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Nanoparticle-mediated thermal treatments have demonstrated high efficacy and versatility as a local anticancer strategy beyond traditional global hyperthermia. Nanoparticles act as heating generators that can trigger therapeutic responses at both the cell and tissue level. In some cases, treatment happens in the absence of a global temperature rise, damaging the tumor cells even more selectively than other nanotherapeutic strategies. The precise determination of the local temperature in the vicinity of such nanoheaters then stands at the heart of thermal approaches to better adjust the therapeutic thermal onset and reduce potential toxicity-related aspects. Herein, we describe an experimental procedure by X-ray absorption spectroscopy, which directly and accurately infers the local temperature of gold-based nanoparticles, single and hybrid nanocrystals, upon laser photoexcitation, revealing significant nanothermal gradients. Such nanothermometric methodology based on the temperature-dependency of atomic parameters of nanoparticles can be extended to any nanosystem upon remote hyperthermal conditions.

The aim of this work is to clarify how in-plane magnetic anisotropy and magnetoelasticity depend on the thickness of Ga-rich FeGa layers. Samples with an Fe72Ga28 composition were grown by sputtering in the ballistic regime in oblique incidence. Although for these growth conditions uniaxial magnetic anisotropy could be expected, in-plane anisotropy is only present when the sample thickness is above 100 nm. By means of differential X-ray absorption spectroscopy, we have determined the influence of both Ga pairs and tetragonal cell distortion on the evolution of the magnetic anisotropy with the increase of FeGa thickness. On the other hand, we have used the cantilever beam technique with capacitive detection to also determine the evolution of the magnetoelastic parameters with the thickness increase. In this case, experimental results can be understood considering the grain distribution. Therefore, the different physical origins for anisotropy and magnetoelasticity open up the possibility to independently tune these two characteristics in Ga-rich FeGa films., This work has been financially supported through the projects MAT2015-66888-C3-3-R and MAT2015-66726-R (MINECO/FEDER) of the Spanish Ministry of Economy and Competitiveness, RTI2018-097895-B-C43 of the Spanish Ministry of Science, Innovation, and Universities, and Gobierno de Aragón (Grant E10-17D) and Fondo Social Europeo. A.M.-N. is thankful for the contract from Universidad Complutense and Comunidad de Madrid “Atracción de Talento” program 2018-T1/IND-10360, and A.B. thanks MINECO for the Ph.D. grant BES-2016-076482.

[EN] The purpose of this work is to fabricate self-assembled microstructures by the sol–gel method and study the morphological, structural and compositional dependence of 3-Fe2O3 nanoparticles embedded in silica when glycerol (GLY) and cetyl-trimethylammonium bromide (CTAB) are added as steric agents simultaneously. The combined action of a polyalcohol and a surfactant significantly modifies the morphology of the sample giving rise to a different microstructure in each of the studied cases (1, 3 and 7 days of magnetic stirring time). This is due to the fact that the addition of these two compounds leads to a considerable increase in gelation time as GLY can interact with the alkoxide group on the surface of the iron oxide precursor micelle and/or be incorporated into the hydrophilic chains of CTAB. This last effect causes the iron oxide precursor micelles to be interconnected forming aggregates whose size and structure depend on the magnetic stirring time of the sol–gel synthetic route. In this paper, crystalline structure, composition, purity and morphology of the sol–gel coatings densified at 960 ºC are examined. Emphasis is placed on the nominal percentage of the different iron oxides found in the samples and on the morphological and structural differences. This work implies the possibility of patterning 3-Fe2O3 nanoparticles in coatings and controlling their purity by an easy one-pot sol–gel method., Spanish Ministry of Industry, Economy and Competitiveness for financing the project MAT2015-65445-C2-1-R, MAT2017-86450-C4-1-R, MAT2015-67557-C2-1-P, by the Comunidad de Madrid S2013/MIT-2850 NANOFRONTMAG and H2020 AMPHIBIAN Project ID: 720853. The authors are also grateful to the BM25-SpLine staff for their valuable technical support beyond their duties and for the financial support from the Spanish Ministry of Science, Innovation and Universities (MICIU) and The Spanish National Research Council (CSIC) under Grant No. PIE 2010- 6OE-013, The ESRF – The European Synchrotron, MICIU and CSIC are acknowledged for provision of synchrotron radiation facilities. A. S. acknowledges the Financial support from the Comunidad de Madrid for an “Atracción de Talento Investigador” contract (No. 2017-t2/IND5395).

We present an extended X-ray absorption fine structure study at the Mo K-edge of A2(Mo1yMny)2O7 (A Gd, Ho; y 0.05 and 0.10) pyrochlores, as a function of temperature and composition, coupled to diffractometric and magnetic characterizations. Extending the study reported in our previous paper on the pristine A2Mo2O7 compounds to these Mo/Mn partially substituted samples, where we hypothesize a competition between double-exchange and superexchange couplings, we aim to check which structure parameters are related to the nature of the nearest-neighbor magnetic interactions, looking for the presence and evolution of order and structure anomalies. Two Ho samples Ho2(Mo1yMny)2O7 (y 0.05 and 0.10) keep the spin-glass nature of the parent compositions with a strong distortion of the MoO(1)6 octahedron and of the MoHo and MoMo second shell. On the other hand, two Gd2(Mo1yMny)2O7 samples, ferromagnetic at low temperature in the undoped case, show the appearance on a local scale of a spin-glass transition mirrored by a quite high structure disorder and by a distortion coherent with a lattice frustration after Mn-doping. Therefore, the Gd and Ho Mn-doped samples display a similar frustrated behavior, differently from the corresponding undoped ones. We gratefully acknowledge the Spanish CRG at the ESRF for providing beamtime under experiment HC-3343. MS thanks Prof. Monica Dapiaggi for useful discussions. GL thanks Prof. Fabio M. Canepa for illuminating discussions. F.R.-M. gratefully acknowledge the support of the AEI (Spanish Government) Project (No. MAT2017-86450-C4-1-R). F.R.-M. is indebted to MINECO for the Ramon y Cajal contract (Ref: RyC-2015-18626), which is co-financed by the European Social Fund.

Little–Parks effect names the oscillations in the superconducting critical temperature as a function of the magnetic field. This effect is related to the geometry of the sample. In this work, we show that this effect can be enhanced and manipulated by the inclusion of magnetic nanostructures with perpendicular magnetization. These magnetic nanodots generate stray fields with enough strength to produce superconducting vortex–antivortex pairs. So that, the L–P effect deviation from the usual geometrical constrictions is due to the interplay between local magnetic stray fields and superconducting vortices. Moreover, we compare our results with a low-stray field sample (i.e. with the dots in magnetic vortex state) showing how the enhancement of the L–P effect can be explained by an increment of the effective size of the nanodots., With funding from the Spanish government through the "María de Maeztu Unit of Excellence" accreditation (MDM-2017-0737)

Progress of thermal tumor therapies and their translation into clinical practice are limited by insufficient nanoparticle concentration to release therapeutic heating at the tumor site after systemic administration. Herein, the use of Janus magneto-plasmonic nanoparticles, made of gold nanostars and iron oxide nanospheres, as efficient therapeutic nanoheaters whose on-site delivery can be improved by magnetic targeting, is proposed. Single and combined magneto- and photo-thermal heating properties of Janus nanoparticles render them as compelling heating elements, depending on the nanoparticle dose, magnetic lobe size, and milieu conditions. In cancer cells, a much more effective effect is observed for photothermia compared to magnetic hyperthermia, while combination of the two modalities into a magneto-photothermal treatment results in a synergistic cytotoxic effect in vitro. The high potential of the Janus nanoparticles for magnetic guiding confirms them to be excellent nanostructures for in vivo magnetically enhanced photothermal therapy, leading to efficient tumor growth inhibition.

The determination of the structure of Ca(II)-acetate in aqueous solution has been addressed by combining Raman and X-ray absorption fine structure spectroscopies. The pH-dependent speciation of the acetate/Ca(II) system has been studied observing modifications in specific Raman bands of the carboxyl group. The current results evidence the Ca(II)-acetate above acetate pKa forms a bidentate complex and presents a coordination 6, in which the Ca-O shell radius decrease of about 0.1 A with respect the hydrated Ca 2+ with coordination 8. The experimental results show the OCO angle of the carboxyl in the complex is close to 124°, being the OCaO angle about 60°.

In this work we present an exhaustive investigation about the possibility of using the electrodeposition technique to grow Ga-Fe-O thin films. The morphological and structural characterization has been performed by means of scanning electron microscopy, X-ray diffractometry and X-ray absorption near edge structure measurements. These results have been complemented with chronoamperometric measurements recorded during growth. We have explored different electrolytes, growth potentials, and pH being observed that it is possible to tune the Fe/Ga ratio by means of the potential whereas the surface morphology is closely related to the Na3-citrate content in the electrolyte. The surface roughness is reduced as the Fe content in the layer is increased upon the raise of citrate in the electrolyte composition. X-ray diffractometry indicates that Ga can become partially oxidized, whereas Fe seems to keep its metallic state in its vast majority since we have not obtained clear evidences of oxidation. Thus, this investigation highlights the inherent difficulties to synthetize Ga-Fe-O compounds by means of the electrodeposition technique.

Porous-Silicon/Zinc Oxide (PS-ZnO) nanocomposites can be processed by a combination of electrochemical etching of PS and sol-gel infiltration of ZnO, which leads to complex interfaces of ZnO permeated in the PS matrix. In this work, an approach consisting on the determination of transport mechanisms and identification of electroluminescence emission bands from the heterojunction, has been followed to derive the energy band diagram. Charge transport at room temperature has been determined in ITO/PS-ZnO/p+-Si/Al structures through current-voltage characteristics, showing that direct and Fowler-Nordheim (FN) tunneling are the main conduction mechanisms at low and high bias voltages, respectively. White electroluminescence composed of three main bands (~490, ~550 and ~620 nm) is observed at forward bias. Emission starts at a threshold voltage of 3.9±0.2 V, in coincidence with the change in conduction mechanism from direct to FN tunneling. A band diagram of the device is derived from the emission and transport properties, which is coherent with previous electronic and microstructural properties of the starting n-ZnO and p+-Si.

Recent studies have revealed that electrochemistry at the nanometer scale is profoundly different from its conventional framework. We reported that the combination of a hydrophobic nanoporous electrode and low-charge-density metal ions resulted in a drastic acceleration in the electrodeposition reaction. In the present study, we analyzed Zn embedded in nanoporous silicon by X-ray absorption fine structure spectroscopy. As a precursor to Zn electrodeposition, Zn(II) chelate was used under different pH conditions. The spectroscopy results clearly suggest that the accumulation of Zn(II) chelate occurred at pH conditions where the Zn(II) chelate had zero charge. The accumulation resulted in the promotion of Zn electrodeposition within confined nanopores. Based on this spectroscopic investigation, we propose a model for the accelerated electrodeposition of Zn in confined nanopores.

The perovskite series Sr2CoNb1-xTixO6-δ (0≤x≤1) is investigated in the full compositional range to assess its potential as cathode material for solid state fuel cell (SOFC). The variation of transport properties and thus, the area specific resistances (ASR) are explained by a detailed investigation of the defect chemistry. Increasing titanium content from x=0 to x=1 produces both oxidation of Co3+ to Co4+ (from 0% up to 40%) and oxygen vacancies (from 6.0 to 5.7 oxygen atom/formula unit) though each charge compensation mechanism predominates in different compositional ranges. Neutron diffraction reveals that samples with high Ti-contents lose a significant amount of oxygen on heating above 600K. Oxygen is partially recovered on cooling since the oxygen release and uptake show noticeably different kinetics. The complex defect chemistry of these compounds, together with the compositional changes upon heating-cooling cycles and atmospheres produce, a complicated behavior of electrical conductivity. Cathodes containing Sr2CoTiO6-δ display low ASR values, 0,13 Ωcm2 at 973 K, comparable to those of the best compounds reported so far, being a very promising cathode material for SOFC.

Materials with the formula Sr2CoNb1−xTixO6−δ (x=1.00, 0.70; δ=number of oxygen vacancies) present a cubic perovskite-like structure. They are easily and reversibly reduced in N2 or Ar and re-oxidized in air upon heating. Oxidation by water (wet N2), involving splitting of water at a temperature as low as 700 °C, produces hydrogen. Both compounds displayed outstanding H2 production in the first thermochemical cycle, the Sr2CoNb0.30Ti0.70O6−δ material retaining its outstanding performance upon cycling, whereas the hydrogen yield of the x=1 oxide showed a continuous decay. The retention of the materials’ ability to promote water splitting correlated with their structural, chemical, and redox reversibility upon cycling. On reduction/oxidation, Co ions reversibly changed their oxidation state to compensate the release/recovery of oxygen in both compounds. However, in Sr2CoTiO6−δ, two phases with different oxygen contents segregated, whereas in Sr2CoNb0.30Ti0.70O6−δ this effect was not evident. Therefore, this latter material displayed a hydrogen production as high as 410 μmolurn:x-wiley:18645631:media:cssc201901484:cssc201901484-math-0001 g−1perovskite after eight thermochemical cycles at 700 °C, which is among the highest ever reported, making this perovskite a promising candidate for thermosolar water splitting in real devices. We thank Agencia Estatal de Investigación (AEI)/Fondo Europeo de Desarrollo Regional (FEDER/UE)for funding the project MAT2016-78632-C4-1-R. We acknowledge CSIC, ILL, and ESRF for financial support and facilitated access to the BM25-SpLine line at ESRF and D2B diffractometer at ILL. The authors also thank "Comunidad de Madrid" and the European Structural Funds for their financial support to the ALCCONES (S2013/MAE-2985) and MATERYENER3-CM (S2013/MIT-2753) projects.

We have investigated the influence of the growth power on the structural properties of Fe100-xGax (x ca. 29) films sputtered in the ballistic regime in the oblique incidence. By means of different structural characterizations, mainly X-ray diffraction and X-ray absorption spectroscopy, we have reached a deeper understanding about the influence of the local and medium range order on the magnetic behavior of Ga-rich FeGa thin films. On the one hand, the increase of the growth power reduces the crystallite size (medium order) that promotes the decrease of the coercive field of the layers. On the other hand, the growth power also determines the local order as it controls the formation of the A2, B2, and D03 structural phases. The increase of the uniaxial in-plane magnetic anisotropy with growth power has been correlated with the enhancement of both Ga pairs and a tetragonal distortion. The results presented in this work give more evidence about the magnetic anisotropy sources in Ga-rich FeGa alloys, and therefore, it helps to understand how to achieve a better control of the magnetic properties in this family of alloys. This work has been financially supported through project MAT2015-66888-C3-3-R (MINECO/FEDER) and RTI2018-097895-B-C43 of the Spanish Ministry of Economy and Competitiveness and through PR26/16-3B-2 of Santander and Universidad Complutense de Madrid. We thank "CAI Difracción de rayos-X" of UCM for the X-ray diffractometry measurements and the "Instituto de Sistemas Optoelectrónicos y Microtecnología" (ISOM) for using its facilities. We also want to thank BM25-Spline, the Spanish CRG at ESRF for providing beamtime.

We have designed, fabricated and tested a robust superconducting ratchet device based on topologically frustrated spin ice nanomagnets. The device is made of a magnetic Co honeycomb array embedded in a superconducting Nb film. This device is based on three simple mechanisms: (i) the topology of the Co honeycomb array frustrates in-plane magnetic configurations in the array yielding a distribution of magnetic charges which can be ordered or disordered with in-plane magnetic fields, following spin ice rules; (ii) the local vertex magnetization, which consists of a magnetic half vortex with two charged magnetic Néel walls; (iii) the interaction between superconducting vortices and the asymmetric potentials provided by the Néel walls. The combination of these elements leads to a superconducting ratchet effect. Thus, superconducting vortices driven by alternating forces and moving on magnetic half vortices generate a unidirectional net vortex flow. This ratchet effect is independent of the distribution of magnetic charges in the array., We thank support from Spanish MINECO grants FIS2016-76058 (AEI/FEDER, UE), Spanish CM grant S2013/MIT2850. IMDEA Nanociencia acknowledges support from the ‘Severo Ochoa’ Programme for Centres of Excellence in R&D (MINECO, Grant SEV-2016-0686). DG acknowledges RYC-2012-09864, S2013/MIT-3007 and ESP2015-65597-C4-3-R for financial support and AG acknowledges financial support from Spanish MINECO Grant ESP2015-65597-C4-1-R.

Porous silicon (PSi) is a versatile matrix with tailorable surface reactivity, which allows the processing of a range of multifunctional films and particles. The biomedical applications of PSi often require a surface capping with organic functionalities. This work shows that visible light can be used to catalyze the assembly of organosilanes on the PSi, as demonstrated with two organosilanes: aminopropyl-triethoxy-silane and perfluorodecyl-triethoxy-silane. We studied the process related to PSi films (PSiFs), which were characterized by X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectroscopy (ToF-SIMS) and field emission scanning electron microscopy (FESEM) before and after a plasma patterning process. The analyses confirmed the surface oxidation and the anchorage of the organosilane backbone. We further highlighted the surface analytical potential of 13 C, 19 F and 29 Si solid-state NMR (SS-NMR) as compared to Fourier transformed infrared spectroscopy (FTIR) in the characterization of functionalized PSi particles (PSiPs). The reduced invasiveness of the organosilanization regarding the PSiPs morphology was confirmed using transmission electron microscopy (TEM) and FESEM. Relevantly, the results obtained on PSiPs complemented those obtained on PSiFs. SS-NMR suggests a number of siloxane bonds between the organosilane and the PSiPs, which does not reach levels of maximum heterogeneous condensation, while ToF-SIMS suggested a certain degree of organosilane polymerization. Additionally, differences among the carbons in the organic (non-hydrolyzable) functionalizing groups are identified, especially in the case of the perfluorodecyl group. The spectroscopic characterization was used to propose a mechanism for the visible light activation of the organosilane assembly, which is based on the initial photoactivated oxidation of the PSi matrix, We acknowledge MSC funding provided by the European Commission through FP7 grant THINFACE (ITN GA 607232) and by Ministerio de Economía y Competitividad through grant NANOPROST (RTC-2016-4776-1)

The symmetry of the room-temperature (RT) structure of title compounds LaSrCoTiO changes with x, from P2/n (0 ≤ x ≤ 0.2) to Pnma (0.3 ≤ x ≤ 0.5) and to R3;c (0.6 ≤ x ≤ 1). For x = 1 the three pseudocubic cell parameters become very close suggesting a transition to a cubic structure for higher Sr contents. Similar phase transitions were expected to occur on heating, paralleling the effect of internal pressure induced by substitution of La by Sr. However, only some of these aforementioned transitions have been thermally induced. The symmetry-adapted modes formalism is used in the structural refinements and fitting of neutron diffraction data recorded from RT to 1273 K. Thus, for x = 1, the out-of-phase tilting of the BO octahedra vanishes progressively on heating, and a cubic structure with Pm3;m symmetry is found at 1073 K. For lower Sr contents this transition is predicted to occur far above the temperature limit of common experimental setups. The analysis of the evolution of the perovskite tolerance factor, t-factor, with both Sr content and temperature indicates that temperature has a limited ability to release structural stress and thus to enable transitions to more symmetric phases. This is particularly true when compared to the effect of internal pressure induced by substitution of La by Sr. The existence of phase transitions in materials for solid oxide fuel cells that are usually exposed to heating-cooling cycles may have a detrimental effect. This work suggests strategies to stabilize the high-symmetry high-temperature phase of perovskite oxides through internal-pressure chemically induced.

This study examined the formation of amorphous platinum (Pt) clusters in nanopores of porous silicon at an initial stage of pore filling. The time dependency of the chemical state and local structure of Pt in the nanoporous silicon were characterized by X-ray absorption fine structure spectroscopy (XAFS). Initially, the Pt deposits showed non-negligible amounts of PtO2, formed by surface oxidation from the atmosphere, suggesting that the particle size was quite small. Deep analysis of extended XAFS (EXAFS) strongly suggested that Pt at the early stage of deposition was amorphous. The mechanism of amorphous Pt formation is discussed based on the confinement effect for Pt complex anions in nanopores. Keywords: Nanoporous, Nanoparticles, Deposition, Platinum, XAFS

The design of phosphorescent materials, highly crystalline, with a submicron particle size is a challenge for industrial applications. Based on molten salt assisted process, the effects of salt/SrAl0 molar ratio on the phase evolution are studied. A significant influence of salt/SrAl0 molar ratio on synthesis and final properties has been observed. Moreover, the phase evolution has been explored as a function of treatment temperature. To remove the salt from the powder, the wash step is carried out with glycerin avoiding hydrolysis reaction due to the sensitivity of strontium aluminates to water. The salt/SrAl0 molar ratio of 3:1 and the thermal treatment at 1000 0C are preferred, avoiding extra wash step. Here, we have obtained highly crystalline SrAl0:Eu, Dy powder with a particle size =0.5 ≤m after a 2 h treatment at 1000 0C employing the molten salt approach. As a result, we believe that the general strategy described in this study opens the possibility of obtaining technologically relevant phosphors with enhanced properties, expanding their application range to radiation detection., The authors express their thanks to the MINECO (Spain) project MAT2013-480089-C04-1-P for their financial support. Dr. F. Rubio-Marcos is also indebted to MINECO and European Social Fund for a “Juan de la Cierva” contract (ref: JCI-2012-14521).

We present a novel and easy synthetic path to prepare ϵ-FeO (∼90%) with a small portion of α-FeO nanoparticles embedded in an amorphous silica matrix. An exhaustive structural study reveals the higher relative concentration of the ϵ-phase, with an average particle size of 17 nm. Confocal Raman microscopy and X-ray absorption spectroscopy are presented as novel techniques to characterize the ϵ-polymorph. The magnetic properties have been studied in a wide range of temperatures (5-1000 K), detecting blocking effects (∼135 K), collapse effects (50-125 K), Morin (∼268 K) and Néel (∼505 K) transitions., This work has been supported by the Ministerio Español de Economía y Competitividad (MINECO) through the projects MAT2012-38045-C04-03, MAT2012-38045-C04-01-P, MAT2013-48009-C04-01-P and FIS-2008-06249. J. L.-S. and M. A. thank the FPI fellowship and the UCM Campus of International Excellence (PICATA Program), respectively. Dr A. del Campo is acknowledged for the assistance with the CRM measurements.

La2-xCoTiO6-delta/Ce0.9Gd0.1O2-delta composites are presented as promising new cathodes for solid oxide fuel cells. The B-site ordering characteristic of double perovskites is present in the whole series. Additionally, increasing amounts of La-vacancies give rise to ordering of alternating La-rich and square-rich (square = vacancy) Layers perpendicular to the c-axis. The introduction of La vacancies produces both oxidation of Co2+ to Co3+ and oxygen vacancies inducing a change of both electrical and electrochemical properties. The best electrochemical performances are obtained for Low x due to a compromise between sufficiently high amount of defects to provide electronic and ionic conductivities, but not so high to induce defect clustering. The material with x = 0.05 exhibits the best performances of the series. Symmetrical cells made of composites of this material and Ce0.9Gd0.1O2-delta deposited on pellets of this electrolyte show a polarization resistance of 0.39 Omega cm(2) at 1073 K.

In this work we show the development of bulk in-plane magnetic anisotropy in high Ga-content (Ga = 28 at. %) Fe100-xGax thin films as the layer thickness increases. This result is in clear contrast with the generally reported decrease of this anisotropy with the film thickness. We propose the interrelation between the enhancement of the Ga-pair correlations and a collinear distortion of the bcc structure within the sample plane as the origin of the magnetic anisotropy. Our results have been obtained by employing a combination of long and local range structural probe techniques with bulk and surface magnetic characterization techniques. The key point shown in this work is that the in-plane structural anisotropy and hence, the magnetic anisotropy, are developed as the layer thickness increases. This fact strongly suggests that the surface to bulk free energy ratio plays a key role in the formation of ordered phases with a distorted bcc cell in Fe100-xGax films with x around 28 at. %. Our work also shows the arising of new phenomena in these high Ga content alloys due to the close correlation between structural and magnetic properties. We thank ‘CAI Difraccion de rayos-X ’ of UCM for x-ray diffractometry measurements and ‘Instituto of Sistemas Optoelectronicos y Microtecnología’ (ISOM) for using its facilities. We also want to thank BM25-Spline, the Spanish CRG at ESRF in Grenoble (France) for providing beamtime. This work has been financially supported through the project MAT2015-66888-C3-3-R of the Spanish Ministry of Economy and Competitiveness (MINECO/FEDER) and project PR26/16-3B-2 of Santander and Universidad Complutense de Madrid.

A novel set-up has been designed and used for synchrotron radiation X-ray high-resolution powder diffraction (SR-HRPD) in transmission geometry (spinning capillary) for in situ solid–gas reactions and processes in an isobaric and isothermal environment. The pressure and temperature of the sample are controlled from 10−3 to 1000 mbar and from 80 to 1000 K, respectively. To test the capacities of this novel experimental set-up, structure deformation in the porous material zeolitic imidazole framework (ZIF-8) by gas adsorption at cryogenic temperature has been studied under isothermal and isobaric conditions. Direct structure deformations by the adsorption of Ar and N2 gases have been observed in situ, demonstrating that this set-up is perfectly suitable for direct structural analysis under in operando conditions. The presented results prove the feasibility of this novel experimental station for the characterization in real time of solid–gas reactions and other solid–gas processes by SR-HRPD., The authors are grateful to the SpLine staff for their assistance. Financial support under grant PIE 201060E013 of the Consejo Superior de Investigaciones Científicas-CSIC and the Spanish Ministry of Economy and Competitiveness MINECO is also acknowledged.

We present an extended X-ray absorption fine structure study of the pyrochlores AMoO (A = Gd, Dy, Ho, Er), as a function of temperature. While in the three spin-glass compositions DyMoO, HoMoO and ErMoO the Debye temperatures are in accordance with other pyrochlores and the static disorder contributions are compatible with a lattice frustration, in the low-temperature-ferromagnetic GdMoO system we point out an anomalous enhancement of the local structure disorder below about 225 K down to low temperatures. Moreover, considering the general pyrochlore predisposition towards structural disorder, we prove the presence on a local scale of at least a bimodal distribution of the Mo-O(1) octahedral interatomic distances for all the studied compounds, consisting of two shorter and four longer bond lengths. Our results suggest that the local structure order parameter plays an important role in the ferromagnetic or spin-glass phase stabilization., F.R.-M. is also indebted to MINECO for a ‘Ramon y Cajal’ contract (ref: RyC-2015-18626), which is co-financed by the European Social Fund 2014-20.

We report on the evolution of uncapped FeGa layers deposited by sputtering and post-growth annealed in oxygen atmosphere in a temperature range from 500 °C to 800 °C. We have investigated the morphology, structure and magnetic properties of films with a thickness of 200 nm deposited on Mo buffer layers on glass substrates. X-ray diffractometry shows a decrease of the lattice parameter up to 600 °C whereas a further increase of the temperature up to 800 °C promotes the transformation to FeO. We have observed by x-ray absorption fine structure the partial oxidation of Ga and the formation of Ga aggregates at 600 °C. These aggregates form Ga-rich bubbles that can be observed on the sample surface from which Ga evaporates leaving a Ga-poor layer that is later oxidized into FeO. The thermal treatment on oxygen atmosphere has also a clear impact on the magnetic properties of the layers. The uniaxial in-plane magnetic anisotropy of the as-grown film evolves to magnetic isotropy when annealed at 600 °C probably due to the segregation and formation of Ga-rich areas. After Ga evaporates from the sample, Fe is fully oxidized and only a weak ferromagnetism related to FeO is detected., This work has been financially supported through the projects MAT2015-66888-C3-3-R of the Spanish Ministry of Economy and Competitiveness (MINECO/FEDER) and PR26/16-3B-2 of Santander and Universidad Complutense de Madrid.

We report on the evolution of the microstructure of Tb-Fe-Ga films deposited by co-sputtering from TbFe and FeGa targets. The sputtering power was fixed (90 W) in the FeGa whereas it was increased from 50 to 90 W in the TbFe target resulting on TbFeGa layers with 7 ≤ x ≤ 11. The local structure was determined by means of x-ray absorption fine structure spectroscopy at Fe-K, Ga-K and Tb-L edges. The increase of Tb in the alloy promotes the phase segregation that produces a larger amount of the TbFe structural phase. The structural results have been correlated with the magnetic characterization that shows the enhancement of the out-of-plane component of the magnetization., This work has been financially supported through projects MAT2015-66888-C3-3-R and PIE-2010-OE-013-200014 of the Spanish Ministry of Economy and Competitiveness (MINECO/FEDER) and through the project PR26/16-3B-2 of Santander and Universidad Complutense de Madrid.

Magnetic porous silicon flakes (MPSF) were obtained from mesoporous silicon layers formed by multi-step anodization and subsequent composite formation with Fe oxide nanoparticles by thermal annealing. The magnetic nanoparticles adhered to the surface and penetrated inside the pores. Their structure evolved as a result of the annealing treatments derived from X-ray diffraction and X-ray absorption analyses. Moreover, by tailoring the magnetic load, the dynamic and hydrodynamic properties of the particles were controlled, as observed by the pressure displayed against a sensor probe. Preliminary functionality experiments were performed using an eye model, seeking potential use of MPSF as reinforcement for restored detached retina. It was observed that optimal flake immobilization is obtained when the MPSF reach values of magnetic saturation >10-4 A m2 g-1. Furthermore, the MPSF were demonstrated to be preliminarily biocompatible in vitro. Moreover, New Zealand rabbit in vivo models demonstrated their short-term histocompatibility and their magnetic functionality as retina pressure actuators., The authors gratefully acknowledge financial support from Comunidad de Madrid (Spain) under Project Microseres, from the European project Magnifyco (Contract NMP4-SL-2009-228622) and the Spanish Ministerio de Ciencia e Innovacion grant FIS-2008-06249.

In this paper we analyze the structure of Fe-Ga layers with a Ga content of ∼30 at.% deposited by the sputtering technique under two different regimes. We also studied the correlation between the structure and magnetic behavior of the samples. Keeping the Ar pressure fixed, we modified the flow regime from ballistic to diffusive by increasing the distance between the target and the substrate. X-ray diffraction measurements have shown a lower structural quality when growing in the diffusive flow. We investigated the impact of the growth regime by means of x-ray absorption fine structure (XAFS) measurements and obtained signs of its influence on the local atomic order. Full multiple scattering and finite difference calculations based on XAFS measurements point to a more relevant presence of a disordered A2 phase and of orthorhombic Ga clusters on the Fe-Ga alloy deposited under a diffusive regime; however, in the ballistic sample, a higher presence of D0_3/B2 phases is evidenced. Structural characteristics, from local to long range, seem to determine the magnetic behavior of the layers. Whereas a clear in-plane magnetic anisotropy is observed in the film deposited under ballistic flow, the diffusive sample is magnetically isotropic. Therefore, our experimental results provide evidence of a correlation between flow regime and structural properties and its impact on the magnetic behavior of a rather unexplored compositional region of Fe-Ga compounds.

The current study unveils the structural origin of the magnetic transition of the ε-Fe2O3 polymorph from an incommensurate magnetic order to a collinear ferrimagnetic state at low temperature. The high crystallinity of the samples and the absence of other iron oxide polymorphs have allowed us to carry out temperature-dependent x-ray absorption fine structure spectroscopy experiments out. The deformation of the structure is followed by the Debye–Waller factor for each selected Fe–O and Fe–Fe sub-shell. For nanoparticle sizes between 7 and 15 nm, the structural distortions between the Fete and Fe-D1oc sites are localized in a temperature range before the magnetic transition starts. On the contrary, the inherent interaction between the other sub-shells (named Fe–O1,2 and Fe–Fe1) provokes cooperative magneto-structural changes in the same temperature range. This means that the Fete with Fe-D1oc polyhedron interaction seems to be uncoupled with temperature dealing with these nanoparticle sizes wherein the structural distortions are likely moderate due to surface effects., This work is supported by the Ministerio Español de Economía y Competitividad (MINECO) through the projects MAT2012-38045-C04-03, MAT2015-64110-C2-1-P, MAT2013-48009-C04-01-P, MAT2015-66888-C3-3-R and FIS-2008-06249. Financial support from Fundación BBVA is also acknowledged. JL-S thank the FPI fellowship. The ESRF, MINECO and CSIC are acknowledged for provision of synchrotron radiation facilities and the financial support for the beamtime (PIE-2010-OE-O13-200014).

In this work we investigate the magnetic properties of iron oxide nanoparticles obtained by two-step synthesis (seeded-growth route) with sizes that range from 6 to 18 nm. The initial seeds result monocrystalline and exhibit ferromagnetic behavior with low saturation field. The subsequent growth of a shell enhances the anisotropy inducing magnetic frustration, and, consequently, reducing its magnetization. This increase in anisotropy occurs suddenly at a certain size (~10 nm). Electronic and structural analysis with X-ray absorption spectroscopy indicates a step reduction in the oxidation state as the particle reaches 10 nm size while keeping its overall structure in spite of the magnetic polydispersity. The formation of antiphase magnetic boundaries due to island percolation in the growing shells is hypothesized to be the mechanism responsible of the magnetic behavior, as a direct consequence of the two-step synthesis route of the nanoparticles., This work was supported by the European project MAGNIFYCO (Contract NMP4-SL-2009-228622); Spanish Ministerio de Economía y Competitividad grants CSD2009-00013, MAT2011-27470-C02-02, and FIS-2008-06249; and Madrid Region Council project NANOBIOMAGNET (S2009/MAT-1726). A. F. acknowledges financial support from the Spanish MICINN through CTQ2009-06959 and for a Ramón y Cajal Fellowship (RYC-2010-05821).

This is an Open Access article distributed under the terms of the Creative Commons Attribution License.-- et al., In the present work, the characterization of cobalt-porous silicon (Co-PSi) hybrid systems is performed by a combination of magnetic, spectroscopic, and structural techniques. The Co-PSi structures are composed by a columnar matrix of PSi with Co nanoparticles embedded inside, as determined by Transmission Electron Microscopy (TEM). The oxidation state, crystalline structure, and magnetic behavior are determined by X-Ray Absorption Spectroscopy (XAS) and Alternating Gradient Field Magnetometry (AGFM). Additionally, the Co concentration profile inside the matrix has been studied by Rutherford Backscattering Spectroscopy (RBS). It is concluded that the PSi matrix can be tailored to provide the Co nanoparticles with extra protection against oxidation., We acknowledge the MEC and Consejo Superior de Investigaciones Científicas for financial support (PE-2010 6 0E 013). We would like to thank the BM25-SpLine staff for the technical support. This work has been supported by MICINN through projects FIS-2008-06249, MAT2009-14578-C03-02, MAT2008-06858-C02-01, and MAT2008-06858-C02-02, as well as Comunidad de Madrid, project NANOBIOMAGNET (S2009/MAT-1726) and European project MAGNIFYCO (Contract NMP4-SL-2009-228622)., Acknowledgements We acknowledge the European Synchrotron Radiation Facility for provision of synchrotron radiation facilities and the MEC and Consejo Superior de Investigaciones Científicas for financial support (PE-2010 6 0E 013). We would like to thank the BM25-SpLine staff for the technical support. This work has been supported by MICINN through projects FIS-2008-06249, MAT2009-14578-C03-02, MAT2008-06858-C02-01, and MAT2008-06858-C02-02, as well as Comunidad de Madrid, project NANOBIOMAGNET (S2009/MAT-1726) and European project MAGNIFYCO (Contract NMP4-SL-2009-228622). Technical support from ICTS Centro Nacional de Microscopia Electrónica (UCM, Madrid) is gratefully acknowleged.