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.     

A microfocus X‐ray fluorescence beamline at Indus‐2 synchrotron radiation facility

A microfocus X‐ray fluorescence spectroscopy beamline (BL‐16) at the Indian synchrotron radiation facility Indus‐2 has been constructed with an experimental emphasis on environmental, archaeological, biomedical and material science applications involving heavy metal speciation and their localization. The beamline offers a combination of different analytical probes, e.g. X‐ray fluorescence mapping, X‐ray microspectroscopy and total‐external‐reflection fluorescence characterization. The beamline is installed on a bending‐magnet source with a working X‐ray energy range of 4–20 keV, enabling it to excite K‐edges of all elements from S to Nb and L‐edges from Ag to U. The optics of the beamline comprises of a double‐crystal monochromator with Si(111) symmetric and asymmetric crystals and a pair of Kirkpatrick–Baez focusing mirrors. This paper describes the performance of the beamline and its capabilities with examples of measured results.     

Total reflection x‐ray fluorescence analysis—a review

Total reflection x‐ray fluorescence analysis (TXRF) is a special energy‐dispersive x‐ray analytical technique extending XRF down to the ultra trace element range. Detection limits of picograms or nanograms per gram levels are reached with x‐ray tube excitation. Using synchrotron radiation as excitation source, femtogram levels are detectable, particularly important for Si wafer surface analysis. TXRF is specially suited for applications in which only a very small amount of sample is available, as only a few micrograms are required for the analysis. In this review, an overview of theoretical principles, advantages, instrumentation, quantification and application is given. Chemical analysis as well as surface analysis including depth profiling and thin‐film characterization is described. Special research results on extension to low‐Z elements, excitation with synchrotron radiation and x‐ray absorption spectroscopy (XAS) for chemical speciation at trace levels are reviewed. Copyright © 2007 John Wiley & Sons, Ltd.     

Measurement of L subshell fluorescence yield ratios of some high Z elements by selective excitation method

The L₁, L₂ and L₃ subshells of Hf, Ta and Re atoms have been excited selectively by using microprobe XRF beam line, Indus‐2, RRCAT, India. The consequent characteristic L X‐ray photons, emitted from the targets due to creations of vacancies in L subshells, are measured using silicon drift detector (X‐123) spectrometer. As the energy of synchrotron radiation increases, the contribution of characteristic L X‐ray intensity increases. The advantage of the increase in the intensity of the characteristic L X‐ray photons with an increase in the energy of synchrotron radiation has been used to determine the L subshell fluorescence yield ratios of Hf, Ta and Re atoms by adopting the selective excitation method. The measured ratios of L subshell fluorescence yield have been compared with theoretical and other experimental values.     

The first microbeam synchrotron X‐ray fluorescence beamline at the Siam Photon Laboratory

The first microbeam synchrotron X‐ray fluorescence (µ‐SXRF) beamline using continuous synchrotron radiation from Siam Photon Source has been constructed and commissioned as of August 2011. Utilizing an X‐ray capillary half‐lens allows synchrotron radiation from a 1.4 T bending magnet of the 1.2 GeV electron storage ring to be focused from a few millimeters‐sized beam to a micrometer‐sized beam. This beamline was originally designed for deep X‐ray lithography (DXL) and was one of the first two operational beamlines at this facility. A modification has been carried out to the beamline in order to additionally enable µ‐SXRF and synchrotron X‐ray powder diffraction (SXPD). Modifications included the installation of a new chamber housing a Si(111) crystal to extract 8 keV synchrotron radiation from the white X‐ray beam (for SXPD), a fixed aperture and three gate valves. Two end‐stations incorporating optics and detectors for µ‐SXRF and SXPD have then been installed immediately upstream of the DXL station, with the three techniques sharing available beam time. The µ‐SXRF station utilizes a polycapillary half‐lens for X‐ray focusing. This optic focuses X‐ray white beam from 5 mm × 2 mm (H × V) at the entrance of the lens down to a diameter of 100 µm FWHM measured at a sample position 22 mm (lens focal point) downstream of the lens exit. The end‐station also incorporates an XYZ motorized sample holder with 25 mm travel per axis, a 5× ZEISS microscope objective with 5 mm × 5 mm field of view coupled to a CCD camera looking to the sample, and an AMPTEK single‐element Si (PIN) solid‐state detector for fluorescence detection. A graphic user interface data acquisition program using the LabVIEW platform has also been developed in‐house to generate a series of single‐column data which are compatible with available XRF data‐processing software. Finally, to test the performance of the µ‐SXRF beamline, an elemental surface profile has been obtained for a piece of ancient pottery from the Ban Chiang archaeological site, a UNESCO heritage site. It was found that the newly constructed µ‐SXRF technique was able to clearly distinguish the distribution of different elements on the specimen.     

An in situ atomic force microscope for normal‐incidence nanofocus X‐ray experiments

A compact high‐speed X‐ray atomic force microscope has been developed for in situ use in normal‐incidence X‐ray experiments on synchrotron beamlines, allowing for simultaneous characterization of samples in direct space with nanometric lateral resolution while employing nanofocused X‐ray beams. In the present work the instrument is used to observe radiation damage effects produced by an intense X‐ray nanobeam on a semiconducting organic thin film. The formation of micrometric holes induced by the beam occurring on a timescale of seconds is characterized.     

An estimation of EDXRF spectrometer properties,based on a two‐layer composite Si‐Ge detector

A mathematical model for the two‐layer composite Si‐Ge energy dispersive X‐ray detector is proposed, based on analyses of radiation and electron transport in the detector, and a mathematical model of an energy dispersive X‐ray fluorescent spectrometer with the detector is considered. The Monte Carlo method is applied to calculate probabilities of photon detection in different parts of the detector's response function. The composite detector with the time anti‐coincidence scheme is proposed; its first layer is Si detector, and the second layer is Ge detector. It is shown that this composite detector has some advantages, such as reduced Ge photo escape peaks intensities and efficiency of detection of high energy photons similar to efficiency of Ge detector. Applying the X‐ray detector for the energy dispersive X‐ray fluorescent spectrometer provides for a lower background level. Copyright © 2012 John Wiley & Sons, Ltd.     

A high‐resolution X‐ray fluorescence spectrometer and its application at SSRF

A high‐resolution X‐ray fluorescence spectrometer based on Rowland circle geometry was developed and installed at BL14W1 XAFS beamline of Shanghai Synchrotron Radiation Facility. The spectrometer mainly consists of three parts: a sample holder, a spherically curved Si crystal, and an avalanche photodiode detector. The simplicity of the spectrometer makes it easily assembled on the general purpose X‐ray absorption beamline. X‐ray emission spectroscopy and high‐resolution X‐ray absorption near edge spectroscopy can be carried out by using this spectrometer. X‐ray emission preliminary results with high‐resolution about 3 eV of Mn compounds were obtained, which confirmed the feasibility of the spectrometer. The application about Eu (III) retention on manganese dioxide was also studied using this spectrometer. Compared with conventional X‐ray absorption fine structure spectroscopy technique, the fluorescence peak of probed element [Eu (III) Lα] and matrix constituents (Mn Kα) were discriminated using this technique, indicating its superiority in fluorescence detection. Copyright © 2013 John Wiley & Sons, Ltd.     

Depth profiling of dopants implanted in Si using the synchrotron radiation based high‐resolution grazing emission technique

We report on the surface‐sensitive grazing emission X‐ray fluorescence technique combined with synchrotron radiation excitation and high‐resolution detection to realize depth‐profile measurements of Al‐implanted Si wafers. The principles of grazing emission measurements as well as the benefits offered by synchrotron sources and wavelength‐dispersive detection setups are presented. It is shown that the depth distribution of implanted ions can be extracted from the dependence of the X‐ray fluorescence intensity on the grazing emission angle with nanometer‐scale precision provided that an analytical function describing the shape of the depth distribution is assumed beforehand. If no a priori assumption is made, except a bell shaped form for the dopant distribution, the profile derived from the measured angular distribution is found to reproduce quite satisfactorily the depth distribution of the implanted ions. Copyright © 2012 John Wiley & Sons, Ltd.     

同步辐射全反射XRF实验

本文叙述了同步辐射全反射X射线荧光分析的实验装置和方法，给出了几种标准物质TXRF实验的检出限，我们已在细胞元素谱、体液和水样方面作了一些研究。并对实验结果进行了讨论。     

Synchrotron X‐ray tests of an L‐shaped laterally graded multilayer mirror for the analyzer system of the ultra‐high‐resolution IXS spectrometer at NSLS‐II

Characterization and testing of an L‐shaped laterally graded multilayer mirror are presented. This mirror is designed as a two‐dimensional collimating optics for the analyzer system of the ultra‐high‐resolution inelastic X‐ray scattering (IXS) spectrometer at National Synchrotron Light Source II (NSLS‐II). The characterization includes point‐to‐point reflectivity measurements, lattice parameter determination and mirror metrology (figure, slope error and roughness). The synchrotron X‐ray test of the mirror was carried out reversely as a focusing device. The results show that the L‐shaped laterally graded multilayer mirror is suitable to be used, with high efficiency, for the analyzer system of the IXS spectrometer at NSLS‐II.     

A scanning Kelvin probe for synchrotron investigations: the in situ detection of radiation‐induced potential changes

A wide range of high‐performance X‐ray surface/interface characterization techniques are implemented nowadays at every synchrotron radiation source. However, these techniques are not always `non‐destructive' because possible beam‐induced electronic or structural changes may occur during X‐ray irradiation. As these changes may be at least partially reversible, an in situ technique is required for assessing their extent. Here the integration of a scanning Kelvin probe (SKP) set‐up with a synchrotron hard X‐ray interface scattering instrument for the in situ detection of work function variations resulting from X‐ray irradiation is reported. First results, obtained on bare sapphire and sapphire covered by a room‐temperature ionic liquid, are presented. In both cases a potential change was detected, which decayed and vanished after switching off the X‐ray beam. This demonstrates the usefulness of a SKP for in situ monitoring of surface/interface potentials during X‐ray materials characterization experiments.     

Nanoresolution interface studies in thin films by synchrotron x‐ray diffraction and by using x‐ray waveguide structure

In the last years we performed several measurements with synchrotron radiation of several facilities to reveal interesting interface phenomena on the nanoscale. We used both x‐ray diffraction [1] , [2] (XRD) and spectrometry techniques. In this paper, we briefly summarize the results obtained from diffraction measurements, which lead us to our recent grazing incidence x‐ray fluorescence analysis (GIXRF) and extended x‐ray absorption fine structure (EXAFS) experiments. We show how a combination of experimental methods of GIXRF analysis and EXAFS spectroscopy in fluorescence detection with x‐ray standing waves (XSW) technique was applied for the depth profiling of a‐Si/Co/a‐Si layers with nanometer resolution to monitor the growth of CoSi intermetallic phase. The investigated layers were placed into the waveguide structure formed by two Ta films to increase sensitivity and accuracy of the measurements. Copyright © 2009 John Wiley & Sons, Ltd.     

肺癌,宫颈癌细胞凋亡前后微量元素的变化

全反射荧光分析（ＴＸＲＦ）比常规荧光分析（ＸＲＦ）具有更高的灵敏度。我们在北京正负电子对撞机同步辐射３ＷＩＡ新光束线改建的同步辐射荧光站上（更换了新探测器及相应谱仪系统）,用ＴＸＦＲ对肺癌细胞和宫颈癌细胞进行了凋亡前后的研究,得到了这些细胞凋亡前后的荧光谱。从分析这些谱的结果我们可以看到。凋亡前后这些癌细胞中某些微量元素的含量有了变化,甚至是明显变化。从这些变化中我们可得到一些启发如果到它们的变化     

Synchrotron microanalysis techniques applied to potential photovoltaic materials

X‐ray synchrotron radiation techniques are used to characterize photovoltaic‐related semiconductors. Micro‐X‐ray‐fluorescence and X‐ray beam induced current mapping of multicrystalline silicon photovoltaic cells show metallic impurities accumulating at the interface of crystallographic defects, and current variations over the cell that are attributed to bulk defects and structural variation of the silicon. Similarly, studies on a single‐crystal GaAs using X‐ray fluorescence and X‐ray excited optical luminescence show an inhomogeneous As distribution correlated with the photoluminescence signal, with higher As concentration regions having stronger photoluminescence signal. Both examples show how the combination of synchrotron microanalysis techniques can contribute to a better understanding of the optical properties of photovoltaic materials.     

石墨炉原子吸收法测定饮料中硒

本文采用Ｐｄ（ＮＯ３）２－ＴｒｉｏｔｎＸ－１００作硒的改进剂，使Ｓｅ的允许灰化温度提高到１２００℃吸光度提高到２．９２倍，用塞曼效应校正背景，有效地克服，Ｐ和Ｆｅ等的光谱干扰，此法检测限为８．０ｎｇ／ｍＬ线性范围为１０－１２０ｎｇ／ｍＬ，线性相关系数为ｒ＝０．９９３１。     

X‐ray excited optical luminescence from crystalline silicon

Synchrotron based X‐ray excited optical luminescence (XEOL) has been measured with many direct bandgap semiconductors. We present XEOL measurements on crystalline silicon (Si), obtained despite of its indirect bandgap and the consequently low luminescence efficiency. Spectra of monocrystalline and multicrystalline (mc) Si at room temperature are compared to theoretical spectra. A possible application in the synchrotron‐based research on mc‐Si is exemplified by combining XEOL, X‐ray fluorescence (XRF) spectroscopy, photoluminescence (PL) spectroscopy, and microscope images of grain boundaries. This approach can be utilized to investigate the recombination activity of metal precipitates, to analyze areas of different lifetimes on mc‐Si samples and to correlate additional material parameters to XRF measurements. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The coherent radiation fraction of low‐emittance synchrotrons

In this work the coherence properties of the synchrotron radiation beam from an X‐ray undulator in a fourth‐generation storage ring are analyzed. A slightly focused X‐ray beam is simulated using a wavefront propagation through a non‐redundant array of slits and the mutual coherence function is directly obtained and compared with the Gaussian–Schell approximation. The numerical wave propagation and the approximate analytical approaches are shown to agree qualitatively, and it is also shown that, when the coherent fraction is selected by a finite aperture before the focusing element, even achromatic focusing systems like total reflection mirrors become slightly chromatic. This effect is also well accounted for in the Gaussian–Schell model. The wavefront propagation simulation through the non‐redundant array was repeated with an imperfect mirror demonstrating that, although the wavefront is distorted, its coherent length is practically unchanged.     

Recent Advances in TXRF

Abstract

Total reflection X‐ray fluorescence analysis (TXRF) is a special method of energy‐dispersive X‐ray fluorescence analysis extending EDXRF to the ultra trace element level. The achievable detection limits depend on the excitation source and are in the range of picograms to femtograms. Only small amounts of sample are required and the quantification by adding one element as an internal standard is easy as thin film approximation is valid. In this article, the recent advances in TXRF are reviewed with over 80 references. The principles, advantages, instrumentation, improvements with X‐ray optics, synchrotron radiation as excitation sources as well as various fields of application, wafer surface analysis, depth profiling, absorption spectroscopy, medical samples, biological samples, environmental monitoring, archeological and polymer samples are described. Related techniques are also mentioned and discussed.     

Mercury in archeological hair samples from Xiongnu burials (Noin‐Ula,Mongolia): SR XRF and CXRM analysis

A technique has been developed for determining mercury content in the concentration range of 1–1000 μg/g in hair samples by X‐ray fluorescence analysis using synchrotron radiation (synchrotron radiation X‐ray fluorescence, Siberian Synchrotron and Terahertz Radiation Center, Budker Institute of Nuclear Physics SB RAS). The mercury content was identified in archeological hair samples from an ancient burial of Xiongnu nobility (Mongolia, mound 22, 1^st century BC–1^st century AD); the content values were elevated (up to 1100 μg/g) in all the samples (n = 41). An X‐ray microanalysis using polycapillary lenses in a confocal scheme (confocal X‐ray microscopy station) was developed at the Synchrotron radiation X‐ray fluorescence to establish mercury distribution in a cross section of hair shaft with a spatial resolution of 5 μm. The findings of the study make it possible to assume exogenous income of mercury (from the burial environment) to the hair.