements reveal that the Fe shell of the Au@Fe NPs mainly consists of paramagnetic Wüstite with a thin surface oxide layer consisting of maghemite or magnetite. Electron transfer from the Au core to the Fe shell effectively suppresses iron oxidation from Fe²⁺ to Fe³⁺ near the interface between the Au and the Fe. The charge‐transfer‐induced electronic modification technique enables us to control the degree of iron oxidation and the resulting magnetic properties.     

Actual Isothermal Effects of Water‐Filtered Infrared A‐Irradiation

In this study, the athermal effects of water‐filtered infrared A (wIRA)‐irradiation (780–1400 nm) on human dermal fibroblasts were investigated. For this purpose, cells were exposed to wIRA‐irradiation (178 mW cm^?2 for 1 h), while a sophisticated experimental setup prevented warming of the samples exceeding 0.1°C. The investigated parameters were the formation of reactive oxygen species (ROS), mitochondrial membrane potential and superoxide release, protein oxidation, proliferation rate, as well as intracellular Ca²⁺‐release in single cells, most of them quantified via fluorescence microscopy and fluorimetric techniques. The existence of actual athermal wIRA‐effects is still intensively discussed, since their detection requires a careful experimental setup and both efficient and powerful temperature regulation of the exposed samples. Here, we can definitively show that some of the supposed athermal wIRA‐effects may be rather artifacts, since wIRA did not reveal any impact on the above mentioned parameters—as long as the temperature of the exposed cells was carefully maintained. Though, we were able to identify an athermal DNA‐protective wIRA‐effect, since the induced DNA damage (quantified via 8‐Oxo‐G‐formation) was significantly decreased after a subsequent UVB‐exposure. These results suggest that many of the supposed athermal wIRA‐effects can be induced by pure warming of the samples, independent from any wIRA‐irradiation.     

Spin Self‐Assembled Clay Nanocomposite Passivation Layers Made from a Photocrosslinkable Poly(vinyl alcohol) and Na+‐Montmorillonite Enhance the Environmental Stability of Organic Thin‐Film Transistors

We investigated the effects of the multilayer polymer‐clay nanohybrid passivation films on the stability of pentacene organic thin‐film transistors (OTFTs) exposed to air and UV irradiation. Well‐ordered multilayer films were deposited by the spin‐assisted layer‐by‐layer assembly method using photocrosslinkable poly(vinyl alcohol) with the N‐methyl‐4(4′‐formylstyryl)pyridinium methosulfate acetal group (SbQ‐PVA) and Na⁺‐montmorillonite in a water‐based solution process. When photocrosslinked, these SbQ‐PVA/clay multilayers were found to serve as excellent barriers to O₂ and UV‐light. Moreover, when used as passivation layers, they enhanced the stability of pentacene OTFT devices exposed to air and UV radiation.     

Site‐Specific Oxidation State Assignments of the Iron Atoms in the [4Fe:4S]2+/1+/0 States of the Nitrogenase Fe‐Protein

The nitrogenase iron protein (Fe‐protein) contains an unusual [4Fe:4S] iron‐sulphur cluster that is stable in three oxidation states: 2+, 1+, and 0. Here, we use spatially resolved anomalous dispersion (SpReAD) refinement to determine oxidation assignments for the individual irons for each state. Additionally, we report the 1.13‐Å resolution structure for the ADP bound Fe‐protein, the highest resolution Fe‐protein structure presently determined. In the dithionite‐reduced [4Fe:4S]¹⁺ state, our analysis identifies a solvent exposed, delocalized Fe^2.5+ pair and a buried Fe²⁺ pair. We propose that ATP binding by the Fe‐protein promotes an internal redox rearrangement such that the solvent‐exposed Fe pair becomes reduced, thereby facilitating electron transfer to the nitrogenase molybdenum iron‐protein. In the [4Fe:4S]⁰ and [4Fe:4S]²⁺ states, the SpReAD analysis supports oxidation states assignments for all irons in these clusters of Fe²⁺ and valence delocalized Fe^2.5+, respectively.     

Air‐Stable Lithium Spheres Produced by Electrochemical Plating

Lithium metal is an ideal anode for next‐generation lithium batteries owing to its very high theoretical specific capacity of 3860 mAh g^?1 but very reactive upon exposure to ambient air, rendering it difficult to handle and transport. Air‐stable lithium spheres (ASLSs) were produced by electrochemical plating under CO₂ atmosphere inside an advanced aberration‐corrected environmental transmission electron microscope. The ASLSs exhibit a core–shell structure with a Li core and a Li₂CO₃ shell. In ambient air, the ASLSs do not react with moisture and maintain their core–shell structures. Furthermore, the ASLSs can be used as anodes in lithium‐ion batteries, and they exhibit similar electrochemical behavior to metallic Li, indicating that the surface Li₂CO₃ layer is a good Li⁺ ion conductor. The air stability of the ASLSs is attributed to the surface Li₂CO₃ layer, which is barely soluble in water and does not react with oxygen and nitrogen in air at room temperature, thus passivating the Li core.     

Surface characterization of pre‐formed alginate fibres incorporated with a protein by a novel entrapment process

A novel physical entrapment process has been explored as an approach to surface incorporation of proteins within pre‐formed alginate fibres under mild conditions. Entrapment of the protein of choice was achieved by exposing the alginate fibres to a Na⁺‐rich NaCl/CaCl₂ mixture solution, which caused the formation of a moderate dissociation layer into which the protein could diffuse. Subsequent addition of a large excess of multi‐valent cations led to the collapse of the surface and entrapment of the protein within the surface. Bovine serum albumin (BSA) was used as a model protein to investigate the effect of process parameters on the entrapment efficiency. Scanning electron microscopy revealed that there was an increase in the surface roughness and a slight increase in the average diameter of the fibres after protein entrapment. The presence of the protein at the surface of alginates after the entrapment process was confirmed by means of confocal laser‐scanning microscopy, X‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). The ion exchanges at the surface were evident, as detected by XPS and ToF‐SIMS. It was found that under fixed pre‐swelling conditions, the entrapment efficiency increased with increasing treatment time and, particularly, with protein concentration in the exposure solution. Copyright © 2005 John Wiley & Sons, Ltd.     

Redox Properties of Ferricyanide Ion on Layer‐by‐Layer Thin Film‐Coated Gold Electrodes; Effects of Type of Polycationic Components in the Film

The surface of a gold (Au) electrode was coated with layer‐by‐layer (LbL) thin films composed of poly(vinyl sulfate) (PVS) and different type of poly(amine)s including poly(allylamine) (PAH), poly(ethyleneimine) (PEI) and poly(diallyldimethylammonium chloride) (PDDA) and redox properties of ferricyanide ion ([Fe(CN)₆]^3?) on the LbL film‐coated Au electrodes were studied. The LbL film‐coated electrodes exhibited redox response to [Fe(CN)₆]^3? ion when the outermost surface of the LbL film was covered with the cationic poly(amine)s while virtually no response was observed on the LbL film‐coated electrodes whose outermost surface was covered with PVS due to an electrostatic repulsion between [Fe(CN)₆]^3? ion and the negatively‐charged PVS layer. The redox properties of [Fe(CN)₆]^3? ion on the LbL film‐coated electrodes significantly depended on the type of polycationic materials in the LbL film. The LbL film‐coated electrodes which had been immersed in the [Fe(CN)₆]^3? solution for 15 min exhibited redox response even in a [Fe(CN)₆]^3? ion‐free buffer solution, suggesting that [Fe(CN)₆]^3? ion is confined in the films. In the buffer solution, redox peaks were observed between +0.1 and 0.4 V depending on the type of polycations in the film. Thus, [Fe(CN)₆]^3? ion can be confined in the film and the redox potential is polycation‐dependent.     

Studies on the migration in PA6‐OMMT nanocomposites: effect of annealing on migration as evidenced by ARXPS (angle resolved X‐ray photoelectron spectroscopy)

The present paper deals with experiments in which the angle resolved X‐ray photoelectron spectroscopy (ARXPS) technique was applied to investigate the phenomenon of migration in polyamide 6 with organically modified montmorillonite (PA6‐OMMT) nanocomposites. This is the first time ARXPS was used, to gain a more detailed insight into the migration process. Curve‐fitting analyses are reported which enable the differentiation between a manual mixture of PA6 with OMMT at room temperature from a nanocomposite structure. The ARXPS technique was applied to annealed samples at 250, 275, and 285°C, for 2 hr, and with three take of angles, α, of 90, 60, and 30°. The depth of the layer investigated is 9 nm in case the sample surface is well defined. By tilting the take‐off angle of the beam‐out electrons one can determine the intensity of the signals at various distances from the surface within the investigated layer. The concentration gradient of the Si signals is observed. The rate of migration is found to be more rapid in the layer closest to the surface. The intensity of the Si signals in the investigated layer is found to be 1.8 to 9.1 times that of the same composite sample at room temperature. This ratio determines the extent of migration. At temperatures higher than 250°C and times of annealing greater than 30 min a decrease in the extent of migration is observed. This decrease is explained by the gradual decomposition of the surfactant and the consequent removal of the polymeric matrix molecules from the migrating exfoliated units, culminating in denuded alumino‐silicate layers. These layers aggregate to noncolloidal microcomposite particles which do not migrate. The concentration of the exfoliated units decreases with consequent decrease in migration. A gradient of decreasing concentration of Si2p signals was observed after various times of annealing, where the gradient becomes more uniform with increase in time. Copyright © 2008 John Wiley & Sons, Ltd.     

Report on the 47th IUVSTA Workshop ‘Angle‐Resolved XPS: the current status and future prospects for angle‐resolved XPS of nano and subnano films’

A summary of the workshop entitled ‘Angle‐Resolved XPS: The Current Status and Future Prospects for Angle‐resolved XPS of Nano and Subnano Films’ is given, which was held at the Riviera Maya, Mexico, 26–30 March 2007, under the main sponsorship of the International Union for Vacuum Science, Technique and Applications (IUVSTA). Angle‐resolved X‐ray photoelectron spectroscopy (ARXPS) can provide detailed chemical as well as depth profile information about the near‐surface composition of materials and thin films. This workshop was held to review the present status and level of understanding of Angle‐resolved XPS, and to stimulate discussions leading to a deeper understanding of current problems and new solutions. The main goal of the workshop was to find better ways to perform experiments and, very importantly, better ways to extract information from the experimental data. This report contains summaries of presentations and discussions that were held in sessions entitled ‘Basics and Present Limits of ARXPS’, the Analysis of ARXPS Data, Applications of ARXPS, Equipment for ARXPS, and Future Developments in ARXPS'. There were 33 participants at the workshop. Copyright © 2009 John Wiley & Sons, Ltd.     

Antioxidant Grain Passivation for Air‐Stable Tin‐Based Perovskite Solar Cells

Tin‐based perovskites with excellent optoelectronic properties and suitable band gaps are promising candidates for the preparation of efficient lead‐free perovskite solar cells (PSCs). However, it is challenging to prepare highly stable and efficient tin‐based PSCs because Sn²⁺ in perovskites can be easily oxidized to Sn⁴⁺ upon air exposure. Here we report the fabrication of air‐stable FASnI₃ solar cells by introducing hydroxybenzene sulfonic acid or its salt as an antioxidant additive into the perovskite precursor solution along with excess SnCl₂. The interaction between the sulfonate group and the Sn²⁺ ion enables the in situ encapsulation of the perovskite grains with a SnCl₂–additive complex layer, which results in greatly enhanced oxidation stability of the perovskite film. The corresponding PSCs are able to maintain 80 % of the efficiency over 500 h upon air exposure without encapsulation, which is over ten times longer than the best result reported previously. Our results suggest a possible strategy for the future design of efficient and stable tin‐based PSCs.     

Enhanced Catalytic Activity in Liquid‐Exfoliated FeOCl Nanosheets as a Fenton‐Like Catalyst

A facile liquid‐phase exfoliation method to prepare few‐layer FeOCl nanosheets in acetonitrile by ultrasonication is reported. The detailed exfoliation mechanism and generated products were investigated by combining first‐principle calculations and experimental approaches. The similar cleavage energies of FeOCl (340 mJ m^?2) and graphite (320 mJ m^?2) confirm the experimental exfoliation feasibility. As a Fenton reagent, FeOCl nanosheets showed outstanding properties in the catalytic degradation of phenol in water at room temperature, under neutral pH conditions, and with sunlight irradiation. Apart from the increased surface area of the nanosheets, the surface state change of the nanosheets also plays a key role in improving the catalytic performance. The changes of charge density, density of states (DOS), and valence state of Fe atoms in the exfoliated FeOCl nanosheets versus plates illustrated that surface atomistic relationships made the few‐layer nanosheets higher activity, indicating the exfoliation process of the FeOCl nanosheets also brought about surface state changes.     

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

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