X-ray Photoelectron Spectroscopy Signal Research Articles

Preparation and characterization of Luminescent nanostructured Gd2O3-Y2O3:Eu synthesized by the solution combustion process

Abstract Microwave-assisted combustion of Europium doped Y2O3–Gd2O3 was investigated using glycine, glucose, glycerol and citric acid as organic fuel. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED) pattern, Brunauer–Emmett–Teller (BET) method, X-ray photoelectron spectroscopy (XPS) and photoluminescence spectroscopy (PL) techniques were used to characterize the nanostructured Gd2O3-Y2O3:Eu. The average crystallite size was in the range of 15 to 45nm. The formation of sponge-like morphologies was confirmed by SEM-TEM images and optimized with glucose and glycine fuels. Glycine fuel was enhanced specific surface area of synthesized sample (7.11 m2/g) as compared to other organic fuel. Gd 4d, Gd 3d and Y 3d peaks were appeared as a strong XPS signal which indicated complete oxidation of Gd and Y in sample. The main emission peaks of photoluminescence spectra which are related to the electric and magnetic dipole transitions were in 5D0→7F2 (610 nm) and 5D0→7F1 (590nm) electron transitions. Glycine sample as a fuel earned the highest emission intensity of red appearance in CIE diagram by one-step combustion synthesis. Photoluminescence property europium doped Y2O3-Gd2O3 was improved using glycine as a fuel.

Tunable carrier density and high mobility of two-dimensional hole gases on diamond: The role of oxygen adsorption and surface roughness

The transport properties of two-dimensional hole gases (2DHGs) on chemical-vapor-deposition (CVD)-grown diamond are investigated. A hydrogen plasma treatment and exposure to ambient atmosphere are used to establish and tailor the properties of the 2DHG. The transport parameters of the 2DHGs (namely carrier density and mobility) are characterized by temperature-dependent Hall measurements. The importance of the surface oxygen adsorption, determined by X-ray photoelectron spectroscopy (XPS), on the carrier density and mobility is shown. Hall measurements reveal that for oxygen concentrations below 2.2% (relative XPS signal) the carrier density is increasing from 1.4 ∙ 1010 cm−2 to 1.5 ∙ 1013 cm−2 with increasing oxygen adsorption. For oxygen concentrations above 2.2%, the charge carrier density decreases again. The carrier density remains constant over a temperature range between 4.2 K and 325 K. At room temperature, the mobility increases with decreasing carrier concentration. The opposite behavior is observed for 4.2 K.By decreasing the surface roughness to 8.2 nm, we were able to increase the mobility to above 250 cm2/V s at room temperature for a carrier density of 1.2 ∙ 1013 cm−2. This is among the highest values reported for 2DHGs on diamond.

In Situ X-ray Photoelectron Spectroscopic and Electrochemical Studies of the Bromide Anions Dissolved in 1-Ethyl-3-Methyl Imidazolium Tetrafluoroborate

Influence of electrode potential on the electrochemical behavior of a 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) solution containing 5 wt % 1-ethyl-3-methylimidazolium bromide (EMImBr) has been investigated using electrochemical and synchrotron-initiated high-resolution in situ X-ray photoelectron spectroscopy (XPS) methods. Observation of the Br 3d5/2 in situ XPS signal, collected in a 5 wt % EMImBr solution at an EMImBF4–vacuum interface, enabled the detection of the start of the electrooxidation process of the Br− anion to Br3− anion and thereafter to the Br2 at the micro-mesoporous carbon electrode, polarized continuously at the high fixed positive potentials. A new photoelectron peak, corresponding to B–O bond formation in the B 1s in situ XPS spectra at E ≤ −1.17 V, parallel to the start of the electroreduction of the residual water at the micro-mesoporous carbon electrode, was observed and is discussed. The electroreduction of the residual water caused a reduction in the absolute value of binding energy vs. potential plot slope twice to ca. dBE dE−1 = −0.5 eV V−1 at E ≤ −1.17 V for C 1s, N 1s, B 1s, F 1s, and Br 3d5/2 photoelectrons.

Identification of Surface Processes in Individual Minerals of a Complex Ore through the Analysis of Polished Sections Using Polarization Microscopy and X-ray Photoelectron Spectroscopy (XPS)

Understanding the changes of a mineral during ore processing is of capital importance for the development of strategies aimed at increasing the efficiency of metal extraction. This task is often difficult due to the variability of the ore in terms of composition, mineralogy and texture. In particular, surface processes such as metal re-adsorption (preg-robbing) on specific minerals are difficult to evaluate, even though they may be of importance as the re-adsorbed material can be blocking the valuable mineral and negatively affect the extraction process. Here, we show a simple yet powerful approach, through which surface processes in individual minerals are identified by combining polarization microscopy (MP) and X-ray photoelectron spectroscopy (XPS). Taking as an example a silver-containing polymetallic sulfide ore from the Peruvian central Andes (pyrite-based with small amounts of galena), we track the changes in the sample during the course of cyanidation. While polarization microscopy is instrumental for identifying mineralogical species, XPS provides evidence of the re-adsorption of lead on a pyrite surface, possibly as lead oxide/hydroxide. The surface of pyrite does not show significant changes after the leaching process according to the microscopic results, although forms of oxidized iron are detected together with the re-adsorption of lead by XPS. Galena, embedded in pyrite, dissolves during cyanide leaching, as evidenced by PM and by the decrease of XPS signals at the positions associated with sulfide and sulfate. At the same time, the rise of a lead peak at a different position confirms that the re-adsorbed lead species cannot be sulfides or sulfates. Interestingly, lead is not detected on covellite surfaces during leaching, which shows that lead re-adsorption is a process that depends on the nature of the mineral. The methodology shown here is a tool of significant importance for understanding complex surface processes affecting various minerals during metal extraction.

In vacuo XPS investigation of Cu(In,Ga)Se2 surface after RbF post-deposition treatment

Latest record efficiencies of Cu(In,Ga)Se2 (CIGSe) solar cells were achieved by means of a rubidium fluoride (RbF) post-deposition treatment (PDT). To understand the effect of the RbF-PDT on the surface chemistry of CIGSe and its interaction with sodium that is generally present in the CIGSe absorber, we performed an X-ray photoelectron spectroscopy (XPS) study on CIGSe thin films as-deposited by a three-stage co-evaporation process and after the consecutive RbF-PDT. The sample transfer from the deposition to the XPS analysis chamber was performed via an ultra-high vacuum transfer system. This allows to minimize air exposure, avoiding oxide formation on the CIGSe surface, especially for alkali-treated absorbers. Beside an expected reduction of Cu- and Ga-content at the surface of RbF-treated CIGSe films, we find that Rb penetrates the CIGSe and, contrary to fluorine, it is not completely removed by subsequent ammonia etching. The remaining Rb contribution at 110.0 eV binding energy, which appears after the RbF-PDT is similar to the one detected on a co-evaporated RbInSe2 reference sample and together with a new Se 3d contribution may hence belong to an Rb-In-Se secondary phase on the CIGSe surface. In addition, Na is driven towards the surface of the CIGSe absorber as a direct result of the RbF-PDT. This proves the ion-exchange mechanism in the absence of moisture and air/oxygen between heavy Rb atoms incorporated via PDT and lighter Na atoms supplied by the glass substrate. A remaining XPS signal of Na 1 s is observed after etching the vacuum transferred RbF-CIGSe sample, indicating that Rb and/or F are not as much a driving force for Na as oxygen usually is.

Influence of Multistep Surface Passivation on the Performance of PbS Colloidal Quantum Dot Solar Cells.

The performance of devices containing colloidal quantum dot (CQD) films is strongly dependent on the surface chemistry of the CQDs they contain. Multistep surface treatments, which combine two or more strategies, are important for creating films with high carrier mobility that are well passivated against trap states and oxidation. Here, we examine the effect of a number of these surface treatments on PbS CQD films, including cation exchange to form PbS/CdS core/shell CQDs, and solid-state ligand-exchange treatments with Cl, Br, I, and 1,2-ethanedithiol (EDT) ligands. Using laboratory-based and synchrotron-radiation-excited X-ray photoelectron spectroscopy (XPS), we examine the compositions of the surface layer before and after treatment, and correlate this with the performance data and stability in air. We find that halide ion treatments may etch the CQD surfaces, with detrimental effects on the air stability and solar cell device performance caused by a reduction in the proportion of passivated surface sites. We show that films made up of PbS/CdS CQDs are particularly prone to this, suggesting Cd is more easily etched from the surface than Pb. However, by choosing a less aggressive ligand treatment, a good coverage of passivators on the surface can be achieved. We show that halide anions bind preferentially to surface Pb (rather than Cd). By isolating the part of XPS signal originating from the topmost surface layer of the CQD, we show that air stability is correlated with the total number of passivating agents (halide + EDT + Cd) at the surface.

Deposition and characterization of nickel gallium thin films

Recent studies have indicated that nickel gallium alloys can be effective catalysts for the hydrogenation of CO2 to methanol. To simplify the characterization of NiGa catalysts, the authors are developing model systems using sputter deposited NiGa thin films. The NiGa thin films used in this study were deposited using an equimolar alloy target and annealed in ultrahigh vacuum. Atomic force microscopy (AFM), x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were used to characterize the NiGa films before and after annealing. AFM results showed that film roughness and grain size significantly increased as the film was annealed above 700 °C. XRD patterns indicated that NiGa thin films were nanocrystalline as deposited and then transitioned to the Ni13Ga9 phase after annealing above 500 °C. XPS results indicated that gallium and oxygen segregated to the surface after annealing up to 600 °C, and formed a surface Ga2O3 layer. For anneals above 600 °C, the Ga2O3 XPS signal was reduced in intensity due to desorption/decomposition of Ga2O3 from the NiGa surface.

Formation of graphitic carbon nitride and boron carbon nitride film on sapphire substrate

As a novel production method of boron carbon nitride (BCN) films, in this paper, we present the incorporation of B into graphitic carbon nitride (g-C3N4). First, we investigated the formation of g-C3N4 films via chemical vapor deposition (CVD) using melamine powder as the precursor. The formation of g-C3N4 films on a c-plane sapphire substrate was confirmed by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Raman spectroscopy measurements. The deposition temperature of g-C3N4 films was found to be suitable between 550 and 600 °C since the degradation and desorption of hexagonal C–N bonds should be suppressed. As for BCN films, we prepared BCN films via two-zone extended CVD using ammonia borane as the B precursor. Several XPS signals from B, C, and N core levels were detected from B-incorporated g-C3N4 films. While the N composition was almost constant, the marked tendencies for increasing B composition and decreasing C composition were achieved with the increase in the B incorporation, indicating the incorporation of B atoms by the substitution for C atoms. Optical absorptions were shifted to the high-energy side by B incorporation, which indicates the successful formation of BCN films using melamine and ammonia borane powders as precursors.

Ultrasound assisted green synthesis of cerium oxide nanoparticles using Prosopis juliflora leaf extract and their structural, optical and antibacterial properties

Abstract Cerium oxide nanoparticles (CONPs) were prepared using ultrasound assisted leaf extract of Prosopis juliflora acting as a reducing as well as stabilizing agent. The synthesized CONPs were characterized by ultraviolet-visible absorption spectroscopy (UV-Vis), particle size analyzer (PSA), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM). From the UV-Vis analysis, the optical band gap of the prepared CONPs (Eg = 3.62 eV) was slightly increased as compared to the bulk ceria (Eg = 3.19 eV). The phytochemicals in the extract reduced the particle size to 3.7 nm ± 0.3 nm, as it is evident from the PSA. FT-IR results confirmed the Ce-O stretching bands by showing the peaks at 452 cm-1. The Raman spectrumshowed a characteristic peak shift for CONPs at 461.2 cm-1. XRD analysis revealed the cubic fluorite structure of the synthesizednanoparticles with the lattice constant, a of 5.415 Å and unit cell volume, V of 158.813 Å3. XPS signals were used to determine the concentration of Ce3+ and Ce4+ in the prepared CONPs and it was found that major amount of cerium exist in the Ce4+ state. HRTEM images showed spherical shaped particles with an average size of 15 nm. Furthermore, the antibacterial activity of the prepared CONPs was evaluated and their efficacies were compared with the conventional antibiotics using disc diffusion assay against a set of Gram positive (G+) bacteria (Staphylococcus aureus, Streptococcus pneumonia) and Gram negative (G-) bacteria (Pseudomonas aeruginosa, Proteus vulgaris). The results suggested that CONPs showed antibacterial activity with significant variations due to the differences in the membrane structure and cell wall composition among the two groups tested.

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

MoS2, 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/MoS2 junction is critical to realizing the potential of MoS2-based devices. In this work, the Schottky barrier height (SBH) and the band structure of high work function Pd metal on MoS2 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 MoS2 is detected by XPS characterization, which gives insight into metal contact physics to MoS2 and suggests that interface engineering is necessary to lower the contact resistance for the future generation electronic applications.

Corrigendum: Chemical Activity of Thin Oxide Layers: Strong Interactions with the Support Yield a New Thin-Film Phase of ZnO.

Small Cu particles supported on and most likely activated by a ZnO substrate are the active component in the industrial catalyst used to convert syngas (H2, CO, CO2) into methanol, the third most important chemical product worldwide. Although a topic of intense research, the nature of the active site is still under debate. Recently, it has been pointed out that Zn atoms present at the surfaces of the Cu particles exhibit pronounced chemical activity and could explain some of the experimental findings. Another interesting suggestion is the presence of a thin layer of ZnOx species which forms on the surface of the Cu particles under reaction conditions. The importance of such thin oxide layers on the surface of metals under reaction conditions has already been pointed out in other contexts, where it was found that their chemical properties may differ substantially from those of the corresponding bulk oxides. In the case of ZnO this question is particularly interesting, since strong interactions between ZnO and the supporting metal have been reported for ZnO/ Cu and in recent work thin layers of ZnO have been shown to adopt a depolarized, graphitic structure, ZnO(gr), different from the wurtzite-type bulk. The properties of oxide thin films supported on metal substrates have been successfully studied in a number of cases, for example, for thin aluminum oxide films grown by oxidation of Ni/Al alloys. In contrast, the chemical activity of ZnO thin films supported on Cu single crystals has been investigated in a few cases only. Maroie et al. have investigated the adsorption and oxidation processes for single-crystal brass(110), brass(100), and brass(111) surfaces by X-ray photoelectron spectroscopy (XPS). Brass(110) and brass(111) show the same behavior with regard to the interaction with oxygen: the dissociative adsorption of oxygen on the surface is followed by the growth of thin ZnO layers. Wiame et al. reported that after oxidation of (111)-oriented Cu0.7Zn0.3 samples at room temperature the surface is covered by ZnO islands; it was suggested that these islands have (0001) and (0001) surface terminations. A more detailed characterization of the chemical properties of the thin ZnO layers was not carried out in this early work. In the present paper we report a detailed multitechnique investigation of a brass(111) single-crystal substrate (Cu/Zn ratio 9:1) subjected to different oxidation procedures using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR) under ultrahigh vacuum (UHV) conditions. The experimental findings are then interpreted by comparison with the results of a rather extensive set of density functional theory (DFT) calculations. Our results reveal the growth of thin ZnO adlayers with chemical properties that are markedly different from those of normal, wurtzite-type ZnO substrates. XPS data recorded for the brass(111) surface before and after different oxidation procedures for two different exit angles of the photoelectrons are shown in Figure 1. Since it is difficult to discriminate between Cu and Cu on the basis of XPS data, also the corresponding results from Auger electron spectroscopy (AES) are shown. For the clean brass(111) substrate the data indicate a Zn atom concentration of 5%, clearly lower than the 10% expected based on the bulk Cu/Zn ratio. Upon oxidation, the XPS data reveal an increase of the surface Zn concentration. Since it is a crucial question whether, in addition to Zn, also Cu or Cu is present, we have carefully analyzed the XPS and AES data. Neither in the Cu2p XPS data nor in the Cu L3M45M45 Auger data were the characteristic signatures of Cu or Cu species resulting from an oxidation of copper atoms detected. Cu exhibits a L3M45M45 peak at electron kinetic energies of 915 eV– 917 eV, which is clearly absent in the present data (see Figure 1). This observation, which agrees with the conclusions presented in a previous study by Rameshan et al., is expected, since in the presence of the less noble Zn one would expect the formation of ZnO to precede that of CuxO. Oxidation at elevated temperatures results in a substantial increase of the Zn signal, revealing the formation of thicker ZnO adlayers. The thickness of these thin ZnO layers was determined from the intensity of the Zn2p3/2 and Cu2p3/2 XPS signals. Exposure of the samples to 500 L of O2 at room temperature yields a ZnO adlayer with an average thickness of about 1.7 , consistent with the presence of a monolayer. More extended exposures to oxygen at room temperature did not result in a significant further increase of the thickness of the ZnO layer. Even the oxidation of the brass substrate at [*] Dr. V. Schott, Dr. A. Birkner, Dr. M. Xu, Dr. Y. Wang Chair of Physical Chemistry Ruhr-University Bochum (Germany)

XPS and SIMS Analysis of Solid Electrolyte Interphases on Lithium Formed by Ether-Based Electrolytes

The chemical composition and microstructure of the solid electrolyte interphase (SEI) on lithium metal in ether-based electrolytes are investigated using X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectrometry (ToF-SIMS) and scanning electron microscopy (SEM). Electrolytes based on 1,2-dimethoxyethane (DME) and 1,3-dioxolane (DOL) solvents with lithium bis(trifluoromethane)sulfonamide (LiTFSI) conducting salt are employed to passivate lithium surfaces for different periods of time. Two types of model experiments (immersion-type and galvanostatic current load) are performed to generate self- and current-induced SEIs. Reference measurements of predicted SEI components and an advanced XPS signal coupling method facilitate the deconvolution of the spectroscopic and spectrometric data. Both ether solvents showed specific SEI formation for each experimental setup. DME appears to decompose immediately on the lithium surface and forms a thin passivation film of various salts in a lithium-alkoxide framework. DOL shows a slow SEI formation of organic and inorganic salts revealing problems in the lithium surface protection. Under current load the reaction rate is increased in DME maintaining the three-dimensional microstructure. For DOL the current load leads to a multi-layer structure of organic host materials comprising LiTFSI and lithium fluoride. Finally, two-dimensional schematic pictures of the SEI microstructure are developed.

Wettability tailoring of nanotube carpets: morphology-chemistry synergy for hydrophobic–hydrophilic cycling

Carpet-like arrays of carbon nanotubes (CNTs) on graphitic carbon materials have been investigated in order to understand all-carbon hierarchical structures for multifunctional surface-active devices. Pure CNT carpets are seen to be super-hydrophobic as long as they are well aligned. For future applications involving aqueous environments, the ability to tailor the surface wettability and switch it on demand can be very useful, and enable unprecedented devices related to microfluidics, catalysis and sensing/detection systems. In this study, microwave plasma treatments were used to functionalize CNT carpets for a progressive increase in wettability so that they could eventually become super-hydrophilic. This change could be reversed by heating. Alternating between microwave plasma treatment and heating enabled repeated cycling of the CNT carpets between super-hydrophobic and super-hydrophilic states. This paper focuses on the influence of these two treatments on surface chemical states and multiscale morphology of CNT carpets, and their relation to wettability. It was shown by X-ray Photoelectron Spectroscopy (XPS) that oxygen-containing groups attached to surface carbon atoms are created during plasma treatment. These species desorb at temperatures of about 110 °C. The strength of C 1s and O 1s XPS signals from these radicals were seen to have direct correlation with water contact angles. In addition to surface chemistry, carpet morphology plays an important role in contact angle variations. Extreme surface roughness caused by high aspect-ratio of nanotubes would strongly accentuate both hydrophobic and hydrophilic behavior compared to flat surfaces. Classical geometric models of liquid droplets on uneven solids have been considered. Topological image analysis combined with intrinsic contact angle on flat graphene is used to predict the contact angle of these carpets, which matches well with experimental results. This analysis further explains why observed contact angles change if the vertical alignment of CNT is disturbed.

CO2 Adsorption by para-Nitroaniline Sulfuric Acid-Derived Porous Carbon Foam

The expansion product from the sulfuric acid dehydration of para-nitroaniline has been characterized and studied for CO2 adsorption. The X-ray photoelectron spectroscopy (XPS) characterization of the foam indicates that both N and S contents (15 and 9 wt%, respectively) are comparable to those separately reported for nitrogen- or sulfur-containing porous carbon materials. The analysis of the XPS signals of C1s, O1s, N1s, and S2p reveals the presence of a large number of functional groups and chemical species. The CO2 adsorption capacity of the foam is 7.9 wt% (1.79 mmol/g) at 24.5 °C and 1 atm in 30 min, while the integral molar heat of adsorption is 113.6 kJ/mol, indicative of the fact that chemical reactions characteristic of amine sorbents are observed for this type of carbon foam. The kinetics of adsorption is of pseudo-first-order with an extrapolated activation energy of 18.3 kJ/mol comparable to that of amine-modified nanocarbons. The richness in functionalities of H2SO4-expanded foams represents a valuable and further pursuable approach to porous carbons alternative to KOH-derived activated carbons.

Insights into Silica Bilayer Hydroxylation and Dissolution

Hydroxylation and dissolution of well-structured silica bilayer films grown on a ruthenium single-crystal support (SiO2/Ru(0001)) was studied by temperature programmed desorption and X-ray photoelectron spectroscopy (XPS). Water desorption signals from SiO2/Ru(0001) hydroxylated by electron-bombardment of adsorbed ice at 100 K were found to be comparable to those of hydroxylated bulk silica samples and attributed to adsorbed molecular water and silanol groups (vicinal and terminal). Isotopic exchange between 18O-labeled SiO2 and 16O-labeled water suggests the occurrence of dynamic siloxane bond cleavage and re-formation during electron bombardment. Together with the observed strong dependence of hydroxylation activity on ice coverage, which is found to increase with increasing thickness of the ice layer, a hydroxylation mechanism based on the activation of siloxane bonds by water radiolysis products (e.g. hydroxyls) and subsequent water dissociation is proposed. Dissolution rates obtained from the attenuation of Si 2p and O 1s XPS signal intensities upon exposure of bilayer SiO2/Ru(0001) to alkaline conditions at various temperatures are in agreement with the proposed rate model for bulk silica dissolution by OH− attack and provide further corroboration of the proposed hydroxylation mechanism.

Chemical engineering of Cu(In,Ga)Se2 surfaces: An absolute deoxidation studied by X-ray photoelectron spectroscopy and Auger electron spectroscopy signatures

CIGS (Cu(In,Ga)Se2) absorbers are among the most efficient for photo-conversion. As part of their manufacturing cycle, absorber surface preparation is crucial for both the success of processes and the outcome of characterizations actions. This work tackles the question of an efficient deoxidation of CIGS surfaces. Chemical composition of surface is investigated thanks to XPS (X-ray Photoelectron Spectroscopy) characterizations. Present study focuses on the possible control of the CIGS absorber surface associated with simple HCl treatment and subsequent atmosphere ageing up to 20days. Using 1.0M HCl concentration solution, remarkable oxide elimination is achieved. Starting from an air aged as-grown surface (Cu and Se-poor), this treatment enables the generation of a deoxidized chalcopyrite reference sample. Furthermore, the reoxidation process of the treated surface at ambient atmosphere is studied considering the global evolution of the XPS signals as the best probe of the ageing process. The surface composition evolution represents a key parameter for the achievement of the following interfaces engineering. The main result is that the reoxidation process is not instantaneous (no significant oxide content before 2days) and involves In, Ga and Se elements while the Cu seems less affected, leading again to a Cu-poor surface different from the initial one.

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

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 coatings and shells. However, care is required to produce reliable and consistent information. Here we report XPS spectra from gold/silver core-shell nanoparticles of nominal size 20 nm removed from a citrate saturated solution after one washing cycle. The Simulation of Electron Spectra for Surface Analysis (SESSA) program has 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 in digital form 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.

Reduction and structural modification of zirconolite on He+ ion irradiation

The immobilization of minor actinides and alkaline-earth metal is a major concern in nuclear industry due to their long-term radioactive contribution to the high level waste (HLW). Materials having zirconolite, pyrochlore, and perovskite structure are promising candidates for immobilization of HLW. The zirconolite which exhibits high radiation stability and corrosion resistance behavior is investigated for its radiation stability against alpha particles in the present study. CaZrTi2O7 pellets prepared using solid state reaction techniques, were irradiated with 30keV He+ ions for the ion fluence varying from 1×1017 to 1×1021ions/m2. Scanning electron microscopy (SEM) images of the un-irradiated sample exhibited well separated grains with average size of about 6.8μm. On the ion irradiation, value of the average grains size was about 7.1μm, and change in the microstructure was insignificant. The X-ray photoelectron spectroscopy (XPS) studies showed a shift in the core level peak position (of Ca 2p, Ti 2p and Zr 3d) towards lower binding energy with respect to pristine sample as well as loss of oxygen was also observed for sample irradiated with the ion fluence of 1×1020ions/m2. These indicate a decrease in co-ordination number and the ionic character of MO bond. Moreover, core level XPS signal was not detected for sample irradiated with ion fluence of 1×1021ions/m2, suggesting surface damage of the sample at this ion fluence. However, X-ray diffraction (XRD) studies showed that zirconolite was not amorphized even on irradiation up to a fluence order of 1×1021ion/m2. But, significant decrease in peak intensity due to creation of defects and a marginal positive peak shift due to tensile strain induced by irradiation, were observed. Thus, XRD along with XPS investigation suggests that reduction, decrease in co-ordination number, and increase in covalency are responsible for the radiation damage in zirconolite.

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

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 electrolyteinterface. These experiments are often paired with complementary molecular dynamics (MD) simulations in an attempt to provide a complete description of the liquidinterface. 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 liquidinterfaces are discussed.

Quantifying the Impact of Nanoparticle Coatings and Nonuniformities on XPS Analysis: Gold/Silver Core-Shell Nanoparticles.

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, nonspherical, and contain off-centered Au-cores. Using the average NP dimensions determined from STEM analysis, SESSA spectral modeling indicated that washed Au/Ag-core-shell NPs were stabilized with a 0.8 nm layer of sodium citrate and a 0.05 nm (one wash) or 0.025 nm (two wash) layer of adventitious hydrocarbon, but did not fully account for the observed XPS signal from the Au-core. This was addressed by a series of simulations and normalizations to account for contributions of NP nonsphericity and off-centered Au-cores. Both of these nonuniformities reduce the effective Ag-shell thickness, which effect the Au-core photoelectron intensity. The off-centered cores had the greatest impact for the particles in this study. When the contributions from the geometrical nonuniformities are included in the simulations, the SESSA generated elemental compositions that matched the XPS elemental compositions. This work demonstrates how spectral modeling software such as SESSA, when combined with experimental XPS and STEM measurements, advances the ability to quantitatively assess overlayer thicknesses for multilayer core-shell NPs and deal with complex, nonideal geometrical properties.