Low‐energy ion scattering: Determining overlayer thickness for functionalized gold nanoparticles

With the widespread use of engineered nanoparticles for biomedical applications, detailed surface characterization is essential for ensuring reproducibility and the quality/suitability of the surface chemistry to the task at hand. One important surface property to be quantified is the overlayer thickness of self‐assembled monolayer (SAM) functionalized nanoparticles, as this information provides insight into SAM ordering and assembly. We demonstrate the application of high sensitivity low‐energy ion scattering (HS‐LEIS) as a new analytical method for the fast thickness characterization of SAM functionalized gold nanoparticles (AuNPs). HS‐LEIS demonstrates that a complete SAM is formed on 16‐mercaptohexadecanoic acid (C16COOH) functionalized 14 nm AuNPs. HS‐LEIS also experimentally provides SAM thickness values that are in good agreement with previously reported results from simulated electron spectra for surface analysis of X‐ray photoelectron spectroscopy data. These results indicate HS‐LEIS is a valuable surface analytical method for the characterization of SAM functionalized nanomaterials. Copyright © 2013 John Wiley & Sons, Ltd.     

Surface Compositions of Oxide Supported Bimetallic Catalysts: A Compared Study by High‐Sensitivity Low Energy Ion Scattering Spectroscopy and X‐Ray Photoemission Spectroscopy

It is well known that there is a critical relationship between the surface composition and catalytic performance for a bimetallic catalyst. However, in most cases, the surface composition is obviously different from that of the bulk. Moreover, the surface is normally reconstructed under reaction conditions. In this personal account, our recent progresses in determining the surface compositions of oxide supported bimetal catalysts by high‐sensitivity low energy ion scattering spectroscopy (HS‐LEIS) and X‐ray photoemission spectroscopy (XPS) are summarized. Phase diagrams of the surface compositions under various conditions as a function of the bulk composition are established and compared. It is found that oxidation induces de‐alloying and enrichment of PdO, CuO, SnO₂ on the surface, while H₂ reduction results in re‐alloying. The addition of the second component not only modifies the nature of the active site, but also varies the dispersion of the active components. The support effects are discussed. The compared studies reveal that HS‐LEIS can achieve a more reliable surface composition for oxide supported catalysts.     

Surface composition of PdCuAu ternary alloys: a combined LEIS and XPS study

PdCuAu ternary alloy samples with different composition were synthesized on top of ZrO₂‐modified porous stainless steel disks by the sequential electroless deposition technique. The structure, morphology and bulk composition of the samples were characterized by X‐ray diffraction (XRD), scanning electron microscopy and energy dispersive X‐ray spectroscopy (EDX). Complete alloy formation with a pure fcc phase for the Pd₇₁Cu₂₆Au₃, Pd₇₀Cu₂₅Au₅ and Pd₆₇Cu₂₄Au₉ samples and a bcc structure for the Pd₆₂Cu₃₆Au₂ and Pd₆₀Cu₃₇Au₃ samples were obtained upon annealing at 500 °C for 120 h as revealed by XRD. A combination of low‐energy ion scattering (LEIS) and X‐ray photoelectron spectroscopy (XPS) was used to investigate the surface properties of the PdCuAu alloys. XPS results confirmed alloy formation under the annealing conditions. XPS analysis also revealed that the near‐surface regions of the alloys became enriched in Pd with respect to the bulk composition determined by EDX. In contrast, LEIS and angle‐resolved XPS analyses showed that the top‐most surface layers in all samples were copper‐rich compared with the bulk composition. This high Cu surface concentration could impart resistance to bulk sulfide formation to the PdCuAu alloy membranes. Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of compaction and surface roughness on low‐energy ion scattering signals

Investigation of the surface composition of powders often requires compaction. To study the effect of compaction on surface analysis, samples have been compacted at various pressures ranging from 0 Pa (i.e. no compaction) up to 2000 MPa (2 × 10⁴ kg cm^?2) Low‐energy ion scattering (LEIS) was used to determine the composition of the outermost atomic surface layer. Using scanning electron microscopy, changes in the morphology due to compaction have been detected in the SiO₂ test samples. The LEIS yield of a compacted silica powder is found to be independent of the applied pressure during compaction between 2 MPa and 2000 MPa (2 × 10⁴ kg cm^?2). Analysis of a submonolayer of Ta₂O₅ on a silica support shows that the composition of the outermost atomic layer is not changed after compaction up to a pressure of at least 300 MPa. When compaction is applied, the absolute LEIS yield appears to be independent of the specific surface area of silica supports in the range 50–380 m² g^?1. A minor difference in LEIS signals is observed between compacted silica supports and flat quartz samples. In order to determine the surface roughness factor independently, and to study the material dependence of the surface roughness factor, angle‐dependent LEIS measurements have been carried out on oxidized silicon, gallium and gold surfaces. The results on the oxidized silicon confirm the small influence of surface roughness for silica particles, whereas measurements on the more closely packed metallic gallium and gold surfaces indicate a significant surface roughness effect. Copyright © 2004 John Wiley & Sons, Ltd.     

Carbon nanotube/metal oxide dispersed poly(ortho‐aminophenol) as a ternary nanocomposite film: Facile electrosynthesis,surface characterization,and electrochemical pseudocapacitive performance

In this work, CNT‐NiCo₂O₄ was first synthesized via a chemical strategy in order to fabricate the ternary nanocomposite of a p‐type conductive polymer. Subsequently, hybrid poly(o‐aminophenol) POAP/CNT‐NiCo₂O₄ ternary composite films were prepared via the electropolymerization of POAP in the presence of CNT‐NiCo₂O₄ to be used in electrochemical storage devices as the active electrode. Electrochemical analyses including galvanostatic charge–discharge experiments, cyclic voltammetry, and electrochemical impedance spectroscopy were conducted to study the system performance. Furthermore, surface analyses were carried out to characterize the POAP/CNT‐NiCo₂O₄ composite film. Novel nanocomposite materials with the merits of extraordinarily high active surface area, ease of fabrication, and superior stability in aqueous electrolytes are presented for use in electrochemical redox capacitors.     

Epitaxial growth of single-crystalline Al(2)O(3) films on Cr(2)O(3)(0001)

Thin, crystallographically oriented single-crystalline Al2O3 films can be grown epitaxially on Cr2O3(0001) by codeposition of Al vapor and O2 at a substrate temperature of 825 K. The properties and growth of these films were monitored by Auger electron spectroscopy (AES), low-energy electron diffraction (LEED), low-energy ion scattering (LEIS), and X-ray photoelectron spectroscopy (XPS). Two routes of preparation were investigated: (i) stepwise growth by alternating deposition of Al at room temperature and subsequent exposure to O2 at elevated temperatures; (ii) codeposition of Al and O2 at T > 800 K. The first route was consistently found to result in the growth of a complex interfacial oxide followed by the growth of polycrystalline Al2O3. The second mode of preparation provided homogeneous and ordered, probably (0001)-oriented, films of Al2O3 that maintained a LEED pattern up to a thickness around 10 A. The surface sensitive Cr MVV Auger transition at 34 eV was completely attenuated once the Al2O3 layer had reached a thickness of 6 A, pointing to film homogeneity at an early stage. This was confirmed by the absence of a significant Cr signal in LEIS spectra.     

The growth of silver on an ordered alumina surface

The growth of Ag on an ordered Al2O3 surface was studied by low energy ion scattering spectroscopy (LEIS), scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and temperature programmed desorption (TPD). Three-dimensional (3D) growth of Ag clusters was observed with STM and LEIS, with the cluster size increasing with Ag coverage. The XPS core level binding energies and the Auger parameters indicate a weak interaction between the Ag clusters and the Al2O3 support. Final state effects are determined to be the primary contribution to the Ag core level binding energy shift. Nonzero order kinetics was observed for Ag desorption in TPD with the Ag sublimation energy decreasing with decreasing cluster size.     

Electronic and adsorption properties of Ce‐Ag layers

Silver has rarely been considered as the catalyst for CO oxidation, although it has been recognized to be very active in several partial oxidation reactions such as ethylene epoxidation and formaldehyde synthesis. It is generally believed that a metal support interaction plays an important role in catalytic processes. Therefore in our study, we examined electronic and adsorption properties of cerium deposited onto a polycrystalline silver substrate. Layers of approximately one monolayer of cerium deposited on a clean silver substrate were examined in situ using surface‐sensitive techniques—by XPS, ultraviolet photoelectron spectroscopy (UPS) and low energy ion scattering (LEIS). CO molecular adsorption was observed by UPS and LEIS; experimental results exhibited CO adsorption on Ce atoms sites. Oxygen adsorption on deposited layers led to a strong oxidation; stoichiometry of oxidized layers was given by amount of adsorbed oxygen and by temperature. Copyright © 2011 John Wiley & Sons, Ltd.     

Axis‐Oriented,Continuous Anatase Titania Films with Exposed Reactive {100} Facets

Homogeneous TiO₂ single crystals with high exposure of {100} reactive facets were constructed as a seed monolayer on transparent conductive substrates with the desired orientation of reactive facets. A secondary growth process was subsequently carried out on the monolayer seed film to form an axis‐oriented continuous reactive film. Performing secondary growth with different precursors led to optimized conditions for high‐performance photoelectrochemical activity of anatase TiO₂ films. Experimental techniques such as UV/Vis absorption spectroscopy, X‐ray diffraction, high‐resolution SEM, and photoelectrochemistry were used to characterize the structural, optical, and photoelectrochemical properties of the as‐synthesized films. As a photoanode in a photoelectrochemical cell, the axis‐oriented reactive film shows a maximum photocurrent density of 0.3 mA cm^?2, as opposed to 0.075 mA cm^?2 for non‐axis‐oriented (randomly oriented) TiO₂ film.     

Influence of thermal annealing on the microstructure,hardness and corrosion behavior of TiAlSiCuN nanocomposite films

Nanocomposite TiAlSiCuN films were deposited on high speed steels by filtered magnetic arc ion plating. Detailed properties of the films annealed at various temperatures are studied. After thermal annealing at different temperatures ranging from 400 to 800 °C, changes in the film micro‐structure, chemical and phase composition, surface morphology, hardness and polarization curve properties were systematically characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy, scanning electron microscopy, nano‐indenter and electrochemical workstation, respectively. It was found that the TiAlSiCuN films could be fully oxidized at 800 °C, Al and Ti atoms all diffused outwards and formed dense protective Al₂O₃ and TiO₂ layer. Simultaneously, the TiAlN phase gradually disappeared. The films annealed at 400 °C obtained the highest hardness because of the certain grain growth and little generated oxides. Besides, the certain formation of dense protective Al₂O₃ layer made the TiAlSiCuN film annealed at 600 °C present the least corrosion current density and the corrosion voltage. Copyright © 2016 John Wiley & Sons, Ltd.     

Patterning of cells on a PVC film surface functionalized by ion irradiation

Micropatterns of cells on a poly(vinyl chloride) (PVC) film surface were created by using ion irradiation. A PVC film was irradiated with H⁺ ions through a pattern mask in order to create patterns of the hydrophilic/hydrophobic regions on the PVC surface. The effect of ion irradiation on the surface properties of the PVC film was characterized by using Fourier transform‐infrared spectroscopy (FT‐IR), water contact angle measurement, and X‐ray photoelectron spectroscopy (XPS). The results revealed that the chemical environment of the PVC film surface was effectively changed by ion irradiation due to dehydrochlorination and oxidation. The in vitro cell culture on the patterned PVC film surface showed selective adhesion and proliferation of the cells on the ion‐irradiated regions. Well‐defined 50 µm patterns of the cells were obtained on the PVC film surface irradiated to 1 × 10¹⁵ ions/cm². Copyright © 2009 John Wiley & Sons, Ltd.     

Evaluating the electrochemical properties of PEO‐based nanofibrous electrolytes incorporated with TiO2 nanofiller applicable in lithium‐ion batteries

In the present work, nanofibrous composite polymer electrolytes consist of polyethylene oxide (PEO), ethylene carbonate (EC), propylene carbonate (PC), lithium perchlorate (LiClO₄), and titanium dioxide (TiO₂) were designed using response surface method (RSM) and synthesized via an electrospinning process. Morphological properties of the as‐prepared electrolytes were studied using SEM. FTIR spectroscopy was conducted to investigate the interaction between the components of the composites. The highest room temperature ionic conductivity of 0.085 mS.cm^?1 was obtained with incorporation of 0.175 wt. % TiO₂ filler into the plasticized nanofibrous electrolyte by EC. Moreover, the optimum structure was compared with a film polymeric electrolyte prepared using a film casting method. Despite more amorphous structure of the film electrolyte, the nanofibrous electrolyte showed superior ion conductivity possibly due to the highly porous structure of the nanofibrous membranes. Furthermore, the mechanical properties illustrated slight deterioration with incorporation of the TiO₂ nanoparticles into the electrospun electrolytes. This investigation indicated the great potential of the electrospun structures as all‐solid‐state polymeric electrolytes applicable in lithium ion batteries.     

ToF‐SIMS and XPS surface characterization of novel perfluoropolyether–urethane ionomers from aqueous dispersions

In this work a new class of ionomeric block perfluropolyether (PFPE) polyurethanes are presented; these polymers are obtained in the form of aqueous dispersions due to the presence of hydrophilic sites (ionomeric groups such as acetates or trialkylammonium salts) along the macromolecular chain, offering the chance to combine PFPEs in a variety of possible structures for coating or surface treatments with an environmentally friendly use. X‐ray photoelectron spectroscopy analysis at two different sampling depths, as well as time‐of‐flight secondary ion mass spectrometry analysis modelled by the use of principal component analysis (PCA), were used to investigate the first nanometres of the surface samples. It resulted in a clear surface enrichment in fluorine, and the different extent of the fluorine stratification will be discussed in relation to the ionic character, film‐forming from water and cross‐linking. Copyright © 2003 John Wiley & Sons, Ltd.     

Growth and sintering of Pd clusters on alpha-Al2O3(0001)

The growth and sintering of Pd nanoparticles on alpha-Al(2)O(3)(0001) have been studied by noncontact atomic force microscopy (NC-AFM), low-energy ion scattering spectroscopy (LEIS), temperature-programmed desorption (TPD) and x-ray photoelectron spectroscopy (XPS). This is the first study of metal nanoparticles on a well-defined oxide surface where both NC-AFM and LEIS are used for characterization. These prove to be a powerful combination in assessing particle dimensions. The clean alumina surface showed atomically flat, 200-700 nm wide terraces. The sharp step edges are straight (within our resolution) for lengths of >300 nm and have heights in multiples of 0.2 nm. The Pd grows initially as two-dimensional (2D) islands at 300 K, with the transition to 3D particle growth at 0.25 ML (ML=monolayers). Upon heating at 1 K/s, the Pd starts to sinter below 400 K, and sinters at a nearly constant rate with increasing temperature, covering approximately 50% less of the alumina surface by approximately 1000 K, with a doubling in particle diameter and an eightfold decrease in particle number density. By approximately 1000 K, the number density was approximately 9 x 10(11)cm(2) for 0.8 ML of Pd, with an average diameter of 5 nm and an average thickness of 1 nm.     

The fabrication of layer‐by‐layer mode LaCoO3 film by pulsed laser deposition

The relationship between strain and growth conditions in LaCoO₃ thin film was obtained to control the magnetic‐electric characteristics. The LaCoO₃ thin films on the SrTiO₃ substrates have been achieved by the pulsed laser deposition method, and the reflection high‐energy electron diffraction method (RHEED) was applied to monitor the growth process in situ; the layer‐by‐layer growth mode was discovered. The X‐ray diffraction and atomic force microscopy were applied to the phase analysis, and the layer thickness and the layer‐by‐layer growth mode were uncovered. Compared with the 100‐nm LaCoO₃ thin films, the strain in the layer‐by‐layer ultra thin film was more controllable. The enhanced magnetic properties of the layer‐by‐layer mode ultra‐thin films could be tested in future work.     

XPS study of impurities in Si‐doped AlN film

This paper reports an XPS study of impurities in a 100‐nm‐thick AlN film grown by metalorganic chemical vapor deposition (MOCVD) under low pressure on the n‐type 6H‐SiC substrate. The Si‐doped AlN film was characterized by the X‐ray photoelectron spectroscopy (XPS) in a high vacuum system, which reveals the content distribution and chemical states of impurities along depth. The XPS analysis of AlN film before and after argon‐ion etching indicates that there always exist Ga, O and C contaminations in AlN film. Especially, O contamination on the AlN film surface is mostly introduced during the growth of AlN layer by MOCVD. Meanwhile, most of O atoms bind with Al or Ga in Al―O and Ga―O chemical states. In particular, the Ga atoms in AlN film are always in two chemical states, i.e. Ga―Ga bond and Ga―O bond, which demonstrates that the aggregation of Ga is accompanying with AlN growth. Copyright © 2016 John Wiley & Sons, Ltd.     

Time‐of‐flight secondary ion mass spectroscopic characterization of the nitrogen profile of shallow gate oxynitride thermally grown on a silicon substrate

Silicon oxynitride has been used as a shallow gate oxide material for microelectronics and its thickness has been reduced over the years to only a few tens of angstroms due to device size scaling. The nitride distribution and density characteristic in the gate oxide thus becomes imperative for the devices. The shallow depth profiling capability using time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) has huge potential for the nitrogen characterization of the shallow gate oxide film. In this article, both positive and negative spectra of TOF‐SIMS on silicon oxynitride have been extensively studied and it was found that the silicon nitride clusters Si_xN^? (x = 1–4) are able to represent the nitrogen profiles because their ion yields are high enough, especially for the low‐level nitride doping in the oxide, which is formed by the annealing of nitric oxide on SiO₂/Si. The gate oxide thickness measured by the TOF‐SIMS profiling method using ¹⁸O or CsO profile calibration was found to correlate very well with transmission electron microscope measurement. The nitrogen concentration in the gate oxide measured using the TOF‐SIMS method was consistent with the results obtained using the dynamic SIMS method, which is currently applied to relatively thicker oxynitride films. Copyright © 2012 John Wiley & Sons, Ltd.     

Surface film formation on a graphite electrode in Li‐ion batteries: AFM and XPS study

The formation of a passivation film (solid electrolyte interphase, SEI) at the surface of the negative electrode of full LiCoO₂/graphite lithium‐ion cells using LiPF₆ (1M ) in carbonate solvents as electrolyte was investigated by means of x‐ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The analyses were carried out at different potentials of the first and the fifth cycles, showing the potential‐dependent character of the surface‐film species formation. These species were mainly identified as Li₂CO₃ up to 3.8 V and LiF up to 4.2 V. This study shows the formation of the SEI during charging and its partial dissolution during discharge. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis,characterization, and application of silver nanoparticle‐thiophenol nanocomposite film on the glassy carbon surface

In this study, 4‐thiophenol modified glassy carbon electrode was prepared by the reduction of 4‐diazothiophenol tetrafluoroborate salt. Silver nanoparticles were attached to the thiophenol modified surface to prepare a thiophenol‐silver nanoparticle composite film. 4‐Aminothiopenol molecules were deposited by self‐assembling technique to form multi‐layered nanofilms of TP/SNP/PhNH₂ on glassy carbon substrate. These surfaces were characterized by cyclic voltammetry, electrochemical impedance spectroscopy, X‐ray photoelectron spectroscopy, reflectance‐absorption infrared spectroscopy, and ellipsometry at each multilayer film growth process. Atomic force microscopic images of GC/TP/SNP/PhNH₂ surfaces were also acquired. The characterization methods show that the amine group containing surface permits the subsequent modification by a variety of coupling reactions for the immobilization of more complex systems. An application of the electrode modification for the determination of uric acid with a significantly lower detection limit is described. Copyright © 2013 John Wiley & Sons, Ltd.     

Low energy ion bombardment of Ti and TiNx films

The influence of low energy ion bombardment on TiN_x film growth and film properties was investigated. The discharge was characterized using Langmuir probe technique as well as energy resolved mass spectrometry with a plasma monitor (Hiden HAL 301 S/EQP). The deposited films were investigated by means of X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Increasing the N₂ gas flow as well as increasing the negative substrate voltage at constant gas flow effect an increase of the N/Ti ratio in the films determined by XPS. The influence of the energy flux to the surface due to ion bombardment was mainly recognized in the substructure of the films. In addition, pure Ti films were modified by nitrogen ion bombardment after deposition using an ion gun. An increase of the N/Ti ratio was observed with increasing ion energy. Finally saturation is reached.