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Hydrodechlorination reaction of 3-(benzo-1,3-dioxol-5-yl)-3-chloro-2-methylacrylaldehyde in the presence of different low metal content heterogeneous mono- or bimetallic catalysts was tested for the synthesis of the fragrance Helional® (3-[3,4-methylendioxyphenyl]-2-methyl-propionaldehyde). In particular, mono Pd/Al2O3, Rh/Al2O3 or bimetallic Pd-Cu/Al2O3, Rh-Cu/Al2O3 catalysts were tested in different reaction conditions from which it emerged that mono-Rh/Al2O3 was the best performing catalyst, allowing achievement of 100% substrate conversion and 99% selectivity towards Helional® in 24 h at 80 °C, p(H2) 1.0 MPa in the presence of a base. To establish correlations between atomic structure and catalytic activity, catalysts were characterized by Cu, Rh and Pd K-edge XANES, EXAFS analysis. These characterizations allowed verification that the formation of Pd-Cu alloys and the presence of Cu oxide/hydroxide species on the surface of the Al2O3 support are responsible for the very low catalytic efficiency of bimetallic species tested. [ABSTRACT FROM AUTHOR]

The β phase of tungsten has attracted great interest for spintronic applications due to its higher spin Hall angle compared to other elemental solids and large spin–orbit torque, but the stability of this phase is yet to be well understood as many different results are there in the literature mainly based on the film thickness, temperature, and overall growth conditions. The growth of films by sputter deposition has emerged as a promising technique to achieve β-W owing to its compatibility with current spintronic technology. We demonstrate here the efficient ability of dc magnetron sputtering to grow stable β-W films up to a thickness of ∼180 nm at room temperature by varying a set of deposition parameters like pressure, power, and deposition time and discuss the various underlying mechanisms. From these results, the optimized set of deposition parameters for growing β-W films is given. A clear understanding of the influence of oxygen in the atomic structure of β-W is obtained by varying the thickness of the films. This is confirmed from the ab initio molecular dynamics (MD) simulations, where the atomic structure is influenced by the oxygen doping concentration. A stable polycrystalline β phase can be achieved by controlled doping of oxygen. Additionally, a phase transformation from α to β with the doping of oxygen is also evident by MD simulations. [ABSTRACT FROM AUTHOR]

HoCrO3, a member of the rare-earth chromate family, is known to exhibit an orthorhombic structure with Pbnm space group in bulk at room temperature. We have employed the pressure driven powder consolidation technique, spark plasma sintering, for synthesizing HoCrO3 powder-compact, which exhibits a superior quality with fewer defects over that synthesized by conventional solid-state sintering (resulting in a large reduction of charge carrier mediated extrinsic dielectric contribution). The powder compact shows magneto-dielectric coupling but does not exhibit a detectable ferroelectric phase in the range of 50 K to 300 K. Low temperature Raman spectra show structural distortions below 250 cm−1, indicating Ho ion displacements. Temperature evolution of the crystal structure using synchrotron x-ray diffraction reveals a probable structural phase transition below 240 K. Pyrocurrent measurement, together with synchrotron x-ray diffraction analysis, further points to a magneto-structural transition at 100 K. [ABSTRACT FROM AUTHOR]

FeGa3 is a well known intermetallic semiconductor with a band gap, which is induced by d-p hybridization. In this work, we present the results of experimental and theoretical studies on the effect of Al substitution in FeGa3, obtained by X-ray diffraction (XRD) study, temperature dependent resistivity measurement, room temperature Mössbauer measurement, and density functional theory based electronic structure calculations. It is observed that up to x=0.178 in Fe(AlxGa1-x)3, which is the maximum range studied in this work, Al substitution reduces the lattice parameters a and c, preserving the parent tetragonal P42/mnm crystal structure of FeGa3. Rietveld refinement of the XRD data shows that Al atoms replace Ga atoms located at the 8j sites in FeGa3. A comparison of the trends of the lattice parameters and energy band gap obtained from the calculations and experimental measurements also confirms that Al atoms primarily replace the Ga atoms in the 8j site. The band gap of Fe(AlxGa1-x)3 for x=0.178 is reduced by ≈24% as compared to FeGa3. The system thus has a lot of promise for applications in band gap engineering in infra-red devices. [ABSTRACT FROM AUTHOR]

Dispersion of metal nanoparticles on flat surfaces has attracted considerable interest in many technological applications. Numerous advantages of functionalized patterned nanostructures especially in medical physics, chemistry, biology, and semiconductor quantum dot applications have rapidly driven the growth of this field in the last two decades. In particular, for applications involving biomedical imaging, the nanoparticles have attracted perhaps the greatest attention as these materials provide a direct interface at the subcellular length scale. Reliable characterization methods are thus often needed to infer their detailed structural properties such as average particle size, particle shape, internal structure, surface morphology, distribution of particles, and their chemical composition. As a nondestructive probe, X-ray fluorescence measurements at grazing incidence provide sensitive information about the physical and chemical nature of the nanoparticles over the large surface area of a substrate. Herein, we demonstrate the potential capabilities of the X-ray fluorescence technique for reliable and precise determination of surface morphology of metal nanoparticles, dispersed on a flat surface. Our results show that X-ray standing wave assisted fluorescence measurements are markedly sensitive to the nature of dispersion of nanoparticles on a substrate surface. We have analyzed different types of nanostructured materials; e.g. a W thin film structure and Au nanoparticles deposited on a Si surface. The average size of the Au nanoparticles estimated, using X-ray standing wave fluorescence analysis, was found to closely agree with the atomic force microscopy measurements. The inherent features of the X-ray fluorescence technique permit us to analyze distribution of all kinds of metal and metalloid nanoparticles on a flat surface. Copyright © 2017 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

This paper is a continuation and extension of our earlier work ( X-ray Spectrom. 2010, 39, 127-134, DOI:10.1002/xrs.1215) on the development of a software platform CATGIXRF, as a solution to provide non-destructive evaluation of nanostructured materials. Here, we describe an interactive graphical user interface (GUI) for the CATGIXRF program. The newly developed GUI interface facilitates determination of microstructural parameters on angstrom length scale for the nanostructured thin layered materials using synchrotron as well as laboratory X-ray sources. It allows combined analysis capabilities for both the X-ray reflectivity and grazing incidence X-ray fluorescence (GIXRF) data simultaneously, thus enabling us a greater sensitivity for the determination of microstructural parameters such as thickness, interface mixing, and roughness of a thin film medium with improved accuracies. The utility and various newly added salient features of the GUI-CATGIXRF program are described by providing example calculations as well as by analyzing experimentally a few thin film structures with different surface-interface properties. Copyright © 2016 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Long-term durability of a thin film device is strongly correlated with the nature of interface structure associated between different constituent layers. Synthetic periodic multilayer structures are primarily employed as artificial X-ray Bragg reflectors in many applications, and their reflection efficiency is predominantly dictated by the nature of the buried interfaces between the different layers. Herein, we demonstrate the applicability of the combined analysis approach of the X-ray reflectivity and grazing incidence X-ray fluorescence measurements for the reliable and precise determination of a buried interface structure inside periodic X-ray multilayer structures. X-ray standing wave field (XSW) generated under Bragg reflection condition is used to probe the different constituent layers of the W-B4C multilayer structure at 10 keV and 12 keV incident X-ray energies. Our results show that the XSW assisted fluorescence measurements are markedly sensitive to the location and interface morphology of a buried layer structure inside a periodic multilayer structure. The cross sectional transmission electron microscopy results obtained on the W-B4C multilayer structure provide a deeper look on the overall reliability and accuracy of the XSW method. The method described here would also be applicable for nondestructive characterization of a wide range of thin film based semiconductor and optical devices. [ABSTRACT FROM AUTHOR]

Dopant-profile independent electron transport has been observed through a combined study of temperature dependent electrical resistivity and magnetoresistance measurements on a series of Ti incorporated ZnO thin films with varying degree of static-disorder. These films were grown by atomic layer deposition through in-situ vertical stacking of multiple sub-monolayers of TiOx in ZnO. Upon decreasing ZnO spacer layer thickness, electron transport smoothly evolved from a good metallic to an incipient non-metallic regime due to the intricate interplay of screening of spatial potential fluctuations and strength of static-disorder in the films. Temperature dependent phase-coherence length as extracted from the magnetotransport measurement revealed insignificant role of inter sub-monolayer scattering as an additional channel for electron dephasing, indicating that films were homogeneously disordered three-dimensional electronic systems irrespective of their dopant-profiles. Results of this study are worthy enough for both fundamental physics perspective and efficient applications of multi-stacked ZnO/TiOx structures in the emerging field of transparent oxide electronics. [ABSTRACT FROM AUTHOR]

The effect of longitudinal (or temporal) coherence on total reflection assisted x-ray standing wave (TR-XSW) analysis of nanoscale materials is quantitatively demonstrated by showing how the XSW fringe visibility can be strongly damped by decreasing the spectral resolution of the incident x-ray beam. The correction for nonzero wavelength dispersion (δλ ≠ 0) of the incident x-ray wave field is accounted for in the model computations of TR-XSW assisted angle dependent fluorescence yields of the nanostructure coatings on x-ray mirror surfaces. Given examples include 90 nm diameter Au nanospheres deposited on a Si(100) surface and a 3 nm thick Zn layer trapped on top a 100 nm Langmuir-Blodgett film coating on a Au mirror surface. Present method opens up important applications, such as enabling XSW studies of large dimensioned nanostructures using conventional laboratory based partially coherent x-ray sources. [ABSTRACT FROM AUTHOR]

A new multipurpose x-ray reflectometer station has been developed and augmented at the microfocus beamline (BL-16) of Indus-2 synchrotron radiation source to facilitate synchronous measurements of specular x-ray reflectivity and grazing incidence x-ray fluorescence emission from thin layered structures. The design and various salient features of the x-ray reflectometer are discussed. The performance of the reflectometer has been evaluated by analyzing several thin layered structures having different surface interface properties. The results reveal in-depth information for precise determination of surface and interface properties of thin layered materials demonstrating the immense potential of the combined measurements of x-ray reflectivity and grazing incidence fluorescence on a single reflectometer. [ABSTRACT FROM AUTHOR]

Total reflection X-ray fluorescence (TXRF) spectroscopy has seen remarkable progress over the past years. Numerous applications in basic and applied sciences prove its importance. The large spectral background, which is a major detrimental factor in the conventional X-ray fluorescence technique, limits the element detection sensitivities of the technique to the µg g-1 (ppm) range. This spectral background is reduced to a great extent in the TXRF technique due to the low extinction depth of the primary incident X-ray beam. In synchrotron radiation (SR) based TXRF measurements the spectral background is reduced further because of the polarization of the synchrotron X-ray beam. Here, we show in detail the influence of synchrotron polarization on the spectral background in a fluorescence spectrum and its significance towards TXRF detection sensitivities. We have performed TXRF measurements on standard reference materials to show that one obtains approximately one order of magnitude enhancement in the spectral signal strength by utilizing the anisotropic nature of the scattered synchrotron radiation in the horizontal detection geometry. [ABSTRACT FROM AUTHOR]

In this work, sol–gel ZnO thin films were implanted with Al ions of various fluences to study their electrical transport properties as transparent conducting oxide (TCO) layers. Additionally, formation of structural defects and modifications of the optical emission properties due to implantation have been investigated extensively to correlate the resultant electrical properties. By varying the ion fluence over two orders of magnitude from 1 × 1013 to 6 × 1015 ions/cm2, interestingly the electrical transport properties have been seen to be degraded in an unexpected manner as soon as Al is implanted and beyond a certain fluence (5 × 1013 ions/cm2), the electrical properties begin to improve. For the highest fluence (6 × 1015 ions/cm2), the sheet resistance is found to be 156 Ω/sq with an average visible transmission of 82%. The figure of merit value of our Al implanted ZnO film for an Al fluence of 5 × 1015 ions/cm2 is the highest till date, which may be prospective as a TCO layer. Detailed investigation on the evolution of the electrical and photoluminescence properties with an increase in the Al ion fluence reveals that zinc vacancy type defects are formed in large number which on healing produces further higher conductivity in the films. Image 1 • Sol-gel ZnO thin films were implanted with Al ions followed by annealing at 450 °C. • Film with 156 Ω/sq sheet resistance and >80% visible transmittance is produced. • Maximum FOM value of 9.57 × 10 −4 Ω −1 has been achieved. • Zinc vacancy plays a vital role in controlling the observed electrical properties. • The study is useful for understanding implantation effect and utilization of films as TCO. [ABSTRACT FROM AUTHOR]

Nanocrystalline La0.15Ca0.85MnO3 samples of various grain sizes ranging from ∼17 to 42 nm have been prepared by sol-gel technique. Phase purity and composition were verified by room temperature x-ray diffraction and SEM-EDAX analysis. The bulk La0.15Ca0.85MnO3 is known to order antiferromagnetically around 170 K and to undergo a simultaneous crystal structural transition. DC magnetization measurements on 17 nm size La0.15Ca0.85MnO3 show a peak at ∼130 K (TN) in zero-field-cooled (ZFC) state. Field-cooled magnetization bifurcates from ZFC data around 200 K hinting a weak ferromagnetic component near room temperature due to surface moments of the nanoparticle sample. Low temperature powder neutron diffraction experiments reveal that the incomplete structural transition from room temperature orthorhombic to low temperature orthorhombic-monoclinic state also occurs in the nanoparticle sample as in the bulk. Magnetization in the ordered state decreases as particle size increases, thus indicating the reduction of the competing ferromagnetic surface moments. [ABSTRACT FROM AUTHOR]

We report results of simultaneous x-ray reflectivity and grazing incidence x-ray fluorescence measurements in combination with x-ray standing-wave-assisted depth-resolved near-edge x-ray absorption measurements to reveal new insights on chemical speciation of W in a W-B4C multilayer structure. Interestingly, our results show the existence of various unusual electronic states for the W atoms especially those near to the surface and interface boundary of a thin film medium as compared to those of the bulk. These observations are found to be consistent with the results obtained using first-principles calculations. Unlike the conventional x-ray absorption measurements the present approach has an advantage that it permits the determination of the depth-resolved chemical nature of an element in the thin-layered materials at atomic length scale resolution. [ABSTRACT FROM AUTHOR]

• 10 keV Ar+ ion implantation induced modifications has been explored in Co 20 Fe 60 B 20 /SmCo 5 bilayers. • Magnetic Coercivity has been increased by more than ten times after implantation. • X-ray reflectivity study revealed ion implantation causes significant microstructural modifications. • Enhancement of coercivity attributed to mixing of elements at the interface and Ar implantation induced defects creation. 10 keV Ar+ ion implantation induced modifications of nanoscale Co 20 Fe 60 B 20 /SmCo 5 /Si-substrate heterostructures have been investigated. Magneto-optic Kerr effect study reveals that the coercivity enhances by more than ten times after implantation. Implantation gives rise to an increase in surface roughness and densely packed grains as evident from the Atomic Force Microscopy study. X-ray reflectivity analysis manifests ion beam induced intermixing between elements of two layers at the interface and significant changes in the internal structure. Monte Carlo simulation study corroborates the x-ray reflectivity results. Enhancement of coercivity attributed to interface mixing and implantation induced defect creation in the films. [ABSTRACT FROM AUTHOR]

Violacein is a naturally found pigment that is used by some gram negative bacteria to defend themselves from various gram positive bacteria. As a result, this molecule has caught attention for its potential biomedical applications and has already shown promising outcomes as an antiviral, an antibacterial, and an anti-tumor agent. Understanding the interaction of this molecule with a cellular membrane is an essential step to extend its use in the pharmaceutical paradigm. Here, the interaction of violacein with a lipid monolayer formed at the air–water interface is found to depend on electrostatic nature of lipids. In presence of violacein, the two dimensional (2D) pressure–area isotherms of lipids have exhibited changes in their phase transition pressure and in-plane elasticity. To gain insights into the out-of-plane structural organization of lipids in a membrane, X-ray reflectivity (XRR) study on a solid supported lipid monolayer on a hydrophilic substrate has been performed. It has revealed that the increase in membrane thickness is more pronounced in the zwitterionic and positively charged lipids compared to the negatively charged one. Further, the lipid molecules are observed to decrease their tilt angle made with the normal of lipid membrane along with an alteration in their in-plane ordering. This has been quantified by grazing incidence X-ray diffraction (GIXD) experiments on the multilayer membrane formed in an environment with controlled humidity. The structural reorganization of lipid molecules in presence of violacein can be utilized to provide a detailed mechanism of the interaction of this molecule with cellular membrane. [Display omitted] • Interaction of violacein with cellular membrane may control its activities. • Violacein can condense the in-plane organization of lipids in a cellular membrane. • Tilt angle of lipids in membranes changes due to the condensing effect of violacein. • Lipid membrane thickness increases as violacein penetrates into the membrane. [ABSTRACT FROM AUTHOR]