The complexity and heterogeneity of bone chemistry makes it difficult to discern information on physiological and taphonomic processes stored within the bone matrix. Analysis of archaeological and palaeontological bone becomes more difficult because in many cases the most pivotal specimens are too scientifically valuable for destructive analysis. This problem is further escalated by the fact that the heterogeneity of the bone may cause small "pockets" of preservation that can be missed during sampling. Therefore, a non-destructive technique that can spatially resolve such heterogeneity within the bone is needed. Here we use microfocus, non-destructive synchrotron-based X-Ray Fluorescence (XRF) imaging and X-ray Absorption Spectroscopy (XAS) to map the organic constituents within extant and fossil bovid bones. XAS analysis of sulfur allowed organic sulfur (within collagen as methionine) to be distinguished from inorganic sulfate (within bone apatite). Mapping and quantification of organic sulfur within the samples were made by setting the beam to the methionine resonance, allowing for the detection, distribution and quantification of collagen present by using organic sulfur as an internal marker. Results show organic sulfur to be distributed in small "pockets" throughout the bone matrix in both extant and fossil specimens. Significant loss of organic sulfur was seen in specimens between 100 ka and 650 ka with little organic sulfur preservation persisting after this date. Comparison of residual organic sulfur concentrations as a function of sample age revealed a second order rate law for organic sulfur oxidation (k approximate to 1 x 10(-5 )y(-1)) within bone. These results show that non-destructive, synchrotron-based XRF mapping of organic sulfur is a useful tool for not only calculating rates of collagen degradation through time, but also identifying areas of potential collagen preservation for other paleobiological applications such as proteomics and stable isotope analyses.

We have studied the structural mechanisms responsible for the magnetic reorientation between in-plane and out-of-plane magnetization in the (25 nm Pt)/(3 and 10 nm Co)/(3 nm Pt) trilayer systems irradiated with nanosecond XUV pulses generated with laser-driven gas-puff target plasma source of a narrow continuous spectrum peaked at wavelength of 11 nm. The thickness of individual layers, their density, chemical composition and irradiation-induced lateral strain were deduced from symmetric and asymmetric X-ray diffraction (XRD) patterns, grazing-incidence X-ray reflectometry (GIXR), grazing incidence X-ray fluorescence (GIXRF), extended X-ray absorption fine structure (EXAFS) and transmission electron microscopy (TEM) measurements. In the as grown samples we found, that the Pt buffer layers are relaxed and that the layer interfaces are sharp. As a result of a quasi-uniform irradiation of the samples, the XRD, EXAFS, GIXR and GIXRF data reveal the formation of two distinct layers composed of Pt1-xCox alloys with different Co concentrations, dependent on the thickness of the as grown magnetic Co film but with similar similar to 1% lateral tensile residual strain. For smaller exposure dose (lower number of accumulated pulses) only partial interdiffusion at the interfaces takes place with the formation of a tri-layer composed of Co-Pt alloy sandwiched between thinned Pt layers, as revealed by TEM. The structural modifications are accompanied by magnetization changes, evidenced by means of magneto-optical microscopy. The difference in magnetic properties of the irradiated samples can be related to their modification in Pt1xCox alloy composition, as the other parameters (lateral strain and alloy thickness) remain almost unchanged. The out-of-plane magnetization observed for the sample with initially 3 nm Co layer can be due to a significant reduction of demagnetization factor resulting from a lower Co concentration. (C) 2018 Elsevier B.V. All rights reserved.

The confocal mu XRF spectrometer of Atominstitut (ATI) was transported and set up at the X-ray Fluorescence beamline at Elettra -Sincrotrone Trieste. It was successfully adjusted to the incoming beam (9.2 keV). Test measurements on a free-standing Cu wire were performed to determine the size of the focused micro-beam (non-confocal mode, 56 x 35 mu m(2)) and the size of the confocal volume (confocal mode, 41 x 24 x 34 mu m(2)) for the Cu-K alpha emission. In order to test the setup's capabilities, two areas on different human bone samples were measured in confocal scanning mode. For one of the samples the comparison with a previous mu XRF measurement, obtained with a low power X-ray tube in the lab, is presented.

Telluride films are widely applied in data storage devices (advanced resistive memories, DVDs and Blue-rays disks), photovoltaic cells and infrared detectors. The properties of thin telluride alloys are deeply influenced by their chemical composition and compositional depth profile, whereas surface/interface effects may become preponderant in ultrathin films. The combination of X-ray reflectometry (XRR) and grazing-incidence X-ray fluorescence (GIXRF) is particularly adequate to probe these complex thin layered materials. In this paper, we evaluate the performances of Lab-based and synchrotron-based XRR/GIXRF strategies to characterize ultrathin (< 10 nm) amorphous titanium-tellurium films elaborated by Physical Vapor Deposition (PVD), and capped in situ with 5 nm-tantalum passivation layer. We highlighted the impact of the instrumental setup on the qualitative XRR and GIXRF data and on the quantitative information deduced from the combined analysis. Both synchrotron-based and Lab-based strategies were sensitive enough to track the impact of small PVD process changes on the chemical depth-profiles, and to unambiguously reveal undesired tantalum-tellurium inter-diffusion that was confirmed by X-Ray Photoelectron Spectroscopy.

X‐ray fluorescence (XRF) analysis is an established technique for quantitative elemental analysis. Grazing incidence X‐ray fluorescence analysis (GIXRF) extends the application of XRF to thin films because of the improved sensibility. GIXRF shares the phenomenological basis with X‐ray reflectivity, a scattering technique typically used for thin‐film metrology, offering sensitivity to elemental depth. This work presents the GIMPy (Grazing Incidence Material analysis with Python) software developed for the analysis of GIXRF spectra by combining a fundamental parameter approach to quantitative XRF analysis and the electric field calculation in stratified media, which also delivers the total reflected intensity as measured in X‐ray reflectivity experiments. An XRF experiment can be modelled from the source, modulation of the primary beam, interactions with a layered sample, absorption of the emitted fluorescence intensities, and the response function of semiconductor energy dispersive detectors obtaining a simulation of the expected spectrum that can be directly compared with the acquired one. The fundamental parameter part includes signal enhancements by cascade effect and secondary fluorescence. The code offers the possibility to take into account the effects originated by deviations from ideal conditions: non‐monochromatic excitation, beam divergence, beam size and shape, sample‐inspected area, and solid angle of detection. The functionality of the code is demonstrated on a set of semiconductor substrates (Si, Ge, and GaAs) and shallow dopant distributions of arsenic in silicon. Copyright © 2017 John Wiley & Sons, Ltd.

GIXRF (Grazing incidence X-Ray Fluorescence) is an analytical technique with high potential in the study of depth profiles and in the characterization of thin layered structures. To extract information from a GIXRF measurement and determine the layer composition it is necessary to compare the experimental data with simulation. However at the moment this thesis has been written, there is no software widely recognized from the scientific community as the reference software for the analysis. For this reason this work of thesis deals with the development of an analytical software and its application to several case studies. A program called GIMPy is presented. The program is capable to perform simulations of the expected GIXRF signal from a given model, but also of the expected fluorescence signal at high angle of incidence and the reflectivity (XRR). The use of a programming language like Python makes the library extremely portable, easily extendible and flexible thanks to its object oriented syntax and scripting capabilities. GIMPy bases the modelling of the electric field propagation inside the sample and the expected fluorescence from the theoretical description found in literature. Moreover a series of methods were developed to account for the effect of the instrumental set-up geometry, the detector response, indirect excitation and primary beam shape and energy composition. A round-robin related to GIXRF comparison with several institutes developing an analytical software has been organised. The comparison showed a good agreement between the results obtained with GIMPy and the other programs. GIXRF has then been applied to the characterisation of several systems. A combined XRR and GIXRF analysis of multi-layered transparent and conductive oxide films (TCO) of technological interest resulted in a nondestructive and precise characterization of their structures. Measurements were performed at the ESRF synchrotron facility and in the laboratory using a Cu tube as source. Combining the measurements performed with dif- ferent instrumental set-ups the effectiveness of the combined XRR-GIXRFapproach, that has proved already effective in the past, has been further shown. It has been possible to evidence the existence of a thin inter dif- fusion profile induced by annealing the samples, showing a sensitivity to structural changes in the depth of 0.5-1 nm. GIXRF measurements performed on Sn implants in Ge provided information about the total dose retained by the sample after an implantation process. Synchrotron tunable excitation energy was extremely valuable for the fluorescence analysis.The two different modelling strategies used for data fitting, one using a SIMS profile as an input the other an analytical description of the depth profile, and returned values close to the one obtained with other techniques. A new technology based on the deposition of ALD coatings for the preservation of cultural heritage object has been characterised with XRR and GIXRF. The XRR measurements were effective in revealing the deterioration of the coatings after the effect of an accelerated ageing process. Moreover the analysis of GIXRF also revealed the formation of nano-particles at the top of the surface, and allowed the characterisation of their size and composition. The last chapter shows some theoretical calculations investigating GIXRF potential in the size and chemical characterisation of nano-particles. It is shown how the experimental setup and the sample preparation can influ- ence the outcome of the measurement. The theoretical calculations are also reinforced by the result obtained on some preliminary experiments on Gold nano-particles.

The combination of X-ray reflectivity and grazing incidence X-ray fluorescence has been applied to the characterization of an In2O3/Ag/In2O3 stack for advanced photovoltaic applications. X-ray reflectivity is a well-known method for the characterization of multilayered structures by providing information on the thickness and the in-depth electronic density. Grazing incidence X-ray fluorescence provides information about the elemental depth distribution. As these techniques are based on similar measurement procedures and data evaluation approaches, their combination reduces the uncertainties of the individual techniques and provides an accurate depth-resolving analysis of multi-layers.It has been shown that the combination of the techniques give insight into the material composition and the layers structure (thickness, density) as well as modifications induced by a thermal annealing.As X-ray fluorescence signals have been acquired at different excitation energies, the influence of this parameter on the sensitivity of the measurements to the structural properties has been shown. (C) 2015 Elsevier B.V. All rights reserved.

(1) CEA, LETI, MINATEC Campus, 17 rue des Martyrs, 38054 Grenoble Cedex 9, France (2) MNF, CMM–Irst, Fondazione Bruno Kessler, Via Sommarive 18, 38123 Povo, Trento, Italy (3) Atominstitut, Vienna University of Technology , 1020 , Vienna , Austria (4) Dpt. of Industrial Engineering, University of Trento, via Sommarive 9, 38123 Povo, Trento, Italy (5) CIMAP , 6 boulevard du Maréchal Juin , 14050 Caen Cedex 4, France (6) CRISMAT-Ensicaen, IUT-Caen UCBN, 6 boulevard du Maréchal Juin, 14050 Caen Cedex 4, France