X-ray Photoelectron Spectroscopy (XPS) Analysis of Ultrafine Au Nanoparticles Supported over Reactively Sputtered TiO2 Films.

The impact of a titania (TiO2) support film surface on the catalytic activity of gold nanoparticles (Au NP) was investigated. Using the reactive dc-magnetron sputtering technique, TiO2 films with an amorphous, anatase, and nitrogen-doped anatase crystal structure were produced for a subsequent role as a support material for Au NP. Raman spectra of these TiO2 films revealed that both vacuum and NH3 annealing treatments promoted amorphous to anatase phase transformation through the presence of a peak in the 513-519 cm-1 spectral regime. Furthermore, annealing under NH3 flux had an associated blue shift and broadening of the Raman active mode at 1430 cm-1, characteristic of an increase in the oxygen vacancies (VO). For a 3 to 15 s sputter deposition time, the Au NP over TiO2 support films were in the 6.7-17.1 nm size range. From X-ray photoelectron spectroscope (XPS) analysis, the absence of any shift in the Au 4f core level peak implied that there was no change in the electronic properties of Au NP. On the other hand, spontaneous hydroxyl (-OH) group adsorption to anatase TiO2 support was instantly detected, the magnitude of which was found to be enhanced upon increasing the Au NP loading. Nitrogen-doped anatase TiO2 supporting Au NP with ~21.8 nm exhibited a greater extent of molecular oxygen adsorption. The adsorption of both -OH and O2 species is believed to take place at the perimeter sites of the Au NP interfacing with the TiO2 film. XPS analyses and discussions about the tentative roles of O2 and -OH adsorbent species toward Au/TiO2 systems corroborate very well with interpretations of density functional theory simulations.

ZnO/Carbon xerogel photocatalysts by low-pressure plasma treatment, the role of the carbon substrate and its plasma functionalization.

ZnO is known to be photocatalytic, but with limited performances due to the strong electron-hole recombination after irradiation. The integration of ZnO nanomaterials on a conductive and high surface area carbon substrate is thus a potential alternative to obtain a significant improvement of the photocatalytic performance. Moreover, the carbon functionalization is expected to have a significant role in the adsorption/degradation mechanisms of dye, due to the difference in wettability or surface charge. In this view, ZnO photocatalytic nanoparticles have been deposited on high surface area carbon xerogel substrate (CXG), using a new and original plasma process, consisting in the degradation of a solid organometallic directly on the carbon substrate (no gaseous precursor). In addition to the ZnO nanoparticle formation, the plasma treatment allows the carbon functionalization. The ZnO/CXG composite has been tested for the degradation of Rhodamine B (RhB) in aqueous media and compared with and O2 or NH3 plasma-treated xerogels (without nanoparticles) to identify the significant role of the substrate and its modification in the RhB adsorption and degradation mechanism. The high photocatalytic activity of ZnO/CXG composite is attributed to (i) the formation of small (8-10 nm) and well-crystallized ZnO nanoparticles anchored to the carbon substrate and (ii) to the modification of the xerogel surface chemistry. Indeed, O2 plasma treatment of the CXG promotes the generation of hydroxyl, carbonyl and carboxyl surface functional groups, which are polar and acidic, while the NH3 plasma treatment mainly leads to the formation of polar and basic amino groups. While both plasma treatments promote the formation of polar functional groups, which enhance the CXG wettability, the formation of acidic groups is identified as beneficial for the adsorption of the RhB dye, while basic groups are detrimental.

High performance of 3D silicon nanowires array@CrN for electrochemical capacitors.

Silicon nanowire (SiNW) arrays were coated with chromium nitride (CrN) for use as supercapacitor electrodes. The CrN layer of different thicknesses was deposited onto SiNWs using bipolar magnetron sputtering method. The areal capacitance of the SiNWs-CrN, as measured in 0.5 M H2SO4 electrolyte, was as high as 180 mF cm-2 at a scan rate of 5 mV s-1 (equivalent to 31.8 mF cm-2 at 1.6 mA cm-2) with an excellent electrochemical retention of 92% over 15 000 cycles. This work paves the way toward using CrN modified 3D SiNWs arrays for micro-supercapacitor application.

Orange/Red Photoluminescence Enhancement Upon SF6 Plasma Treatment of Vertically Aligned ZnO Nanorods.

Although the origin and possible mechanisms for green and yellow emission from different zinc oxide (ZnO) forms have been extensively investigated, the same for red/orange PL emission from ZnO nanorods (nR) remains largely unaddressed. In this work, vertically aligned zinc oxide nanorods arrays (ZnO nR) were produced using hydrothermal process followed by plasma treatment in argon/sulfur hexafluoride (Ar/SF6) gas mixture for different time. The annealed samples were highly crystalline with ~45 nm crystallite size, (002) preferred orientation, and a relatively low strain value of 1.45 × 10-3, as determined from X-ray diffraction pattern. As compared to as-deposited ZnO nR, the plasma treatment under certain conditions demonstrated enhancement in the room temperature photoluminescence (PL) emission intensity, in the visible orange/red spectral regime, by a factor of 2. The PL intensity enhancement induced by SF6 plasma treatment may be attributed to surface chemistry modification as confirmed by X-ray photoelectron spectroscopy (XPS) studies. Several factors including presence of hydroxyl group on the ZnO surface, increased oxygen level in the ZnO lattice (OL), generation of F-OH and F-Zn bonds and passivation of surface states and bulk defects are considered to be active towards red/orange emission in the PL spectrum. The PL spectra were deconvoluted into component Gaussian sub-peaks representing transitions from conduction-band minimum (CBM) to oxygen interstitials (Oi) and CBM to oxygen vacancies (VO) with corresponding photon energies of 2.21 and 1.90 eV, respectively. The optimum plasma treatment route for ZnO nanostructures with resulting enhancement in the PL emission offers strong potential for photonic applications such as visible wavelength phosphors.

Chemical Analysis of the Interface in Bulk-Heterojunction Solar Cells by X-ray Photoelectron Spectroscopy Depth Profiling.

Despite the wide use of blends combining an organic p-type polymer and molecular fullerene-based electron acceptor, the proper characterization of such bulk heterojunction materials is still challenging. To highlight structure-to-function relations and improve the device performance, advanced tools and strategies need to be developed to characterize composition and interfaces with sufficient accuracy. In this work, high-resolution X-ray photoelectron spectroscopy (XPS) is combined with very low energy argon ion beam sputtering to perform a nondestructive depth profile chemical analysis on full Al/P3HT:PCBM/PEDOT:PSS/ITO (P3HT, poly(3-hexylthiophene); PCBM, [6,6]-phenyl-C61-butyric acid methyl ester; PEDOT, poly(3,4-ethylenedioxythiophene; PSS, polystyrenesulfonate; ITO, indium tin oxide) bulk-heterojunction solar cell device stacks. Key information, such as P3HT and PCBM composition profiles and Al-PCBM chemical bonding, are deduced in this basic device structure. The interface chemical analysis allows us to evidence, with unprecedented accuracy, the inhomogeneous distribution of PCBM, characterized by a strong segregation toward the top metal electrode. The chemical analysis high-resolution spectra allows us to reconstruct P3HT/PCBM ratio through the active layer depth and correlate with the device deposition protocol and performance. Results evidence an inhomogeneous P3HT/PCBM ratio and poorly controllable PCBM migration, which possibly explains the limited light-to-power conversion efficiency in this basic device structure. The work illustrates the high potential of XPS depth profile analysis for studying such organic/inorganic device stacks.

Correlation of annealing time with crystal structure, composition, and electronic properties of CH3NH3PbI3-xClx mixed-halide perovskite films.

Using 3D imaging with time-of-flight secondary ion mass spectrometry (ToF-SIMS) complemented by grazing-incidence X-ray diffraction (GIXRD), we spatially resolve changes in both the composition and structure of CH3NH3I3-xClx perovskite films on conducting polymer substrates at different annealing stages, in particular, before and after complete perovskite crystallization. The early stage of annealing is characterized by phase separation throughout the entire film into domains with perovskite and domains with a dominating chloride-rich phase. After sufficiently long annealing, one single perovskite phase of homogeneous composition on the (lateral) micrometer scale is observed, along with pronounced film texture. This composition evolution is accompanied by diffusion of chloride from the perovskite layer towards the conducting polymer substrate, and even accumulation there. Photoelectron spectroscopy analysis further shows that perovskite films become increasingly n-type with annealing time and upon full conversion, which correlates with the change of film composition. Our results accentuate the importance of chloride for the formation of crystalline and textured films, which are crucial for enhancing the PV performance of perovskite-based solar cells.

Mesoscopic Perovskite Light-Emitting Diodes.

Solution-processed hybrid bromide perovskite light-emitting-diodes (PLEDs) represent an attractive alternative technology that would allow overcoming the well-known severe efficiency drop in the green spectrum related to conventional LEDs technologies. In this work, we report on the development and characterization of PLEDs fabricated using, for the first time, a mesostructured layout. Stability of PLEDs is a critical issue; remarkably, mesostructured PLEDs devices tested in ambient conditions and without encapsulation showed a lifetime well-above what previously reported with a planar heterojunction layout. Moreover, mesostructured PLEDs measured under full operative conditions showed a remarkably narrow emission spectrum, even lower than what is typically obtained by nitride- or phosphide-based green LEDs. A dynamic analysis has shown fast rise and fall times, demonstrating the suitability of PLEDs for display applications. Combined electrical and advanced structural analyses (Raman, XPS depth profiling, and ToF-SIMS 3D analysis) have been performed to elucidate the degradation mechanism, the results of which are mainly related to the degradation of the hole-transporting material (HTM) and to the perovskite-HTM interface.

Interface and Composition Analysis on Perovskite Solar Cells.

Organometal halide (hybrid) perovskite solar cells have been fabricated following four different deposition procedures and investigated in order to find correlations between the solar cell characteristics/performance and their structure and composition as determined by combining depth-resolved imaging with time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), and analytical scanning transmission electron microscopy (STEM). The interface quality is found to be strongly affected by the perovskite deposition procedure, and in particular from the environment where the conversion of the starting precursors into the final perovskite is performed (air, nitrogen, or vacuum). The conversion efficiency of the precursors into the hybrid perovskite layer is compared between the different solar cells by looking at the ToF-SIMS intensities of the characteristic molecular fragments from the perovskite and the precursor materials. Energy dispersive X-ray spectroscopy in the STEM confirms the macroscopic ToF-SIMS findings and allows elemental mapping with nanometer resolution. Clear evidence for iodine diffusion has been observed and related to the fabrication procedure.

A novel dry chemical path way for diene and dienophile surface functionalization toward thermally responsive metal-polymer adhesion.

In this paper, we report a new and easily up-scalable dry chemical method to functionalize with diene and dienophile groups a large range of surfaces, such as metal, polymer, or glass, and we demonstrate the potentiality of this technique to realize thermally responsive adhesion between these materials. A complete and extensive surface chemistry analysis of the grafted surfaces, based on the deposition of an anhydride-rich thin plasma polymer layer by using an atmospheric pressure dielectric barrier discharge (DBD) plasma process, and its subsequent gas phase aminolysis reaction with specific diene or dienophile compound is discussed. The optimization of the assembling condition for these tailored surfaces has led to achieve a Diels-Alder adhesion force up to 0.6 N/mm at ambient temperature, which can be reduced by a factor of 50 when the retro Diels-Alder is ignited at a heating temperature around 200 °C. The study of the failure interface produced after peeling tests is presented and a mechanism of failure is proposed, based on forensic analyses involving surface analytical techniques such as XPS, ToF-SIMS, and SEM combined to AFM analyses for the retrieving of chemical and morphological information.

Single- and double-sided chemical functionalization of bilayer graphene.

An experimental study on the interaction between the top and bottom layer of a chemically functionalized graphene bilayer by mild oxygen plasma is reported. Structural, chemical, and electrical properties are monitored using Raman spectroscopy, transport measurements, conductive atomic force microscopy and X-ray photoelectron spectroscopy. Single- and double-sided chemical functionalization are found to give very different results: single-sided modified bilayers show relatively high mobility (200-600 cm(2) V(-1) s(-1) at room temperature) and a stable structure with a limited amount of defects, even after long plasma treatment (>60 s). This is attributed to preferential modification and limited coverage of the top layer during plasma exposure, while the bottom layer remains almost unperturbed. This could eventually lead to decoupling between top and bottom layers. Double-sided chemical functionalization leads to a structure containing a high concentration of defects, very similar to graphene oxide. This opens the possibility to use plasma treatment not only for etching and patterning of graphene, but also to make heterostructures (through single-sided modification of bilayers) for sensors and transistors and new graphene-derivatives materials (through double-sided modification).

Synthesis and Characterization of Ca and Ba Doped LAMOX Materials and Surface Study by X-ray Photoelectron Spectroscopy.

(La1-xCax)2Mo2O9-d and (La1-xBax)2Mo2O9-d (x = 0.05, 0.1, 0.15, 0.2) materials were prepared at 800 °C by co-precipitation method and characterized by X-ray diffraction and scanning electron microscope. The XRD diagrams showed the presence of CaMoO4 and BaMoO4 secondary phases only at high contents of the dopants. X-ray photoelectron spectroscopy was used to study the surface chemical structure of doped and undoped materials (La2Mo2O9). It was found that the La and Mo atoms had 3+ and 6+ valence states, respectively. The absence of carbides and carbonates at surface suggests that, the unavoidable carbon contamination did not interact with the metal atoms, which allows applications using carbonaceous fuels, and, that the formation of secondary phases did not influence the surface state. XPS spectra show that the covalent character of the La-O bond was enhanced with calcium doping as compared to barium, predicting interesting conductive and catalytic properties of the materials.

Gas sensing with Au-decorated carbon nanotubes.

The sensing properties of carbon nanotubes (CNTs) decorated with gold nanoparticles have been investigated by means of combined theoretical and experimental approaches. On one hand, first-principles and nonequilibrium Green's functions techniques give access to the microscopic features of the sensing mechanisms in individual nanotubes, such as electronic charge transfers and quantum conductances. On the other hand, drop coating deposition of carbon nanotubes decorated with gold nanoparticles onto sensor substrates and their characterization in the detection of pollutants such as NO(2), CO, and C(6)H(6) provide insight into the sensing ability of nanotube mats. Using the present combined approaches, the improvement in the detection of some specific gases (NO(2) and CO) using Au-functionalized nanotubes is explained. However, for other gases such as C(6)H(6), the Au nanoparticles do not seem to play a crucial role in the sensing process when compared with pristine CNTs functionalized with oxygen plasma. Indeed, these different situations can be explained by identifying the relationship between the change of resistance (macroscopic feature) and the shift of the Fermi level (microscopic feature) after gas adsorption. The understanding of the sensing ability at the atomic level opens the way to design new gas sensors and to tune their selectivity by predicting the nature of the metal that is the most appropriate to detect specific molecular species.

Influence of the 316 L stainless steel interface on the stability and barrier properties of plasma fluorocarbon films.

Coatings are known to be one of the more suited strategies to tailor the interface between medical devices and the surrounding cells and tissues once implanted. The development of coatings and the optimization of their adhesion and stability are of major importance. In this work, the influence of plasma etching of the substrate on a plasma fluorocarbon ultrathin coating has been investigated with the aim of improving the stability and the corrosion properties of coated medical devices. The 316 L stainless steel interface was subjected to two different etching sequences prior to the plasma deposition. These plasma etchings, with H(2) and C(2)F(6) as gas precursors, modified the chemical composition and the thickness of the oxide layer and influenced the subsequent polymerization. The coating properties were evaluated using flat substrates submitted to deformation, aging into aqueous medium and corrosion tests. X-ray photoelectron spectroscopy (XPS), time of flight-secondary ion mass spectrometry (ToF-SIMS), ellipsometry, and atomic force microscopy (AFM) were performed to determine the effects of the deformation and the aging on the chemistry and morphology of the coated samples. Analyses showed that plasma etchings were essential to promote reproducible polymerization and film growth. However, the oxide layer thinning due to the etching lowered the corrosion resistance of the substrate and affected the stability of the interface. Still, the deformed samples did not exhibited adhesion and cohesion failure before and after the aging.

Measuring point defect density in individual carbon nanotubes using polarization-dependent X-ray microscopy.

The presence of defects in carbon nanotubes strongly modifies their electrical, mechanical, and chemical properties. It was long thought undesirable, but recent experiments have shown that introduction of structural defects using ion or electron irradiation can lead to novel nanodevices. We demonstrate a method for detecting and quantifying point defect density in individual carbon nanotubes (CNTs) based on measuring the polarization dependence (linear dichroism) of the C 1s --> pi* transition at specific locations along individual CNTs with a scanning transmission X-ray microscope (STXM). We show that STXM can be used to probe defect density in individual CNTs with high spatial resolution. The quantitative relationship between ion dose, nanotube diameter, and defect density was explored by purposely irradiating selected sections of nanotubes with kiloelectronvolt (keV) Ga(+) ions. Our results establish polarization-dependent X-ray microscopy as a new and very powerful characterization technique for carbon nanotubes and other anisotropic nanostructures.

Study of the interface between rhodium and carbon nanotubes.

X-ray photoelectron spectroscopy at 3.5 keV photon energy, in combination with high-resolution transmission electron microscopy, is used to follow the formation of the interface between rhodium and carbon nanotubes. Rh nucleates at defect sites, whether initially present or induced by oxygen-plasma treatment. More uniform Rh cluster dispersion is observed on plasma-treated CNTs. Experimental results are compared to DFT calculations of small Rh clusters on pristine and defective graphene. While Rh interacts as strongly with the carbon as Ti, it is less sensitive to the presence of oxygen, suggesting it as a good candidate for nanotube contacts.

Transition metal deposition on graphene and carbon nanotubes.

We present a combined theoretical and experimental comparative study of the deposition of five different metals on perfect and defective graphene and multi-walled carbon nanotubes (MWNTs): Ti, Ni, Pd, Pt and Au. Atomistic modelling successfully provides a comprehensive picture of surface binding, diffusion and aggregation properties for these metals, highlighting some fundamental differences in their surface chemical and electronic behaviour. We correlate these theoretical results with experimental TEM images of metal deposited MWCNTs.

The role of oxygen at the interface between titanium and carbon nanotubes.

We study the interface between carbon nanotubes (CNTs) and surface-deposited titanium using electron microscopy and photoemission spectroscopy, supported by density functional calculations. Charge transfer from the Ti atoms to the nanotube and carbide formation is observed at the interface which indicates strong interaction. Nevertheless, the presence of oxygen between the Ti and the CNTs significantly weakens the Ti-CNT interaction. Ti atoms at the surface will preferentially bond to oxygenated sites. Potential sources of oxygen impurities are examined, namely oxygen from any residual atmosphere and pre-existing oxygen impurities on the nanotube surface, which we enhance through oxygen plasma surface pre-treatment. Variation in literature data concerning Ohmic contacts between Ti and carbon nanotubes is explained via sample pre-treatment and differing vacuum levels, and we suggest improved treatment routes for reliable Schottky barrier-free Ti-nanotube contact formation.

Polarization dependence of the C 1s X-ray absorption spectra of individual multi-walled carbon nanotubes.

The polarization dependence (linear dichroism) of the C 1s X-ray absorption spectrum of individual multi-walled carbon nanotubes (MWCNTs) is measured using scanning transmission X-ray microscopy. A very strong dichroic effect is found in the C 1s --> pi* transition, with almost complete disappearance of this transition when the electric-field (E)-vector is aligned parallel to high-quality (low-defect) MWCNTs and maximum intensity when the E-vector is orthogonal to the tube axis. In contrast, there is very little dichroism in the C 1s --> sigma* transitions. The origin of this polarization effect is explained. The magnitude of the polarization dependence is found to differ in MWCNTs synthesized by different methods (arc discharge versus chemical vapor deposition). This is ascribed to differences in densities of sp(2)-type defects. The potential for use of this signal to characterize defects in single-carbon-nanotube devices is discussed.

Study of interlayer spacing collapse during polymer/clay nanocomposite melt intercalation.

The influence of the chemical structure of alkylammonium organo-modifying montmorillonite clays on the ability to form nanocomposites by melt blending, depending on the processing temperature and the organoclay thermal treatment, has been investigated. On one side chlorinated polyethylene/Cloisite 30B (nano)composite has been prepared by melt intercalation at 175 degrees C and its wide angle X-ray diffraction pattern revealed that the peak characteristic of the interlayer spacing of the organoclay was shifted to lower d-spacing, indicating a collapse of the organoclay structure. On the other side, (nano)composites based on ethylene-vinyl acetate copolymer/Cloisite 30B have been prepared by melt intercalation at 140 degrees C. At this temperature, exfoliation was observed with the as-received organoclay while the same organo-modified clay, simply dried at 180 degrees C for 2 hours, induced again the formation of a composite with a collapsed structure. The effect of the Cloisite 30B thermal treatment on the morphology and mechanical properties of ethylene-vinyl acetate-based (nano)composites was investigated using wide angle X-ray diffraction and tensile tests. In order to shed some light on the origin of this clay interlayer collapse, organoclay modified with various ammonium cations bearing long alkyl chains with different amounts of unsaturations were studied using wide angle X-ray diffraction and X-ray photoelectron spectroscopy before and after thermal treatment at 180 degrees C for 2 hours. Isothermal thermogravimetric analysis of all organoclays was also investigated. The layers collapse effect is discussed depending upon the level of unsatured hydrocarbon present in the organic surfactant.