Scientific Papers in SCI

2014


Title: Interpretation of electron Rutherford backscattering spectrometry for hydrogen quantification
Author(s): Alvarez, R; Yubero, F
Source: Surface and Interface Analysis, 46 (2014) 812-816

abstract | fulltext

In the last few years, several papers have appeared showing the capabilities of electron Rutherford backscattering spectrometry (eRBS) to quantify the H content at surfaces. The basis of the H detection in this technique relies on the difference in recoil energy of the incident electrons depending on the mass of the atoms located at the surface that act as scatter centers. In this paper, we address the interpretation of eRBS spectra of hydrogen containing surfaces. The aim is to compare the naive single elastic scattering approximation with a more realistic description of eRBS spectra including multiple elastic scattering using the HQ-eRBS (hydrogen quantification eRBS) software based on a Monte Carlo algorithm. It is concluded that multiple elastic scattering is a significant contribution to experimentally measured eRBS spectra of a polyethylene surface. It induces significant broadening of the distribution of the maximum elastic scattering angle along the electron trajectories contributing to the measured spectra. However, it has weak effect in the energy distribution of the collected electrons (about 10% overestimation of the H content in the particular case of a polyethylene surface with respect to the corresponding ratio of elastic scattering cross sections).

October, 2014 | DOI: 10.1002/sia.5486

Title: Modeling of X-ray photoelectron spectra: surface and core hole effects
Author(s): Pauly, N; Tougaard, S; Yubero, F
Source: Surface and Interface Analysis, 46 (2014) 920-923

abstract | fulltext

The shape and intensity of photoelectron peaks are strongly affected by extrinsic excitations due to electron transport out of the surface and by intrinsic excitations induced by the sudden creation of the static core hole. Besides, elastic electron scattering may also be important. These effects should be included in the theoretical description of the emitted photoelectron peaks. To investigate the importance of surface and core hole effects relative to elastic scattering effect, we have calculated full XPS spectra for the Cu 2p emissions of Cu and CuO with the simulation of electron spectra for surface analysis (SESSA) software and with a convolution procedure using the differential inelastic electron scattering cross-section obtained with the quantitative analysis of electron energy loss in XPS (QUEELS-XPS) software. Surface and core hole effects are included in QUEELS-XPS but absent in SESSA while elastic electron scattering effects are included in SESSA but absent in QUEELS-XPS. Our results show that the shape of the XPS spectra are strongly modified because of surface and core hole effects, especially for energy losses smaller than about 20eV.

October, 2014 | DOI: 10.1002/sia.5372

Title: Mechanochemically synthesized nanocrystalline Sb2S3 particles
Author(s): Dutkova, E; Sayagues, MJ; Real, C; Zorkovska, A; Balaz, P; Satka, A; Kovac, J; Ficeriova, J
Source: Acta Physica Polonica A, 126 (2014) 943-946

abstract | fulltext

Nanocrystalline Sb2S3 particles have been synthesized from Sb and S powders by high-energy milling in a planetary mill using argon protective atmosphere. X-ray diffraction, particle size analysis, scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, electron diffraction, high resolution transmission electron microscopy, UV-VIS, and differential scanning calorimetry methods for characterization of the prepared particles were applied. The powder X-ray diffraction pattern shows that Sb2S3 nanocrystals belong to the orthorhombic phase with calculated crystallite size of about 36 nm. The nanocrystalline Sb2S3 particles are constituted by randomly distributed crystalline nanodomains (20 nm) and then these particles are forming aggregates. The monomodal distribution of Sb2S3 particles with the average hydrodynamic parameter 210 nm was obtained. The quantification of energy dispersive X-ray spectroscopy analysis peaks give an atomic ratio of 2:3 for Sb:S. The optical band gap determined from the absorption spectrum is 4.9 eV, indicating a considerable blue shift relative to the bulk Sb2S3. Differential scanning calorimetry curves exhibit a broad exothermic peak between 200 and 300°C, suggesting recovery processes. This interpretation is supported by X-ray diffraction measurements that indicate a 23-fold increase of the crystallite size to about 827 nm as a consequence of application of high temperature process. The controlled mechanochemical synthesis of Sb2S3nanoparticles at ambient temperature and atmospheric pressure remains a great challenge.

October, 2014 | DOI: 10.12693/APhysPolA.126.943

Title: Impregnation of carbon black for the examination of colloids using TEM
Author(s): Gontard, LC; Knappett, BR; Wheatley, AEH; Chang, SLY; Fernandez, A
Source: Carbon, 76 (2014) 464-468

abstract | fulltext

Nanoparticles are frequently synthesised as colloids, dispersed in solvents such as water, hexane or ethanol. For their characterisation by transmission electron microscopy (TEM), a drop of colloid is typically deposited on a carbon support and the solvent allowed to evaporate. However, this method of supporting the nanoparticles reduces the visibility of fine atomic details, particularly for carbonaceous species, due to interference from the 2-dimensional carbon support at most viewing angles. We propose here the impregnation of a 3 dimensional carbon black matrix that has been previously deposited on a carbon film as an alternative means of supporting colloidal nanoparticles, and show examples of the application of this method to advanced TEM techniques in the analysis of monometallic, core@shell and hybrid nanoparticles with carbon-based shells.

Nanoparticles represent one of the most studied structures in nanotechnology and nanoscience because of the wide range of applications arising from their unique optical, physical and chemical properties [1]. Often they have core@shell structures, or are coated with organic molecules. Nanoparticle functionality is largely affected by the specific configuration of the outer surface atoms. For example, in heterogeneous catalysis activity and selectivity are mostly determined by the type of atomic defects present at the surface of metallic nanoparticles, and in the field of biomedicine the surface coating of hybrid (inorganic core@organic shell) nanoparticles regulates their stability, solubility and targeting.

Nanoparticles are frequently synthesised using solution techniques that yield colloids, i.e., a solid–liquid mixture containing solid particles that are dispersed to various degrees in a liquid medium; most frequently water, ethanol or hexane. Colloid characterisation generally employs a variety of techniques to establish understanding and control over nanoparticle synthesis and properties. Electron microscopy in transmission mode (TEM) and in scanning transmission mode (STEM) are widely used for particle characterisation, and advances in these techniques mean that it is now routinely possible to resolve single atoms at the surfaces of nanoparticles using aberration-corrected microscopes, to elucidate the three-dimensional shapes of nanoparticles using electron tomography, and to enhance the contrast in very low density materials (e.g., carbonaceous materials) using electron holography [2] and [3]. However, the significant potential of these (S)TEM techniques is ultimately limited by the sample and the techniques available for sample preparation.

Typically, examination by (S)TEM requires that a nanoparticulate sample be prepared by depositing a drop of colloid on a thin, electron-transparent support. It is usual that an amorphous carbon film, silicon nitride film or graphene layers deposited on a copper grid constitute the support [4]. Crucially, these sample preparation techniques suffer from the major limitation that the contrast from the support often shadows atomic details at the particle surface. Moreover, it has been established that the thinnest supports can degrade under electron-beam irradiation, affecting particle stability [5], and also that hydrocarbon contamination can be an issue [6]. The most widely used commercially available TEM support is holey carbon, which comprises of a perforated carbon thin film. In this case, sample preparation aims to locate at least some of the nanoparticles of interest at the edges of the perforations. However, the concave nature of the holes means that solvent contaminants tend to accumulate preferentially at these sites. Moreover, if the TEM sample holder is tilted a particle attached to the edge of a hole is very likely to be shadowed by the carbon film. Taken together, these drawbacks significantly limit the application of techniques such as electron tomography [6].

We propose here a method of circumventing some of these fundamental problems by developing a technique for mounting nanoparticulate samples using a carbon matrix that is inspired by the way samples used in electrocatalysis are prepared [7]. Fig. 1 shows an image of a typical Pt-based electrocatalyst supported on carbon black as used in proton-electron membrane fuels cells, and which consists of Pt nanoparticles formed by calcination of a carbon black impregnated with a solution of salt precursor. Carbon black is a low-grade form of graphite, which is composed of nanocrystallites and no long-range order [8]. In Fig. 1 the carbon black is Vulcan XC-72R, which is widely used as a catalyst support in fuel cells because it provides high electrical conductivity, good reactant gas access, adequate water handling and good corrosion resistance, whilst allowing high dispersion of the particles. In electrocatalyst samples it is common to find particles, like the 5 nm Pt particle shown in Fig. 1, attached strongly to the surface of the support and viewed edge-on against a vacuum so as to provide optimal conditions for high-resolution TEM (HRTEM). Fig. 1B is a quantitative phase image of a Pt particle obtained from a defocus series of 20 images at intervals of 5 nm acquired in a FEGTEM JEOL 2020 at 200 kV with spherical aberration of −30 μm and applying the exit-wave restoration technique [2]. The contrast between details of the particle finestructure is very high compared to conventional HRTEM images, and details such as the presence of monoatomic carbon ribbons surrounding the particle can be seen.

September, 2014 | DOI: 10.1016/j.carbon.2014.05.006

Title: Morphological and structural behavior of TiO2 nanoparticles in the presence of WO3: crystallization of the oxide composite system
Author(s): Kubacka, A; Iglesias-Juez, A; di Michiel, M; Becerro, AI; Fernandez-Garcia, M
Source: Physical Chemistry Chemical Physics, 16 (2014) 19540-19549

abstract | fulltext

Composite TiO2-WO3 oxide materials were prepared by a single pot microemulsion method and studied during calcination treatments under dry air in order to analyze the influence of tungsten on the behavior of the dominant titania component. To this end, the surface and bulk morphological and structural evolution of the solid precursors was studied using X-ray diffraction and infrared spectroscopy. In the calcination process, differences in the dominant titania component behavior appeared as a function of the W/Ti atomic ratio of the precursor. First, the crystallization of the anatase phase is affected by tungsten through an effect on the primary particle size growth. Furthermore, such an effect also influences the anatase to rutile phase transformation. The study provides evidence that the W-Ti interaction develops differently for a low/high W/Ti atomic ratio below/above 0.25 affecting fundamentally the above-mentioned anatase primary particle size growth process and the subsequent formation of the rutile phase and showing that addition of tungsten provides a way to control morphology and phase behavior in anatase-based oxide complex materials.

September, 2014 | DOI: 10.1039/c4cp02181a

Title: Multidirectional Light-Harvesting Enhancement in Dye Solar Cells by Surface Patterning
Author(s): Lopez-Lopez, C; Colodrero, S; Jimenez-Solano, A; Lozano, G; Ortiz, R; Calvo, ME; Miguez, H
Source: Advanced Optical Materials, 2 (2014) 879-884

abstract | fulltext

One dimensional gratings patterned on the surface of nanocrystalline titania electrodes are used as a light harvesting strategy to improve the overall performance of dye solar cells under both frontal and rear illumination conditions. A soft-lithography-based micromoulding approach is employed to replicate a periodic surface relief pattern onto the surface of the electrode, which is later sensitized with a dye. As the patterned surface acts as an optical grating both in reflection and transmission modes, its effect is to increase the light path of diffracted beams within the absorbing layer when it is irradiated either from the electrode or the counter electrode for a broad range of angles of incidence on each surface. Full optical and photovoltaic characterization demonstrates not only the optical quality of the patterned surfaces but also the multidirectional character of the enhancement of light harvesting and conversion efficiency. The approach herein presented thus permits to preserve the operation of the cell when irradiated from its two faces while increasing its overall power conversion efficiency. This feature is a key advantage over other light harvesting efficiency enhancing methods, such as the deposition of a back diffuse scattering layer, in which the performance of the cell under illumination from one of its sides is enlarged at the expense of reducing the output under reverse irradiation conditions.

September, 2014 | DOI: 10.1002/adom.201400160

Title: On the formation of the porous structure in nanostructured a-Si coatings deposited by dc magnetron sputtering at oblique angles
Author(s): Godinho, V; Moskovkin, P; Alvarez, R; Caballero-Hernandez, J; Schierholz, R; Bera, B; Demarche, J; Palmero, A; Fernandez, A; Lucas, S
Source: Nanotechnology, 25 (2014) 355705

abstract | fulltext

The formation of the porous structure in dc magnetron sputtered amorphous silicon thin films at low temperatures is studied when using helium and/or argon as the processing gas. In each case, a-Si thin films were simultaneously grown at two different locations in the reactor which led to the assembly of different porous structures. The set of four fabricated samples has been analyzed at the microstructural level to elucidate the characteristics of the porous structure under the different deposition conditions. With the help of a growth model, we conclude that the chemical nature of the sputter gas not only affects the sputtering mechanism of Si atoms from the target and their subsequent transport in the gaseous/plasma phase towards the film, but also the pore formation mechanism and dynamics. When Ar is used, pores emerge as a direct result of the shadowing processes of Si atoms, in agreement with Thornton's structure zone model. The introduction of He produces, in addition to the shadowing effects, a new process where a degree of mobility results in the coarsening of small pores. Our results also highlight the influence of the composition of sputtering gas and tilt angles (for oblique angle deposition) on the formation of open and/or occluded porosity.

September, 2014 | DOI: 10.1088/0957-4484/25/35/355705

Title: Reticulated bioactive scaffolds with improved textural properties for bone tissue engineering: Nanostructured surfaces and porosity
Author(s): Ramiro-Gutierrez, ML; Will, J; Boccaccini, AR; Diaz-Cuenca, A
Source: Journal of Biomedical Materials Research Part A, 102 (2014) 2982-2992

abstract | fulltext

Organised nanoporous SBA-15 type silica precursor (SP) particulate material has been processed into three-dimensional macroporous, reticulated structures using a novel strategy consisting of blending increasing percentages of SP with a SiO2-CaO-P2O5 (80Si15Ca5P) mesoporous bioactive glass (MBG) sol. The procedure successfully produced consolidated and functionally competent open-cell scaffolds while preserving the nanoporous order of the SP. Scaffolds were prepared using four different (MBG)/(SP) ratios. These structures were then characterized using field emission gun scanning electron microscopy, X-ray diffraction (XRD), nitrogen adsorption-desorption measurements, and compressive strength testing. Open-cell interconnected structures with dual macro (150-500 mu m) and nano (4-6 nm)-organised porosity were produced. Both the textural and mechanical properties were found to improve with increasing SBA-15 content. The in vitro bioactive response using simulated body fluid confirmed high reactivity for all prepared scaffolds. In addition, the SBA-15 containing scaffolds exhibited a superior ability to delay the pH-triggered lysozyme release with antibiotic activity. (C) 2013 Wiley Periodicals, Inc.

September, 2014 | DOI: 10.1002/jbm.a.34968

Title: Technological Proposals for Recycling Industrial Wastes for Environmental Applications
Author(s): Romero-Hermida, I; Morales-Florez, V; Santos, A; Villena, A; Esquivias, L
Source: Minerals, 4 (2014) 746-757

abstract | fulltext

A two-fold objective is proposed for this research: removing hazardous and unpleasant wastes and mitigating the emissions of green house gasses in the atmosphere. Thus, the first aim of this work is to identify, characterize and recycle industrial wastes with high contents of calcium or sodium. This involves synthesizing materials with the ability for CO2 sequestration as preliminary work for designing industrial processes, which involve a reduction of CO2 emissions. In this regard, phosphogypsum from the fertilizer industry and liquid wastes from the green olive and bauxite industries have been considered as precursors. Following a very simple procedure, Ca-bearing phosphogypsum wastes are mixed with Na-bearing liquid wastes in order to obtain a harmless liquid phase and an active solid phase, which may act as a carbon sequestration agent. In this way, wastes, which are unable to fix CO2 by themselves, can be successfully turned into effective CO2 sinks. The CO2 sequestration efficiency and the CO2 fixation power of the procedure based on these wastes are assessed.

September, 2014 | DOI: 10.3390/min4030746

Title: Tailor-made directional emission in nanoimprinted plasmonic-based light-emitting devices
Author(s): Lozano, G; Grzela, G; Verschuuren, MA; Ramezani, M; Rivas, JG
Source: Nanoscale, 6 (2014) 9223-9229

abstract | fulltext

We demonstrate an enhanced and tailor-made directional emission of light-emitting devices using nanoimprinted hexagonal arrays of aluminum nanoparticles. Fourier microscopy reveals that the, luminescence of the device is not only determined by the material properties of the organic dye molecules but is also strongly influenced by the coherent scattering resulting from periodically arranged metal nanoparticles. Emitters can couple to lattice-induced hybrid plasmonic-photonic modes sustained by plasmonic arrays. Such modes enhance the spatial coherence of an emitting layer, allowing the efficient beaming of the emission along narrow angular and spectral ranges. We show that tailoring the separation of the nanoparticles in the array yields an accurate angular distribution of the emission. This combination of large-area metal nanostructures fabricated by nanoimprint lithography and light-emitting devices is beneficial for the design and optimization of solid-state lighting systems.

August, 2014 | DOI: 10.1039/c4nr01391c

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