Characterization of a submicro-X-ray fluorescence setup on the B16 beamline at Diamond Light Source.

An X-ray fluorescence setup has been tested on the B16 beamline at the Diamond Light Source synchrotron with two different excitation energies (12.7 and 17 keV). This setup allows the scanning of thin samples (thicknesses up to several micrometers) with a sub-micrometer resolution (beam size of 500 nm × 600 nm determined with a 50 µm Au wire). Sensitivities and detection limits reaching values of 249 counts s-1 fg-1 and 4 ag in 1000 s, respectively (for As Kα excited with 17 keV), are presented in order to demonstrate the capabilities of this setup. Sample measurements of a human bone and a single cell performed at B16 are presented in order to illustrate the suitability of the setup in biological applications.

Combined evaluation of grazing incidence X-ray fluorescence and X-ray reflectivity data for improved profiling of ultra-shallow depth distributions.

The continuous downscaling of the process size for semiconductor devices pushes the junction depths and consequentially the implantation depths to the top few nanometers of the Si substrate. This motivates the need for sensitive methods capable of analyzing dopant distribution, total dose and possible impurities. X-ray techniques utilizing the external reflection of X-rays are very surface sensitive, hence providing a non-destructive tool for process analysis and control. X-ray reflectometry (XRR) is an established technique for the characterization of single- and multi-layered thin film structures with layer thicknesses in the nanometer range. XRR spectra are acquired by varying the incident angle in the grazing incidence regime while measuring the specular reflected X-ray beam. The shape of the resulting angle-dependent curve is correlated to changes of the electron density in the sample, but does not provide direct information on the presence or distribution of chemical elements in the sample. Grazing Incidence XRF (GIXRF) measures the X-ray fluorescence induced by an X-ray beam incident under grazing angles. The resulting angle dependent intensity curves are correlated to the depth distribution and mass density of the elements in the sample. GIXRF provides information on contaminations, total implanted dose and to some extent on the depth of the dopant distribution, but is ambiguous with regard to the exact distribution function. Both techniques use similar measurement procedures and data evaluation strategies, i.e. optimization of a sample model by fitting measured and calculated angle curves. Moreover, the applied sample models can be derived from the same physical properties, like atomic scattering/form factors and elemental concentrations; a simultaneous analysis is therefore a straightforward approach. This combined analysis in turn reduces the uncertainties of the individual techniques, allowing a determination of dose and depth profile of the implanted elements with drastically increased confidence level. Silicon wafers implanted with Arsenic at different implantation energies were measured by XRR and GIXRF using a combined, simultaneous measurement and data evaluation procedure. The data were processed using a self-developed software package (JGIXA), designed for simultaneous fitting of GIXRF and XRR data. The results were compared with depth profiles obtained by Secondary Ion Mass Spectrometry (SIMS).

A monochromatic confocal micro-x-ray fluorescence (µXRF) spectrometer for the lab.

Confocal micro-x-ray fluorescence (µXRF) is a powerful tool to analyze the spatial distribution of major, minor, and trace elements in three dimensions. Typical (confocal) µXRF measurements in the lab use polychromatic excitation, complicating quantification and fundamental parameter-based corrections and furthermore deteriorating peak-to-background ratios due to scattered bremsstrahlung. The goal for the new setup was to remedy these problems, without sacrificing spatial resolution, and keep it flexible for different excitation energies and transportation to other sources. The source assembly consists of a water-cooled fine-focus x-ray diffraction tube and a parallel beam-mirror, which produces a quasi-parallel, monochromatic beam. The presented results were obtained using a 2 kW molybdenum tube and a mirror for Mo-Kα. The confocal setup itself consists of two polycapillary half-lenses, one for the source side and the other for the detector side, where a 50 mm2 silicon drift detector is mounted. Both polycapillaries have a focus size of ∼15 µm for Mo-Kα. The second polycapillary can also be exchanged for a custom-designed collimator in order to perform non-confocal µXRF. Details of the technical setup and results from technical and biological samples are presented. Detection limits for selected elements from Ca to Pb in the confocal and non-confocal mode were established (e.g., 1 µg/g non-confocal and 20 µg/g confocal for As) using the NIST standard reference materials (SRMs) 621 and 1412. Furthermore, the results of the measurements of SRM 621 were evaluated using the fundamental parameter based quantification software ATI-QUANT. The results are compared with the certified values and generally are in good agreement.

Elemental imaging of trace elements in bone samples using micro and nano-X-ray fluorescence spectrometry.

Our group employs micro- and nano-X-ray fluorescence spectrometry (XRF) for the investigation of bone tissue. The manuscript presents the results of 3 various projects, in which spatial distribution of trace elements in bone samples was studied. The first study investigated the distribution of the elemental constituents of Mg-based implants at various stages of the degradation process in surrounding bone tissue with a focus on magnesium (Mg) and yttrium (Y). The analysis was performed in laboratory of Atominstitut using a special micro-XRF spectrometer for light element detection. The second study is devoted to the spatial distribution of Zn in high-grade sclerosing osteosarcoma mapped by confocal synchrotron radiation induced micro-XRF. Tumor zinc levels were compared with adjacent normal tissue. For discrimination between healthy and diseased bone quantitative backscattered electron imaging was used. The third experiment demonstrates the performance of synchrotron radiation induced nano-XRF with beam size of about 500 nm for bone tissue investigation. Special emphasis is set to advantages of micro- and nano-XRF in bone analysis as well as overcoming possible limitations.

A novel vacuum spectrometer for total reflection x-ray fluorescence analysis with two exchangeable low power x-ray sources for the analysis of low, medium, and high Z elements in sequence.

The extension of the detectable elemental range with Total Reflection X-ray Fluorescence (TXRF) analysis is a challenging task. In this paper, it is demonstrated how a TXRF spectrometer is modified to analyze elements from carbon to uranium. Based on the existing design of a vacuum TXRF spectrometer with a 12 specimen sample changer, the following components were renewed: the silicon drift detector with 20 mm(2) active area and having a special ultra-thin polymer window allowing the detection of elements from carbon upwards. Two exchangeable X-ray sources guarantee the efficient excitation of both low and high Z elements. These X-ray sources were two light-weighted easily mountable 35 W air-cooled low-power tubes with Cr and Rh anodes, respectively. The air cooled tubes and the Peltier-cooled detector allowed to construct a transportable tabletop spectrometer with compact dimensions, as neither liquid nitrogen cooling for the detector nor a water cooling circuit and a bulky high voltage generator for the X-ray tubes are required. Due to the excellent background conditions as a result of the TXRF geometry, detection limits of 150 ng for C, 12 ng for F, and 3.3 ng for Na have been obtained using Cr excitation in vacuum. For Rh excitation, the detection limits of 90 pg could be achieved for Sr. Taking 10 to 20 µl of sample volume, extrapolated detection limits in the ng/g (ppb) range are resulting in terms of concentration.

Combination of grazing incidence x-ray fluorescence with x-ray reflectivity in one table-top spectrometer for improved characterization of thin layer and implants on/in silicon wafers.

As Grazing Incidence X-ray Fluorescence (GIXRF) analysis does not provide unambiguous results for the characterization of nanometre layers as well as nanometre depth profiles of implants in silicon wafers by its own, the approach of providing additional information using the signal from X-ray Reflectivity (XRR) was tested. As GIXRF already uses an X-ray beam impinging under grazing incidence and the variation of the angle of incidence, a GIXRF spectrometer was adapted with an XRR unit to obtain data from the angle dependent fluorescence radiation as well as data from the reflected beam. A θ-2θ goniometer was simulated by combining a translation and tilt movement of a Silicon Drift detector, which allows detecting the reflected beam over 5 orders of magnitude. HfO2 layers as well as As implants in Silicon wafers in the nanometre range were characterized using this new setup. A just recently published combined evaluation approach was used for data evaluation.