Synchrotron‐based spectroscopy of X‐ray channeling through hollow capillary microchannels inside glass plates

Here, soft X‐ray synchrotron radiation transmitted through microchannel plates is studied experimentally. Fine structures of reflection and XANES Si L‐edge spectra detected on the exit of silicon glass microcapillary structures under conditions of total X‐ray reflection are presented and analyzed. The phenomenon of the interaction of channeling radiation with unoccupied electronic states and propagation of X‐ray fluorescence excited in the microchannels is revealed. Investigations of the interaction of monochromatic radiation with the inner‐shell capillary surface and propagation of fluorescence radiation through hollow glass capillary waveguides contribute to the development of novel X‐ray focusing devices in the future.     

X‐ray fluorescence induced by standing waves in the grazing‐incidence and grazing‐exit modes: study of the Mg–Co–Zr system

The characterization of Mg–Co–Zr tri‐layer stacks using X‐ray fluorescence induced by X‐ray standing waves, in both the grazing‐incidence (GI) and the grazing‐exit (GE) modes, is presented. The introduction of a slit in the direction of the detector improves the angular resolution by a factor of two and significantly improves the sensitivity of the technique for the chemical characterization of the buried interfaces. By observing the intensity variations of the Mg Kα and Co Lα characteristic emissions as a function of the incident (GI mode) or detection (GE mode) angle, it is shown that the interfaces of the Si/[Mg/Co/Zr]_×30 multilayer are abrupt, whereas in the Si/[Mg/Zr/Co]_×30 multilayer a strong intermixing occurs at the Co‐on‐Zr interfaces. An explanation of this opposite behavior of the Co‐on‐Zr and Zr‐on‐Co interfaces is given by the calculation of the mixing enthalpies of the Co–Mg, Co–Zr and Mg–Zr systems, which shows that the Co–Zr system presents a negative value and the other two systems present positive values. Together with the difference of the surface free energies of Zr and Co, this leads to the Mg/Zr/Co system being considered as a Mg/Co_xZr_y bi‐layer stack, with x/y estimated around 3.5.     

Current status of the TwinMic beamline at Elettra: a soft X‐ray transmission and emission microscopy station

The current status of the TwinMic beamline at Elettra synchrotron light source, that hosts the European twin X‐ray microscopy station, is reported. The X‐ray source, provided by a short hybrid undulator with source size and divergence intermediate between bending magnets and conventional undulators, is energy‐tailored using a collimated plane‐grating monochromator. The TwinMic spectromicroscopy experimental station combines scanning and full‐field imaging in a single instrument, with contrast modes such as absorption, differential phase, interference and darkfield. The implementation of coherent diffractive imaging modalities and ptychography is ongoing. Typically, scanning transmission X‐ray microscopy images are simultaneously collected in transmission and differential phase contrast and can be complemented by chemical and elemental analysis using across‐absorption‐edge imaging, X‐ray absorption near‐edge structure or low‐energy X‐ray fluorescence. The lateral resolutions depend on the particular imaging and contrast mode chosen. The TwinMic range of applications covers diverse research fields such as biology, biochemistry, medicine, pharmacology, environment, geochemistry, food, agriculture and materials science. They will be illustrated in the paper with representative results.     

Relationship between the structural distortion and the Mn electronic state in La1−xCaxMnO3: a Mn K‐edge XANES study

A theoretical study of the X‐ray absorption near‐edge structure (XANES) spectra at the Mn K‐edge in the La_1?xCa_xMnO₃ series is reported. The relationship between the edge shift, the Ca–La substitution and the distortion of the MnO₆ octahedra in these systems has been studied. It is shown that, by correctly considering these effects simultaneously, the experimental XANES data are consistent with the presence of two different Mn local environments in the intermediate La_1?xCa_xMnO₃ compounds. By taking into account the energy shift associated with the modification of the MnO₆ distortion as Ca substitutes for La, it is possible to reproduce the XANES spectra of the intermediate‐doped compounds starting from the experimental spectra of the end‐members LaMnO₃ and CaMnO₃. These results point out the need to re‐examine the conclusions derived in the past from the simple analysis of the Mn K‐edge XANES edge‐shift in these materials. In particular, it is shown that the modification of the Mn K‐edge absorption through the La_1?xCa_xMnO₃ series is well reproduced by considering the simultaneous presence of both distorted and undistorted octahedra and, consequently, that the existence of charge‐ordering phenomena cannot be ruled out from the XANES data.     

平行光栅对在刻线不平行时的色散研究

利用三维空间光线追迹法,分析了啁啾脉冲放大系统中的压缩光栅对,在刻线不平行而光栅面平行时光的衍射特性。导出了此时光通过光栅对的群延时,数值计算了系统2阶和3阶色散量,以及这些色散量在光栅对严格平行时的相对误差。得出了中心波长光的接收位置相对于光栅对严格平行时的偏移量,并且分析了它与入射角的变化关系。     

Investigation of the multiplet features of SrTiO3 in X‐ray absorption spectra based on configuration interaction calculations

Synchrotron‐based L_2,3‐edge absorption spectra show strong sensitivities to the local electronic structure and chemical environment. However, detailed physical information cannot be extracted easily without computational aids. Here, using the experimental Ti L_2,3‐edges absorption spectrum of SrTiO₃ as a fingerprint and considering full multiplet effects, calculations yield different energy parameters characterizing local ground state properties. The peak splitting and intensity ratios of the L₃ and L₂ set of peaks are carefully analyzed quantitatively, giving rise to a small hybridization energy around 1.2 eV, and the different hybridization energy values reported in the literature are further addressed. Finally, absorption spectra with different linearly polarized photons under various tetragonal crystal fields are investigated, revealing a non‐linear orbital–lattice interaction, and a theoretical guidance for material engineering of SrTiO₃‐based thin films and heterostructures is offered. Detailed analysis of spectrum shifts with different tetragonal crystal fields suggests that the e_g crystal field splitting is a necessary parameter for a thorough analysis of the spectra, even though it is not relevant for the ground state properties.     

Determination of the Surface Facets of Gold Nanorods in Wet‐Coated Thin Films with Grazing‐Incidence Wide Angle X‐Ray Scattering

This work studies the surface facets of gold nanorods (AuNRs) in wet‐coated nanoparticle thin films with synchrotron‐light‐based grazing‐incidence wide angle X‐ray scattering (GIWAXS), which provides statistically relevant results on many nanoparticles. Air‐brush spraying deposits the monodisperse AuNRs into sparse monolayers where the long axis of rods is parallel to the substrate surface. It is found that the crystalline facets of individual AuNRs in the sparse monolayer are all in the same orientation, as indicated by narrow azimuthal widths of (200) reflections, over a macroscopic scale comparable to the substrate. This alignment is probably due to the rods' sitting on high‐index surface facets such as (520) and (250). A quantitative analysis of the angles between bulk facets and the surface facets leads to a “nested‐octagon” model for the cross sections of AuNRs: shell octagon with high‐index crystalline facets (520), (5‐20), (2‐50), (‐2‐50), (‐5‐20), (‐520), (‐250), and (250), and core octagon consisting of low‐index crystalline facets (100), (1‐10), (0‐10), (‐1‐10), (‐100), (‐110), (010), and (110).     

Diffraction of X‐ray free‐electron laser femtosecond pulses on single crystals in the Bragg and Laue geometry

A solution of the problem of dynamical diffraction for X‐ray pulses with arbitrary dimensions in the Bragg and Laue cases in a crystal of any thickness and asymmetry coefficient of reflection is presented. Analysis of pulse form and duration transformation in the process of diffraction and propagation in a vacuum is conducted. It is shown that only the symmetrical Bragg case can be used to avoid smearing of reflected pulses.     

Spectroscopic investigation of modern pigments on purportedly medieval miniatures by the ‘Spanish Forger’

Five miniatures by the so‐called ‘Spanish Forger’ were acquired by the Victoria and Albert Museum in 2008. Believed to be authentic medieval miniatures until the mid‐twentieth century, they are now considered to have been painted around the end of the nineteenth and the beginning of the twentieth century. To investigate this attribution and to gather detailed knowledge about the materials used by the artist, a comprehensive pigment analysis by Raman microscopy and X‐ray fluorescence was carried out. Although traditional materials such as vermilion, carbon black, red lead, lead white and indigo were identified, many others (chrome yellow, Scheele's green, emerald green and ultramarine blue) are modern and synthetic pigments, a result which provides a firm scientific basis for stating that the miniatures are forgeries. Copyright © 2009 John Wiley & Sons, Ltd.     

Distinct effect of xenobiotics on the metal‐binding properties of protein molecules

The X‐ray standing‐wave method was applied to study the elemental composition and molecular organization of ordered protein films of alkaline phosphatase exposed to different xenobiotics (drug compounds, lead). Binding of metal ions from triply distilled water to protein molecules has been experimentally observed. Definite differences in the arrangement of impurity metal ions in the films have been established. The considerable enhancement of protein–metal interactions is attributed to partial rearrangement of the protein native structure, induced by xenobiotics.     

Blueprint XAS: a Matlab‐based toolbox for the fitting and analysis of XAS spectra

Blueprint XAS is a new Matlab‐based program developed to fit and analyse X‐ray absorption spectroscopy (XAS) data, most specifically in the near‐edge region of the spectrum. The program is based on a methodology that introduces a novel background model into the complete fit model and that is capable of generating any number of independent fits with minimal introduction of user bias [Delgado‐Jaime & Kennepohl (2010), J. Synchrotron Rad. 17 , 119–128]. The functions and settings on the five panels of its graphical user interface are designed to suit the needs of near‐edge XAS data analyzers. A batch function allows for the setting of multiple jobs to be run with Matlab in the background. A unique statistics panel allows the user to analyse a family of independent fits, to evaluate fit models and to draw statistically supported conclusions. The version introduced here (v0.2) is currently a toolbox for Matlab. Future stand‐alone versions of the program will also incorporate several other new features to create a full package of tools for XAS data processing.     

Raman spectroscopy of very small Cd1−xCoxS quantum dots grown by a novel protocol: direct observation of acoustic‐optical phonon coupling

Glass‐embedded Cd_1−xCo_xS quantum dots (QDs) with mean radius of R ≈ 1.70 nm were successfully synthesized by a novel protocol on the basis of the melting‐nucleation synthesis route and herein investigated by several experimental techniques. Incorporation of Co²⁺ ions into the QD lattice was evidenced by X‐ray diffraction and magnetic force microscopy results. Optical absorption features with irregular spacing in the ligand field region confirmed that the majority of the incorporated Co²⁺ ions are under influence of a low‐symmetry crystal field located near to the Cd_1−xCo_xS QD surface. Electron paramagnetic resonance data confirmed the presence of Co²⁺ ions in a highly inhomogeneous crystal field environment identified at the interface between the hosting glass matrix (amorphous) and the crystalline QD. The acoustic‐optical phonon coupling in the Cd_1−xCo_xS QDs (x ≠ 0.000) was directly observed by Raman measurements, which have shown a high‐frequency shoulder of the longitudinal optical phonon peak. This effect is tuned by the size‐dependent sp‐d exchange interaction due to the magnetic doping, causing variations in the coupling between electrons and longitudinal optical phonon. Copyright © 2013 John Wiley & Sons, Ltd.     

Structure of van der Waals bound hybrids of organic semiconductors and transition metal dichalcogenides: the case of acene films on MoS2

Transition metal dichalcogenides (TMDC) are important representatives in the emerging field of two‐dimensional materials. At present their combination with molecular films is discussed as it enables the realization of van der Waals bound organic/inorganic hybrids which are of interest in future device architectures. Here, we discuss the potential use of molybdenum disulfide (MoS₂) as supporting substrate for the growth of well‐defined, crystalline organic adlayers. By this means, hybrid systems between the TMDC surface and organic compounds can be prepared, allowing for the profound investigation of mutual optical and electronic coupling mechanisms. As model system, we choose pentacene and perfluoropentacene as prototypical organic semiconductors and analyze their film formation on MoS₂(001) surfaces. In both cases, we observe smooth, crystalline film growth in lying molecular configuration, hence enabling the preparation of well‐defined hybrid systems. By contrast, on defective MoS₂ surfaces both materials adopt an upright molecular orientation and exhibit distinctly different film morphologies. This emphasizes the importance of highly ordered TMDC surfaces with low defect density for the fabrication of well‐defined hybrid systems.     

Charge‐dependent adsorption of rhodamine 6G on gold nanoparticle surfaces: fluorescence and Raman study

We study the adsorption behaviors of rhodamine dyes on gold nanoparticles (Au NPs) depending on their surface charges. Rhodamine 6G (Rh6G) dye is tested comparatively for positively and negatively charged Au NPs prepared by the reduction of chitosan and citric acid, respectively. The adsorption of Rh6G is found to be weaker on the positively charged Au NPs, whereas more substantial aggregation is found on negatively charged Au NPs. An increase in the concentration of Au NPs enhances the surface‐enhanced Raman scattering (SERS) intensities only for the Au(−) NPs, whereas the Au(+) NPs do not exhibit any strong SERS signals. Our findings suggest that SERS and reciprocal fluorescence measurements of Rh6G can be used to estimate the surface charges and atomic percentages of Au NPs less than ∼5 ppm. Copyright © 2011 John Wiley & Sons, Ltd.     

Nondestructive analysis of jade artifacts from the Cemetery of the Ying State in Henan Province,China using confocal Raman microspectroscopy and portable X‐ray fluorescence spectroscopy

Confocal Raman microspectroscopy and portable X‐ray fluorescence spectroscopy were used nondestructively to characterise 18 intact jade artifacts from the Cemetery of the Ying State in Pingdingshan, Henan Province, China. These jade artifacts date from the early to the middle of the Western Zhou Period (the mid‐11^th to the mid‐9^th century BC). Thirteen jade artifacts made of tremolite and two jade artifacts made of actinolite were discriminated from each other by their hydroxyl stretching modes, and a malachite pendant, a muscovite dagger‐axe, and a crystal pendant were also identified. Black graphite was analysed in three jade artifacts composed of tremolite, and the mineralization temperatures were estimated and compared. A red powder was found on the surface of all of the jade artifacts, and this was found to be cinnabar (HgS), which is thought to have been added to the tomb environments during burial ceremonies. The chemical compositions and the possible provenances of the jade artifacts are briefly discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

A note on medieval microfabrication: the visualization of a prayer nut by synchrotron‐based computer X‐ray tomography

One of the most fascinating objects in the Rijksmuseum (Amsterdam, The Netherlands) is an early 16th century prayer nut. This spherical wooden object measures 4 cm in diameter and consists of two hemispheres connected with a small hinge so that it can be opened. The interior of the nut holds wood carvings with scenes from the life of Christ. These miniature reliefs show an incredible degree of finish with carving details well beyond the millimetre scale. In the present paper it is shown how synchrotron‐based computer X‐ray tomography revealed the structure and fabrication method of the bead. The central part of the relief was cut from a single piece of wood, rather than assembled from multiple components, underlining the extraordinary manual dexterity of its maker. In addition, a piece of fibrous material contained in the inner structure of the bead is revealed. This may have served as a carrier for an odorous compound, which would be in line with the religious function of the prayer nut.     

On easily tunable wide‐bandpass X‐ray monochromators based on refraction in arrays of prisms

Refractive lenses focus X‐rays chromatically owing to a significant variation of the refractive index of the lens material with photon energy. Then, in combination with an exit slit in the focal plane, such lenses can be used as monochromators. The spectral resolution obtainable with refractive lenses based on prism arrays was recently systematically investigated experimentally. This contribution will show that a wide‐bandpass performance can be predicted with a rather simple analytical approach. Based on the good agreement with the experimental data, one can then more rapidly and systematically optimize the lens structure for a given application. This contribution will then discuss more flexible solutions for the monochromator operation. It will be shown that a new monochromator scheme could easily provide tuning in a fixed‐exit slit.     

Zr and Ba edge phenomena in the scintillation intensity of fluorozirconate‐based glass‐ceramic X‐ray detectors

The energy‐dependent scintillation intensity of Eu‐doped fluorozirconate glass‐ceramic X‐ray detectors has been investigated in the energy range from 10 to 40 keV. The experiments were performed at the Advanced Photon Source, Argonne National Laboratory, USA. The glass ceramics are based on Eu‐doped fluorozirconate glasses, which were additionally doped with chlorine to initiate the nucleation of BaCl₂ nanocrystals therein. The X‐ray excited scintillation is mainly due to the 5d–4f transition of Eu²⁺ embedded in the BaCl₂ nanocrystals; Eu²⁺ in the glass does not luminesce. Upon appropriate annealing the nanocrystals grow and undergo a phase transition from a hexagonal to an orthorhombic phase of BaCl₂. The scintillation intensity is investigated as a function of the X‐ray energy, particle size and structure of the embedded nanocrystals. The scintillation intensity versus X‐ray energy dependence shows that the intensity is inversely proportional to the photoelectric absorption of the material, i.e. the more photoelectric absorption the less scintillation. At 18 and 37.4 keV a significant decrease in the scintillation intensity can be observed; this energy corresponds to the K‐edge of Zr and Ba, respectively. The glass matrix as well as the structure and size of the embedded nanocrystals have an influence on the scintillation properties of the glass ceramics.     

平行光栅对在刻线不平行时的色散研究

 利用三维空间光线追迹法，分析了啁啾脉冲放大系统中的压缩光栅对，在刻线不平行而光栅面平行时光的衍射特性。导出了此时光通过光栅对的群延时，数值计算了系统2阶和3阶色散量，以及这些色散量在光栅对严格平行时的相对误差。得出了中心波长光的接收位置相对于光栅对严格平行时的偏移量，并且分析了它与入射角的变化关系。