WhatEELS. A python-based interactive software solution for ELNES analysis combining clustering and NLLS.

The analysis of energy loss near edge structures in EELS is a powerful method for a precise characterization of elemental oxidation states and local atomic coordination with an outstanding lateral resolution, down to the atomic scale. Given the complexity and sizes of the EELS spectrum images datasets acquired by the state-of-the-art instrumentation, methods with low convergence times are usually preferred for spectral unmixing in quantitative analysis, such as multiple linear least squares fittings. Nevertheless, non-linear least squares fitting may be a superior choice for analysis in some cases, as it eliminates the need of calibrated reference spectra and provides information for each of the individual components included in the fitted model. To avoid some of the problems that the non-linear least squares algorithms may suffer dealing with mixed-composition samples and, thus, a model comprised by a large number of individual curves we proposed the combination of clustering analysis for segmentation and non-linear least squares fitting for spectral analysis. Clustering analysis is capable of a fast classification of pixels in smaller subsets divided by their spectral characteristics, and thus increases the control over the model parameters in separated regions of the samples, classified by their specific compositions. Furthermore, along with this manuscript we provide access to a self-contained and expandable modular software solution called WhatEELS. It was specifically designed to facilitate the combined use of clustering and NLLS, and includes a set of tools for white-lines analysis and elemental quantification. We successfully demonstrated its capabilities with a control sample of mesoporous cerium oxide doped with praseodymium and gadolinium, which posed challenging case-study given its spectral characteristics.

Support vector machine for EELS oxidation state determination.

Electron Energy-Loss Spectroscopy (EELS) is a powerful and versatile spectroscopic technique used to study the composition and local optoelectronic properties of nanometric materials. Currently, this technique is generating large amounts of spectra per experiment, producing a huge quantity of data to analyse. Several strategies can be applied in order to classify these data to map physical properties at the nanoscale. In the present study, the Support Vector Machine (SVM) algorithm is applied to EELS, and its effectiveness identifying EEL spectra is assessed. Our results evidence the capacity of SVM to determine the oxidation state of iron and manganese in iron and manganese oxides, based on the ELNES of the white lines of the transition metal. The SVM algorithm is first trained with given datasets and then the resulting models are tested through noisy test data sets. We demonstrate that SVM exhibits a very good performance classifying these EEL spectra, despite the usual level of noise and instrumental energy shifts.

Fast-ADT: A fast and automated electron diffraction tomography setup for structure determination and refinement.

Electron crystallography has focused in the last few years on the analyses of microcrystals, mainly organic compounds, triggered by recent publications on acquisition methods based on direct detection cameras and continuous stage tilting. However, the main capability of a transmission electron microscope is the access to features at the nanometre scale. In this context, a new acquisition method, called fast and automated diffraction tomography (Fast-ADT), has been developed in form of a general application in order to get the most of the diffraction space from a TEM. It consists of two subsequent tilt scans of the goniometric stage; one to obtain a crystal tracking file and a second one to acquire an electron diffraction tomography. This setup has been implemented on both TEM and STEM modes of the microscope, thus it can be installed on any TEM regardless of the availability of a scanning unit. BaSO4 crystals have been measured to demonstrate the validity of the technique for structure determination and refinement. A recently solved layered silicate, RUB-5, has been used to prove the method advantages for fine identification of disorder details. Last, a new polymorph of a DRED1 organic molecule has been solved ab initio and refined by X-ray powder diffraction to show the full application of the presented method.

Quasi-parallel precession diffraction: Alignment method for scanning transmission electron microscopes.

A general method to set illuminating conditions for selectable beam convergence and probe size is presented in this work for Transmission Electron Microscopes (TEM) fitted with µs/pixel fast beam scanning control, (S)TEM, and an annular dark field detector. The case of interest of beam convergence and probe size, which enables diffraction pattern indexation, is then used as a starting point in this work to add 100 Hz precession to the beam while imaging the specimen at a fast rate and keeping the projector system in diffraction mode. The described systematic alignment method for the adjustment of beam precession on the specimen plane while scanning at fast rates is mainly based on the sharpness of the precessed STEM image. The complete alignment method for parallel condition and precession, Quasi-Parallel PED-STEM, is presented in block diagram scheme, as it has been tested on a variety of instruments. The immediate application of this methodology is that it renders the TEM column ready for the acquisition of Precessed Electron Diffraction Tomographies (EDT) as well as for the acquisition of slow Precessed Scanning Nanometer Electron Diffraction (SNED). Examples of the quality of the Precessed Electron Diffraction (PED) patterns and PED-STEM alignment images are presented with corresponding probe sizes and convergence angles.

Memristive behaviour of Si-Al oxynitride thin films: the role of oxygen and nitrogen vacancies in the electroforming process.

The resistive switching properties of silicon-aluminium oxynitride (SiAlON) based devices have been studied. Electrical transport mechanisms in both resistance states were determined, exhibiting an ohmic behaviour at low resistance and a defect-related Poole-Frenkel mechanism at high resistance. Nevertheless, some features of the Al top-electrode are generated during the initial electroforming, suggesting some material modifications. An in-depth microscopic study at the nanoscale has been performed after the electroforming process, by acquiring scanning electron microscopy and transmission electron microscopy images. The direct observation of the devices confirmed features on the top electrode with bubble-like appearance, as well as some precipitates within the SiAlON. Chemical analysis by electron energy loss spectroscopy has demonstrated that there is an out-diffusion of oxygen and nitrogen ions from the SiAlON layer towards the electrode, thus forming silicon-rich paths within the dielectric layer and indicating vacancy change to be the main mechanism in the resistive switching.

The effect of Sb-surfactant on GaInP CuPtB type ordering: assessment through dark field TEM and aberration corrected HAADF imaging.

We report on the effect of Sb on the microstructure of GaInP layers grown by metal organic vapor phase epitaxy (MOVPE). These layers exhibit a CuPtB single variant ordering due to the intentional misorientation of the substrate (Ge(001) substrates with 6° misorientation towards the nearest [111] axis). The use of Sb as a surfactant during the GaInP growth does not modify the type of ordering, but it is found that the order parameter (η) decreases with increasing Sb flux. Dark field microscopy reveals a variation of the angle of the antiphase boundaries (APBs) with Sb amount. The microstructure is assessed through high angle annular dark field (HAADF) experiments and image simulation revealing Z-contrast loss in APBs due to the superposition of ordered domains.

Evidence of a minority monoclinic LaNiO2.5 phase in lanthanum nickelate thin films.

LaNiO3 (LNO) thin films of 14 nm and 35 nm thicknesses grown epitaxially on LaAlO3 (LAO) and (LaAlO3)0.3(Sr2TaAlO6)0.7 (LSAT) substrates are studied using High Resolution Transmission Electron Microscopy (HRTEM) and High Angle Annular Dark Field (HAADF) imaging. The strain state of the films is studied using Geometric Phase Analysis (GPA). Results show the successful in-plane adaptation of the films to the substrates, both in the compressive (LAO) and tensile (LSAT) cases. Through the systematic analysis of HRTEM superstructure contrast modulation along different crystal orientations, localized regions of the monoclinic LaNiO2.5 phase are detected in the 35 nm films.

Electron energy-loss spectroscopic tomography of FexCo(3-x)O4 impregnated Co3O4 mesoporous particles: unraveling the chemical information in three dimensions.

Electron energy-loss spectroscopy-spectrum image (EELS-SI) tomography is a powerful tool to investigate the three dimensional chemical configuration in nanostructures. Here, we demonstrate, for the first time, the possibility to characterize the spatial distribution of Fe and Co cations in a complex FexCo(3-x)O4/Co3O4 ordered mesoporous system. This hybrid material is relevant because of the ferrimagnetic/antiferromagnetic coupling and high surface area. We unambiguously prove that the EELS-SI tomography shows a sufficiently high resolution to simultaneously unravel the pore structure and the chemical signal.

Electron energy loss spectroscopy on semiconductor heterostructures for optoelectronics and photonics applications.

In this work, we present characterization methods for the analysis of nanometer-sized devices, based on silicon and III-V nitride semiconductor materials. These methods are devised in order to take advantage of the aberration corrected scanning transmission electron microscope, equipped with a monochromator. This set-up ensures the necessary high spatial and energy resolution for the characterization of the smallest structures. As with these experiments, we aim to obtain chemical and structural information, we use electron energy loss spectroscopy (EELS). The low-loss region of EELS is exploited, which features fundamental electronic properties of semiconductor materials and facilitates a high data throughput. We show how the detailed analysis of these spectra, using theoretical models and computational tools, can enhance the analytical power of EELS. In this sense, initially, results from the model-based fit of the plasmon peak are presented. Moreover, the application of multivariate analysis algorithms to low-loss EELS is explored. Finally, some physical limitations of the technique, such as spatial delocalization, are mentioned.

Robust antiferromagnetic coupling in hard-soft bi-magnetic core/shell nanoparticles.

The growing miniaturization demand of magnetic devices is fuelling the recent interest in bi-magnetic nanoparticles as ultimate small components. One of the main goals has been to reproduce practical magnetic properties observed so far in layered systems. In this context, although useful effects such as exchange bias or spring magnets have been demonstrated in core/shell nanoparticles, other interesting key properties for devices remain elusive. Here we show a robust antiferromagnetic (AFM) coupling in core/shell nanoparticles which, in turn, leads to the foremost elucidation of positive exchange bias in bi-magnetic hard-soft systems and the remarkable regulation of the resonance field and amplitude. The AFM coupling in iron oxide-manganese oxide based, soft/hard and hard/soft, core/shell nanoparticles is demonstrated by magnetometry, ferromagnetic resonance and X-ray magnetic circular dichroism. Monte Carlo simulations prove the consistency of the AFM coupling. This unique coupling could give rise to more advanced applications of bi-magnetic core/shell nanoparticles.

Ti diffusion in (001) SrTiO3-CoFe2O4 epitaxial heterostructures: blocking role of a MgAl2O4 buffer.

Titanium diffusion from (001) SrTiO3 (STO) substrates into CoFe2O4 (CFO) films grown using pulsed laser deposition is reported. To elucidate the reasons for Ti interdiffusion, a comparative study of CFO films grown on MgAl2O4 (MAO) and STO substrates, buffered by thin STO and MAO layers, has been made. It is shown that whereas bottom STO layers always result in Ti migration, a thin MAO layer, only 8 nm thick, is effective in blocking it. We argue that this success relies on the lower mobility of Ti ions in the MAO lattice compared to that of CFO. This result should contribute to the development of high quality epitaxial heterostructures of dissimilar complex oxides.

The direct magnetoelectric effect in ferroelectric-ferromagnetic epitaxial heterostructures.

Ferroelectric (FE) and ferromagnetic (FM) materials engineered in horizontal heterostructures allow interface-mediated magnetoelectric coupling. The so-called converse magnetoelectric effect (CME) has been already demonstrated by electric-field poling of the ferroelectric layers and subsequent modification of the magnetic state of adjacent ferromagnetic layers by strain effects and/or free-carrier density tuning. Here we focus on the direct magnetoelectric effect (DME) where the dielectric state of a ferroelectric thin film is modified by a magnetic field. Ferroelectric BaTiO3 (BTO) and ferromagnetic CoFe2O4 (CFO) oxide thin films have been used to create epitaxial FE/FM and FM/FE heterostructures on SrTiO3(001) substrates buffered with metallic SrRuO3. It will be shown that large ferroelectric polarization and DME can be obtained by appropriate selection of the stacking order of the FE and FM films and their relative thicknesses. The dielectric permittivity, at the structural transitions of BTO, is strongly modified (up to 36%) when measurements are performed under a magnetic field. Due to the insulating nature of the ferromagnetic layer and the concomitant absence of the electric-field effect, the observed DME effect solely results from the magnetostrictive response of CFO elastically coupled to the BTO layer. These findings show that appropriate architecture and materials selection allow overcoming substrate-induced clamping in multiferroic multi-layered films.

Orientation and phase mapping in the transmission electron microscope using precession-assisted diffraction spot recognition: state-of-the-art results.

A recently developed technique based on the transmission electron microscope, which makes use of electron beam precession together with spot diffraction pattern recognition now offers the possibility to acquire reliable orientation/phase maps with a spatial resolution down to 2 nm on a field emission gun transmission electron microscope. The technique may be described as precession-assisted crystal orientation mapping in the transmission electron microscope, precession-assisted crystal orientation mapping technique-transmission electron microscope, also known by its product name, ASTAR, and consists in scanning the precessed electron beam in nanoprobe mode over the specimen area, thus producing a collection of precession electron diffraction spot patterns, to be thereafter indexed automatically through template matching. We present a review on several application examples relative to the characterization of microstructure/microtexture of nanocrystalline metals, ceramics, nanoparticles, minerals and organics. The strengths and limitations of the technique are also discussed using several application examples.

Optoelectronic properties of InAlN/GaN distributed bragg reflector heterostructure examined by valence electron energy loss spectroscopy.

High-resolution monochromated electron energy loss spectroscopy (EELS) at subnanometric spatial resolution and <200 meV energy resolution has been used to assess the valence band properties of a distributed Bragg reflector multilayer heterostructure composed of InAlN lattice matched to GaN. This work thoroughly presents the collection of methods and computational tools put together for this task. Among these are zero-loss-peak subtraction and nonlinear fitting tools, and theoretical modeling of the electron scattering distribution. EELS analysis allows retrieval of a great amount of information: indium concentration in the InAlN layers is monitored through the local plasmon energy position and calculated using a bowing parameter version of Vegard Law. Also a dielectric characterization of the InAlN and GaN layers has been performed through Kramers-Kronig analysis of the Valence-EELS data, allowing band gap energy to be measured and an insight on the polytypism of the GaN layers.

Strongly exchange coupled inverse ferrimagnetic soft/hard, Mn(x)Fe(3-x)O4/Fe(x)Mn(3-x)O4, core/shell heterostructured nanoparticles.

Inverted soft/hard, in contrast to conventional hard/soft, bi-magnetic core/shell nanoparticles of Mn(x)Fe(3-x)O(4)/Fe(x)Mn(3-x)O(4) with two different core sizes (7.5 and 11.5 nm) and fixed shell thickness (∼0.6 nm) have been synthesized. The structural characterization suggests that the particles have an interface with a graded composition. The magnetic characterization confirms the inverted soft/hard structure and evidences a strong exchange coupling between the core and the shell. Moreover, larger soft core sizes exhibit smaller coercivities and loop shifts, but larger blocking temperatures, as expected from spring-magnet or graded anisotropy structures. The results indicate that, similar to thin film systems, the magnetic properties of soft/hard core/shell nanoparticles can be fine tuned to match specific applications.

[Description of the psychiatric unit in prisons in the autonomous community of Valencia]. / Descripción de la consulta psiquiátrica en centros penitenciarios de la Comunidad Valenciana.

INTRODUCTION: Little work has been done on the contents of psychiatric consultancies in prisons. AIMS: To explore the sociodemographic, clinical and treatment profile of the patients who were assessed in the psychiatric consultancy of three prisons. METHODS: This is a prospective, longitudinal, descriptive and multicenter-based epidemiological study of patients who were assessed in the psychiatric consultacy of three prisons in the Autonomous Community of Valencia from 2009 to 2011. Sociodemographic, clinical and prison data was obtained from each patient. Their frequency was compared with Pearson's Ji² and averages with the ANOVA test or with The Kruskall-Wallis method. The probability of keeping the patients in schedule was calculated with Kaplan-Meier's curves and differences with the Mantel-Haenzsel method (Logrank) were established. A logistic regression model was designed to determine the data linked to frequent users. RESULTS: 786 patients were assessed in 2,006 visits (2.5 visits/patient). 90% were male, 88.2% Spanish and their average age was 36 years. 29.9% suffered from an infectious chronic pathology. 69.5% used some kinds of substance. 59.2% suffered from personality disorder and 11.6% from the spectrum of schizophrenia. The most frequent medical profiles were: 49.1% with anxiety disorder, 20.8% depressive disorder and 11.7% psychotic disorder. These psychotic disorders meant a greater probability of 1.5 times for maintaining in schedule. The most commonly prescribed medications were quetiapine, mirtazapine, pregabalin and diazepam. CONCLUSION: There is a high prevalence of mental disorders in prisons. It is necessary to improve the available resources to deal with these pathologies in the most effective way.

Distinguishing the core from the shell in MnO(x)/MnO(y) and FeO(x)/MnO(x) core/shell nanoparticles through quantitative electron energy loss spectroscopy (EELS) analysis.

The structural and chemical characterization of inverted bi-magnetic MnO(x)(antiferromagnetic)/MnO(y)(ferrimagnetic) and FeO(x)(soft-ferrimagnetic)/MnO(x)(hard-ferrimagnetic) core/shell nanoparticles has been carried out by means of scanning transmission electron microscopy with electron energy loss spectroscopy analysis, (S)TEM-EELS. Quantitative EELS was applied to assess the local composition of the nanoparticles by evaluating the local Mn oxidation state based on the Mn L3/L2 peak intensity ratio and the Mn L3 peak onset. The analysis allows to unambiguously distinguish the core from the shell and to determine the nature of the involved manganese oxides in both cases. The results evidence that the structure of the nanoparticles is, in fact, more complex than the one designed by the synthesis parameters.

A new approach for 3D reconstruction from bright field TEM imaging: beam precession assisted electron tomography.

The successful combination of electron beam precession and bright field electron tomography for 3D reconstruction is reported. Beam precession is demonstrated to be a powerful technique to reduce the contrast artifacts due to diffraction and curvature in thin foils. Taking advantage of these benefits, Precession assisted electron tomography has been applied to reconstruct the morphology of Sn precipitates embedded in an Al matrix, from a tilt series acquired in a range from +49° to -61° at intervals of 2° and with a precession angle of 0.6° in bright field mode. The combination of electron tomography and beam precession in conventional TEM mode is proposed as an alternative procedure to obtain 3D reconstructions of nano-objects without a scanning system or a high angle annular dark field detector.

Blue-green to near-IR switching electroluminescence from Si-rich silicon oxide/nitride bilayer structures.

Blue-green to near-IR switching electroluminescence (EL) has been achieved in a metal-oxide-semiconductor light emitting device, where the dielectric has been replaced by a Si-rich silicon oxide/nitride bilayer structure. To form Si nanostructures, the layers were implanted with Si ions at high energy, resulting in a Si excess of 19%, and subsequently annealed at 1000 °C. Transmission electron microscopy and EL studies allowed ascribing the blue-green emission to the Si nitride related defects and the near-IR band with the emission of the Si-nanoclusters embedded into the SiO(2) layer. Charge transport analysis is reported and allows for identifying the origin of this two-wavelength switching effect.

Plasma-enhanced low temperature growth of silicon nanowires and hierarchical structures by using tin and indium catalysts.

Plasma-enhanced low temperature growth (<300 degrees C) of silicon nanowires (SiNWs) and hierarchical structures via a vapor-liquid-solid (VLS) mechanism are investigated. The SiNWs were grown using tin and indium as catalysts prepared by in situ H(2) plasma reduction of SnO(2) and ITO substrates, respectively. Effective growth of SiNWs at temperatures as low as 240 degrees C have been achieved, while tin is found to be more ideal than indium in achieving a better size and density control of the SiNWs. Ultra-thin (4-8 nm) silica nanowires, sprouting from the dendritic nucleation patterns on the catalyst's surface, were also observed to form during the cooling process. A kinetic growth model has been proposed to account for their formation mechanism. This hierarchical structure combines the advantages of the size and position controllability from the catalyst-on-top VLS-SiNWs and the ultra-thin size from the catalyst-on-bottom VLS-ScNWs.