Applications of synchrotron radiation in materials analysis

The synchrotron radiation (SR) emitted by circulating high-energy electrons has extraordinary properties: The light is intensive and bright, it is tunable and highly collimated, and finally, it is linearly polarized. These exceptional properties have initiated a unique revival of many spectroscopies using electromagnetic radiation. The techniques of special concern for materials analysis which are treated in this article are: X-ray absorption, reflection, fluorescence, diffraction and topography. A number of examples will be given in order to illustrate the possibilities of these techniques when SR is used.On leave of absence from Institut für Festkörperforschung, KFA Jülich, D-5170 Jülich, Federal Republic of Germany     

Bulk and microprobe analysis for trace elements with synchrotron radiation

Blood serum samples were irradiated by monochromatic synchrotron radiation (15 keV) and by 2.4-MeV protons to compare their performance for the detection of trace elements by x-ray fluorescence (XRF) spectrometry. Absolute concentration assignment was based on the addition of an internal standard and on a method which uses the incoherent and coherent radiation as a flux monitor of the incoming beam. Preliminary experiments with a synchrotron XRF microprobe are reported.     

X-ray fluorescence spectrometry with synchrotron radiation

X-ray fluorescence spectrometry (x.r.f.) can be done through excitation with synchrotron radiation. This permits multi-element determinations in the trace region with improved detection limits compared to conventional x.r.f. Detection limits are evaluated and compared with theoretically calculated values. For a beam diameter of 0.5 mm and a sample of 1 mg cm^?2, absolute detection limits are between 0.1 and 0.4 pg. The dependence of the detection limit on the atomic number is reduced, when white synchrotron radiation is used for excitation instead of monochromatic radiation. The optimum of the limit of detection on the Z-scale can be shifted to higher atomic numbers and improved through filtration of the primary radiation by aluminium absorbers. Preparation of samples on different polymeric films is discussed in relation to blank values.     

AZ-1518 Photoresist analysis with synchrotron radiation using high-resolution time-of-flight mass spectrometry

With the aim of identifying molecular modifications among photoresists unexposed and previously exposed to the ultraviolet light the photon stimulated ion desorption (PSID) technique was employed in the study of the AZ-1518 photoresist. Data acquisition was performed at the Brazilian Synchrotron Light Source (LNLS), during a single-bunch operation mode of the storage ring and using high-resolution time-of-flight mass spectrometry (TOF-MS) for ion analysis. PSID mass spectra on both photoresists (unexposed and exposed) were obtained following the S K-shell photoexcitation and desorption ion yield curves have been determined for the main fragments as a function of the photon energy. The AZ-1518 photoresists presented different PSID spectra, showing characteristic fragments. Most of the analyzed ions showed larger relative yields for the exposed photoresist. Fragments related to the photochemical decomposition of the photoresist could be clearly identified. These results showed that the PSID technique is adequate to investigate structural changes in molecular level in unexposed and exposed photoresists.     

Applications of synchrotron radiation in forensic trace evidence analysis

Synchrotron radiation sources have proven to be highly beneficial in many fields of research for the characterization of materials. However, only a very limited proportion of studies have been conducted by the forensic science community. This is an area in which the analytical benefits provided by synchrotron sources could prove to be very important. This review summarises the applications found for synchrotron radiation in a forensic trace evidence context as well as other areas of research that strive for similar analytical scrutiny and/or are applied to similar sample materials. The benefits of synchrotron radiation are discussed in relation to common infrared, X-ray fluorescence, tomographic and briefly, X-ray diffraction and scattering techniques. In addition, X-ray absorption fine structure analysis (incorporating XANES and EXAFS) is highlighted as an area in which significant contributions into the characterization of materials can be obtained. The implications of increased spatial resolution on microheterogeneity are also considered and discussed.     

Non-destructive depth profile analysis using synchrotron radiation excited XPS

We have used synchrotron radiation as excitation source in an X-ray photoelectron spectroscopy (XPS) experiment to analyse surface-near element depth profiles non-dectructively. By tuning the photon energy one can vary the kinetic energy of the photoelectrons and in turn the information depth of the measurement. To quantify the sample geometry (e.g. layer thicknesses) model calculations similar as for angle-resolved XPS (ARXPS) measurements are necessary. We have successfully applied this technique to several samples. We will show how to calculate the relative intensities of the peaks, using photoionization cross sections and an experimentally determined analyzer transmission function and the procedure to quantify the geometry for a model sample: natively oxidized Ta covered by carbon contamination. At Sn-doped indium oxide samples we found a sub-monolayer of segregated Sn at the surface which was expected from previous investigations.     

X-ray fluorescent analysis using synchrotron radiation: Subjects of research

The brief review has been presented about the application of X-ray fluorescent analysis using synchrotron radiation (storage ring VEPP-3, BINP SB RAS) for determination of elemental composition of the samples of different nature–biological and geological samples, objects of environment, archeological objects, and new materials. The feature of the presented research is the employment of the unique properties of synchrotron radiation, which allow analyzing samples of small mass (of the order of several milligrams), and also scanning core of bottom sediments with high resolution (less than 1 mm) that is not practical to realize by traditional analysis methods.     

Chemical imaging of catalytic solids with synchrotron radiation

Heterogeneous catalysis is a term normally used to describe a group of catalytic processes, yet it could equally be employed to describe the catalytic solid itself. A better understanding of the chemical and structural variation within such materials is thus a pre-requisite for the rationalising of structure-function relationships and ultimately to the design of new, more sustainable catalytic processes. The past 20 years has witnessed marked improvements in technologies required for analytical measurements at synchrotron sources, including higher photon brightness, nano-focusing, rapid, high resolution data acquisition and in the handling of large volumes of data. It is now possible to image materials using the entire synchrotron radiative profile, thus heralding a new era of in situ/operando measurements of catalytic solids. In this tutorial review we discuss the recent work in this exciting new research area and finally conclude with a future outlook on what will be possible/challenging to measure in the not-too-distant future.     

EXAFS studies with synchrotron radiation of polystyrene-ruthenium catalyst

The local structure of the metal-atom surroundings in polystyrene-ruthenium complexes (PSt-Ru) has been studied by EXAFS. EXAFS at the Ru K-edge (22,118 keV) has been measured for metallic Ru and PSt-Ru. Numerical elaboration of the data gives the Ru-C distance (d = 2.05 A) and the number of carbon atoms coordinated to the metal (coordination number 6) in PSt-Ru.     

Instrumentation for FT-IR reflection spectroscopy with synchrotron radiation

A versatile experimental set-up for infrared reflectance measurements with synchrotron radiation and its adaptation to a beamline is presented. Particular consideration is given to the collimation and the polarization of incident radiation. The performance is characterized with experimental results. Due to the high brilliance of the synchrotron radiation source, the irradiation of samples smaller than 1 mm(2) was found to be improved by more than one order of magnitude when compared to a globar.     

Extinction correction and synchrotron radiation

The primary extinction factor y_p is defined as the ratio of the integrated reflection from a coherently diffracting domain to the integrated kinematical reflection from the same domain. When y_p is larger than 0.5 it may be approximated by y_p = exp{−(αδ)2}, where α is about 0.5 andδ the average size of the coherent domain when measured in units of the extinction length A,δ = D/λ. Transfer equations are applied to symmetrical Laue diffraction, and the reflectivity per unit length, Σ(ε) is solved from the measured reflecting ratio as a function of the rocking angleε =θ− θ_B. Measurements with conventional x-ray sources are made on single crystal slabs of Be and Si using AgKΒ, MoKα₁ and CuKα radiation. The primary extinction factor y_p(ε) is solved from a point-by-point comparison of two measurements where the extinction length λ is changed by varying the polarization and/or wavelength of the x-ray beam. The results show that primary and secondary extinction are strongly correlated, and that the customary assumption of independent size and orientation distributions of crystal mosaics is unjustified. The structure factors for Be and Si show close agreement with other recent measurements and calculations. The limitations of the method are discussed in length, particularly the effects of beam divergences and incoherence of the rays in the crystal. It is concluded that under typical experimental conditions the requirements of the theory are met. Practical limitations arising from the use of characteristic wavelengths and unpolarized radiation prohibit the use of the full potential of the method. The properties of a synchrotron radiation source are compared with a conventional x-ray source, and it is demonstrated that the experimental limitations can be removed by the use of synchrotron radiation. A diffraction experiment with synchrotron radiation is outlined, as well as generalization of the method to small spherical crystals.     

DVC analysis of a polymer material subjected to tensile loading with synchrotron radiation tomography

Subsurface deformation behavior of a polymeric material is studied through the digital volume correlation (DVC) technique. Fundamental principles of the DVC technique are presented and the supplemental state-of-the-art algorithmic schemes to improve the efficiency and accuracy of the DVC analysis are also introduced. Tensile tests on an epoxy material are performed in conjunction with synchrotron radiation tomography. In order to create randomly distributed grayscale values in the tomograms for the following image analysis, microscale high-density particles are embedded when the epoxy specimens are fabricated. 3D tomographic images taken at multiple loading steps are utilized for the DVC analysis. The performance of the present DVC analysis is evaluated with the experimental data.     

Mid-IR synchrotron radiation for molecular specific detection in microchip-based analysis systems

Microstructures constructed from SU-8 polymer and produced on CaF₂ base plates have been developed for microchip-based analysis systems used to perform FTIR spectroscopic detection using mid-IR synchrotron radiation. The high brilliance of the synchrotron source enables measurements at spot sizes at the diffraction limit of mid-IR radiation. This corresponds to a spatial resolution of a few micrometers (5–20 m). These small measurement spots are useful for lab-on-a-chip devices, since their sizes are comparable to those of the structures usually used in these devices. Two different types of microchips are introduced here. The first chip was designed for time-resolved FTIR investigations of chemical reactions in solution. The second chip was designed for chip-based electrophoresis with IR detection on-chip. The results obtained prove the operational functionality of these chips, and indicate the potential of these new devices for further applications in (bio)analytical chemistry.     

L-subshell Coster-Kronig yields measured with synchrotron radiation

The synchrotron photoionization method was applied to measure L-subshell Coster-Kronig yields. This method is based on the capability of tuning the energy of the synchrotron photons producing a selective subshell ionization. Two foil samples of Yb and Ta were irradiated and their characteristic spectra were recorded. Data were analyzed using a new formalism (based on a matrix representation) for expressing X-ray fluorescence intensities involving Coster-Kronig transitions. The results obtained in this work are f₁₂ = 0.249 ± 0.021, f₁₃ = 0.408 ± 0.055 and f₂₃ = 0.186 ± 0.040 for Yb, and f₁₂ = 0.168 ± 0.039, f₁₃ = 0.322 ± 0.072 and f₂₃ = 0161 ± 0.053 for Ta. These data are very reliable and represent a valuable information for spectroscopists, considering the lack of data for L-shell parameters.     

Instruments and methods for small-angle scattering with synchrotron radiation

Some aspects of small-angle X-ray scattering (SAXS) instrumentation for synchrotron radiation (SR) are considered below. The basic layout of instruments as well as some of the problems arising from the nature of the source and of the type of experiments are discussed. Further, a survey of the instruments available at major SR facilities is given.     

Fluorescence of rare gas clusters excited with synchrotron radiation

A cluster beam experiment for fluorescence measurements on rare gas clusters has been built up. First results on the evolution of energy levels of neutral krypton clusters with a cluster size between 200–8500 atoms/cluster are reported. The well known bulk excitons of solid krypton do not merge into the first atomic lines and appear only in clusters larger than 300 atoms/cluster. Smaller clusters absorb only at energies which fit well with surface excitons of the solid.