Performances of a metallic magnetic calorimeter for the measurement of hard X‐ray emission intensities

The energy spectrum analysis of X‐ray intensities with semiconductor detectors is often difficult because their energy resolution is usually not good enough to separate the different X‐ray lines. Metallic magnetic calorimeters (MMCs) can be an alternative; they can offer both high energy resolution and high intrinsic detection efficiency from 0 to 100 keV. MMCs are thermal detectors; that is to say, the energy of each absorbed photon is measured as a temperature elevation. At very low temperature, typically few tens of mK, a very large pulse height‐to‐noise ratio can be obtained that is an essential condition for high energy resolution. We are involved in the development of MMCs for metrology applications such as the determination of hard X‐ray emission intensities. For that purpose, we conceived an MMC with an energy resolution of 57 eV around 30 keV. The absorber is made of gold providing high intrinsic detection efficiency even for a small volume, greater than 90% below 60 keV. We will describe the physical principle and the practical realisation of this detector and discuss its performances by analysing the energy spectrum obtained from a ¹³³Ba source. Preliminary outcomes of relative emission intensities of the K X‐ray of cesium are presented and compared with other experimental data and theoretical calculations. Copyright © 2012 John Wiley & Sons, Ltd.     

The capabilities of an electrically cooled energy‐dispersive x‐ray detector for quantitative x‐ray fluorescence analysis

The capabilities of the Si PIN diode x‐ray detector were determined and compared with those of a standard Si(Li) detector. The x‐ray fluorescence (XRF) analysis systems assembled with these two detectors included annular radioisotope excitation sources of Cd‐109 and Fe‐55. The systems were calibrated for sensitivity and quantification was performed with fundamental parameters software. Based on the analysis of the standard reference material NIST 2710 (Montana soil), the elemental sensitivities and the limits of detection of both systems were obtained. The elemental sensitivities of the Si PIN detector for fluorescence x‐rays in the energy range up to 10 keV were comparable to those of the Si(Li) detector. At higher fluorescence x‐ray energies the sensitivity of the Si PIN detector gradually decreased and was smaller by a factor of ～4 at 20 keV. The reason was mainly the small thickness of the sensitive volume of the Si PIN diode (0.2 mm) and therefore the smaller relative efficiency of this detector. The assessed limits of detection (LODs) were comparable for the two detectors, which was mainly due to the lower spectral background of the Si PIN detector in excitation with the Cd‐109 source as a result of its smaller sensitive thickness. The accuracy of elemental determinations for the two detectors was comparable and within the limits of the assessed uncertainties, which were calculated considering all the steps of the analysis, i.e. spectrum measurement and analysis, sensitivity calibration and quantification. Copyright © 2004 John Wiley & Sons, Ltd.     

Semiconductor Peltier‐cooled detectors for x‐ray fluorescence analysis

We discuss recent results obtained in the development of Si(Li), Si p–i–n, CdTe p–i–n and CdZnTe x‐ray detectors with Peltier coolers for fabrication of laboratory and portable XRF analyzers. The characteristics of Si(Li) Peltier‐cooled detectors are close to those of detectors cooled with the liquid nitrogen and remain the most preferred type of detectors for the tasks of x‐ray fluorescence analysis. Considerable success was obtained in the improvement of the characteristics of CdTe p–i–n detectors and CdZnTe detectors with a metal–semiconductor–metal structure, effective in the energy range up to 100 keV. The spectra of all detectors are presented. Copyright © 2004 John Wiley & Sons, Ltd.     

Energy resolution of the CdTe‐XPAD detector: calibration and potential for Laue diffraction measurements on protein crystals

The XPAD3S‐CdTe, a CdTe photon‐counting pixel array detector, has been used to measure the energy and the intensity of the white‐beam diffraction from a lysozyme crystal. A method was developed to calibrate the detector in terms of energy, allowing incident photon energy measurement to high resolution (approximately 140 eV), opening up new possibilities in energy‐resolved X‐ray diffraction. In order to demonstrate this, Laue diffraction experiments were performed on the bending‐magnet beamline METROLOGIE at Synchrotron SOLEIL. The X‐ray energy spectra of diffracted spots were deduced from the indexed Laue patterns collected with an imaging‐plate detector and then measured with both the XPAD3S‐CdTe and the XPAD3S‐Si, a silicon photon‐counting pixel array detector. The predicted and measured energy of selected diffraction spots are in good agreement, demonstrating the reliability of the calibration method. These results open up the way to direct unit‐cell parameter determination and the measurement of high‐quality Laue data even at low resolution. Based on the success of these measurements, potential applications in X‐ray diffraction opened up by this type of technology are discussed.     

Characterization of an in‐vacuum PILATUS 1M detector

A dedicated in‐vacuum X‐ray detector based on the hybrid pixel PILATUS 1M detector has been installed at the four‐crystal monochromator beamline of the PTB at the electron storage ring BESSY II in Berlin, Germany. Owing to its windowless operation, the detector can be used in the entire photon energy range of the beamline from 10 keV down to 1.75 keV for small‐angle X‐ray scattering (SAXS) experiments and anomalous SAXS at absorption edges of light elements. The radiometric and geometric properties of the detector such as quantum efficiency, pixel pitch and module alignment have been determined with low uncertainties. The first grazing‐incidence SAXS results demonstrate the superior resolution in momentum transfer achievable at low photon energies.     

Measurements of Coster–Kronig enhancement factors of some elements in the atomic number range 66 ≤ Z ≤ 72

The Lι, Lα, Lβ and Lγ x‐ray production cross‐sections in four elements with Z ranging from 66 to 72 at seven different energies in the interval 8.265–11.730 keV were measured. Experimental measurements were carried out on a few elemental samples to examine the effect of Coster–Kronig transitions on fluorescence cross‐sections for the L x‐ray line using an Si(Li) detector system with an energy resolution of 160 eV at 5.96 keV x‐ray energy. Absolute values of L x‐ray cross‐sections were calculated with incorporation of the enhancement due to the Coster–Kronig effect for these elements. The measured enhancement factors are smaller than predicted by theory. Copyright © 2003 John Wiley & Sons, Ltd.     

Fabrication of superconducting tunnel junctions for soft X‐ray spectroscopy

Superconducting tunnel junction (STJ) array detectors with a new design, which has a minimum junction edge coverage of an SiO₂ insulation, passivation layer and an asymmetric tunnel junction layer structure, have been fabricated for a soft X‐ray region between 100 eV and 1 keV. The sensitive area was patterned by removing the SiO₂ deposition layer by a lift‐off technique that ensured no contamination layer on the top Nb electrode surface. The width of the passivation rim was as narrow as 0.5 µm at the junction edge. The clean Nb surface and the narrow SiO₂ rim resulted in almost no artifact photon events in a low‐energy region. The asymmetric layer design is effective in solving a problem of double peak response to monochromatic X‐rays, which is commonly observed in STJ detectors. The performance of a 100 pixel array detector was investigated by the fluorescent X‐ray analysis of oxides and nitrides: an energy resolution of about 30 eV for the total absorption of the Kα lines of oxygen and nitrogen. We plan to realize an energy resolution of better than 20 eV and a counting rate of over 1 Mcps for fluorescence‐yield X‐ray absorption spectroscopy for light trace elements. Copyright © 2011 John Wiley & Sons, Ltd.     

Development of new CdZnTe detectors for room‐temperature high‐flux radiation measurements

Recently, CdZnTe (CZT) detectors have been widely proposed and developed for room‐temperature X‐ray spectroscopy even at high fluxes, and great efforts have been made on both the device and the crystal growth technologies. In this work, the performance of new travelling‐heater‐method (THM)‐grown CZT detectors, recently developed at IMEM‐CNR Parma, Italy, is presented. Thick planar detectors (3 mm thick) with gold electroless contacts were realised, with a planar cathode covering the detector surface (4.1 mm × 4.1 mm) and a central anode (2 mm × 2 mm) surrounded by a guard‐ring electrode. The detectors, characterized by low leakage currents at room temperature (4.7 nA cm^?2 at 1000 V cm^?1), allow good room‐temperature operation even at high bias voltages (>7000 V cm^?1). At low rates (200 counts s^?1), the detectors exhibit an energy resolution around 4% FWHM at 59.5 keV (²⁴¹Am source) up to 2200 V, by using commercial front‐end electronics (A250F/NF charge‐sensitive preamplifier, Amptek, USA; nominal equivalent noise charge of 100 electrons RMS). At high rates (1 Mcounts s^?1), the detectors, coupled to a custom‐designed digital pulse processing electronics developed at DiFC of University of Palermo (Italy), show low spectroscopic degradations: energy resolution values of 8% and 9.7% FWHM at 59.5 keV (²⁴¹Am source) were measured, with throughputs of 0.4% and 60% at 1 Mcounts s^?1, respectively. An energy resolution of 7.7% FWHM at 122.1 keV (⁵⁷Co source) with a throughput of 50% was obtained at 550 kcounts s^?1 (energy resolution of 3.2% at low rate). These activities are in the framework of an Italian research project on the development of energy‐resolved photon‐counting systems for high‐flux energy‐resolved X‐ray imaging.     

A gas‐filled electroluminescence detector for EDXRF Spectrometry

The design and features of a sealed‐off proportional scintillation gas‐filled detector (GSPC) are described. The use of a 50 µm Be window and an Xe‐based gas mixture provides high efficiency of registration in the range 1.5–25 keV. The energy resolution changes from 18% for Al Kα (1.49 keV) to 4.2% for Ag Kα (22.2 keV). When the count rate on the unit output is 5 × 10⁴ s^?1, the energy resolution at the Mn Kα line does not exceed 9% at an entrance window area near 3 cm 2 . The detector is operated at room temperature and does not require maintenance during operation. The service life of the detector is over 5 years and the radiation lifetime is practically unlimited. The detector is designed for use in EDXRF spectrometers instead of gas‐filled proportional counters. Copyright © 2005 John Wiley & Sons, Ltd.     

Determination of phosphorus and other elements in atmospheric aerosols using synchrotron total‐reflection X‐ray fluorescence

In this study, P and other low Z elements were determined in aerosol particulates from ambient air using synchrotron radiation‐induced total‐reflection X‐ray fluorescence analysis. Atmospheric transport of nutrients such as P or Si to the oceans is a key factor to marine plankton growth. Concentration of these elements in marine air masses is generally low (P < 10 ng/m³). Therefore, analytical procedures enabling for low detection limits are of interest. Because particle size is strongly correlated to its origin and sedimentation, the aerosols were collected with the aid of a low‐pressure Berner impactor, which separates the aerosol particulates in nine size fractions with the smallest fraction from 15 to 30 nm. To be able to determine low Z elements, measurements were performed under vacuum conditions at the FLUO beamline at the ANKA synchrotron. An excitation energy of 3.5 keV near the P K‐edge but below the Ca K absorption edge was chosen to avoid interferences of the P K‐line with the detector escape artifact of the Ca‐Kα line. The result showed P was present in concentration from 2 to 180 ng/m³. Detection limits were found to be generally 0.2–0.3 ng/m³ for a collecting time of 1 h for the aerosols, which is an improvement to detection limits reported in other studies. Other elements such as S, Cl, and Si were determined as well. Si like P is a nutrient for marine plankton (diatoms). S and Cl play an important role in cloud formation, e.g. polar stratospheric clouds. Copyright © 2013 John Wiley & Sons, Ltd.     

Novel high‐resolution silicon drift detectors

Silicon drift detectors (SDDs) are used as energy‐dispersive detectors for x‐ray fluorescence analysis in commercial systems. Because of the low capacitance of the readout anode, achieved by the device topology and by the integration of the first FET on the chip, noise contributions are very small, allowing good energy resolution at low shaping times and high count rates. Typical energy resolution is better than 147 eV FWHM at 5.9 keV (Mn Kα), at ?10°C. This allows the chips to be cooled with a thermoelectric element, avoiding the use of liquid nitrogen. SDD chips are produced at MPI‐Halbleiterlabor in Munich with different geometries and areas. Recently, a new SDD has been developed which places the anode and the integrated JFET at the margin of the chip where it can easily be shielded from direct irradiation with the use of a collimator. The new layout allows the design of a readout anode with smaller area and therefore reduces the capacitance to values of about 120 fF compared with 200–250 fF with standard SDDs. The result is an improvement in energy resolution down to 128 eV at ?15°C. A second effect is the enhancement of the peak‐to‐background values to 6000 homogeneously across the active area of the detector. Copyright © 2004 John Wiley & Sons, Ltd.     

Si-PIN与CdTe探测器应用于X射线荧光能谱测量的研究

半导体探测器具有优异的性能因而被广泛应用于能量色散X射线荧光测量,以传统型Si-PIN半导体探测器与复合型CdTe半导体探测器为研究对象,分别从材料属性、探测效率、能量分辨率等方面对两种探测器进行对比,重点分析探测器灵敏区厚度、入射X射线能量、后级电路成型时间等因素对其性能的影响,并对由逃逸峰、空穴拖尾效应所导致的X射线荧光能谱的差异进行分析;同时,针对探测器空穴收集不完全的问题,基于FPGA设计了带有上升时间甄别功能的数字多道脉冲幅度分析器,能够有效消除空穴拖尾的影响,提高能量分辨率。从实验结果可知:对能量低于15keV的射线,Si-PIN与CdTe探测器的探测效率基本相当;对能量大于15keV的射线,CdTe探测器的的探测效率明显占优;Si-PIN探测器的最佳成形时间约为10μs,CdTe探测器的最佳成形时间约为2.6μs,因而CdTe探测器更适用于高计数率条件;对于不同能量的X射线,Si-PIN探测器的能量分辨率优于CdTe探测器;CdTe探测器具有明显的空穴拖尾效应,将CdTe探测器与带上升时间甄别功能的数字多道脉冲幅度分析器配合使用,其能量分辨率显著提高。     

Detective quantum efficiency,modulation transfer function and energy resolution comparison between CdTe and silicon sensors bump‐bonded to XPAD3S

XPAD3S is a single‐photon‐counting chip developed in collaboration by SOLEIL Synchrotron, the Institut Louis Néel and the Centre de Physique de Particules de Marseille. The circuit, designed in the 0.25 µm IBM technology, contains 9600 square pixels with 130 µm side giving a total size of 1 cm × 1.5 cm. The main features of each pixel are: single threshold adjustable from 4.5 keV up to 35 keV, 2 ms frame rate, 10⁷ photons s^?1 mm^?2 maximum local count rate, and a 12‐bit internal counter with overflow allowing a full 27‐bit dynamic range to be reached. The XPAD3S was hybridized using the flip‐chip technology with both a 500 µm silicon sensor and a 700 µm CdTe sensor with Schottky contacts. Imaging performances of both detectors were evaluated using X‐rays from 6 keV up to 35 keV. The detective quantum efficiency at zero line‐pairs mm^?1 for a silicon sensor follows the absorption law whereas for CdTe a strong deficit at low photon energy, produced by an inefficient entrance layer, is measured. The modulation transfer function was evaluated and it was shown that both detectors present an ideal modulation transfer function at 26 keV, limited only by the pixel size. The influence of the Cd and Te K‐edges of the CdTe sensor was measured and simulated, establishing that fluorescence photons reduce the contrast transfer at the Nyquist frequency from 60% to 40% which remains acceptable. The energy resolution was evaluated at 6% with silicon using 16 keV X‐rays, and 8% with CdTe using 35 keV X‐rays. A 7 cm × 12 cm XPAD3 imager, built with eight silicon modules (seven circuits per module) tiled together, was successfully used for X‐ray diffraction experiments. A first result recently obtained with a new 2 cm × 3 cm CdTe imager is also presented.     

Improvements of the low‐energy performance of a micro‐focus x‐ray source for XRF analysis with the SEM

X‐ray Fluorescence (XRF) with a scanning electron microscope (SEM) is a valuable completion of the analytical capabilities of SEMs. Small and compact micro‐focus x‐ray sources are mounted to the microscope chamber, and the x‐ray spectra are monitored with conventional EDS systems. Up to now the x‐ray tubes used for the micro‐focus x‐ray sources are equipped with beryllium windows about 100 µm thick. The poly‐capillary x‐ray lenses have their transmission maximum at photon energies around 10 keV. It drops down in both low‐ and high‐energy ranges. Hence, L‐radiation from an Mo or Rh target will be strongly attenuated, and the excitation of fluorescence in the soft x‐ray range becomes very ineffective. A new micro‐focus x‐ray source was developed. It is characterised by a lower self‐absorption in the tube target, thin beryllium windows and an x‐ray optics having a large distance between its foci and the maximum of transmission at about 5 keV. Thus K line fluorescence of light elements becomes effectively excited by the L‐radiation from Mo or Rh tube targets. The detection limit for sodium oxide in glass was found to be below 1 mass%. Copyright © 2009 John Wiley & Sons, Ltd.     

Measurement of the X‐ray mass attenuation coefficients of silver in the 5–20 keV range

The X‐ray mass attenuation coefficients of silver were measured in the energy range 5–20 keV with an accuracy of 0.01–0.2% on a relative scale down to 5.3 keV, and of 0.09–1.22% on an absolute scale to 5.0 keV. This analysis confirms that with careful choice of foil thickness and careful correction for systematics, especially including harmonic contents at lower energies, the X‐ray attenuation of high‐Z elements can be measured with high accuracy even at low X‐ray energies (<6 keV). This is the first high‐accuracy measurement of X‐ray mass attenuation coefficients of silver in the low energy range, indicating the possibility of obtaining high‐accuracy X‐ray absorption fine structure down to the L₁ edge (3.8 keV) of silver. Comparison of results reported here with an earlier data set optimized for higher energies confirms accuracy to within one standard error of each data set collected and analysed using the principles of the X‐ray extended‐range technique (XERT). Comparison with theory shows a slow divergence towards lower energies in this region away from absorption edges. The methodology developed can be used for the XAFS analysis of compounds and solutions to investigate structural features, bonding and coordination chemistry.     

Superconducting tunnel junctions as detectors for high‐resolution x‐ray spectroscopy

Superconducting tunnel junctions (STJs) are a type of cryogenic detector with a working temperature of about 100 mK. They allow the combination of low energy threshold, high quantum efficiency and good count rate capability with an excellent energy resolution; at an x‐ray energy of 5.9 keV an energy resolution of 10.8 eV (FWHM) has been achieved. The detector system described is based on STJs which consist of two superconducting Al electrodes separated by a thin dielectric tunnel barrier. The tunneling process of quasi‐particles created by deposition of energy in the electrodes leads to a detectable current signal. The STJ is equipped with a superconducting Pb absorber which is read out via phonons. The Pb absorber increases absorption efficiency (～50% at 6 keV) and suppresses detector artefacts. The degeneration of Pb, most probably due to oxidation, is overcome by the introduction of a protective SiO layer on top of the absorber. This layer leads to a slight reduction of energy resolution. Nevertheless, a resolution of 9.7 eV at 1.7 keV and of ～20 eV at 5.9 keV could be realized with a prototype detector. Currently this STJ‐based detector system is being incorporated into a prototype cryogenic spectrometer for XRF analysis. Copyright © 2004 John Wiley & Sons, Ltd.     

HAXPES beamline PES‐BL14 at the Indus‐2 synchrotron radiation source

The Hard X‐ray Photo‐Electron Spectroscopy (HAXPES) beamline (PES‐BL14), installed at the 1.5 T bending‐magnet port at the Indian synchrotron (Indus‐2), is now available to users. The beamline can be used for X‐ray photo‐emission electron spectroscopy measurements on solid samples. The PES beamline has an excitation energy range from 3 keV to 15 keV for increased bulk sensitivity. An in‐house‐developed double‐crystal monochromator [Si (111)] and a platinum‐coated X‐ray mirror are used for the beam monochromatization and manipulation, respectively. This beamline is equipped with a high‐energy (up to 15 keV) high‐resolution (meV) hemispherical analyzer with a microchannel plate and CCD detector system with SpecsLab Prodigy and CasaXPS software. Additional user facilities include a thin‐film laboratory for sample preparation and a workstation for on‐site data processing. In this article, the design details of the beamline, other facilities and some recent scientific results are described.     

Performance of a four‐element Si drift detector for X‐ray absorption fine‐structure spectroscopy: resolution, maximum count rate,and dead‐time correction with incorporation into the ATHENA data analysis software

The performance of a four‐element Si drift detector for energy‐dispersive fluorescence‐yield X‐ray absorption fine‐structure measurements is reported, operating at the National Institute of Standards and Technology beamline X23A2 at the National Synchrotron Light Source. The detector can acquire X‐ray absorption fine‐structure spectra with a throughput exceeding 4 × 10⁵ counts per second per detector element (>1.6 × 10⁶ total counts per second summed over all four channels). At this count rate the resolution at 6 keV is approximately 220 eV, which adequately resolves the Mn Kα and Kβ fluorescence lines. Accurate dead‐time correction is demonstrated, and it has been incorporated into the ATHENA data analysis program. To maintain counting efficiency and high signal to background, it is suggested that the incoming count rate should not exceed ～70% of the maximum throughput.     

Kβ/Kα x‐ray intensity ratios for bromine and iodine compounds

Kβ/Kα x‐ray intensity ratios of some Br and I compounds were studied. The samples were excited by 59.5 keV γ‐rays emitted from an Am‐241 radioisotope source and characteristic K x‐rays emitted from the samples were counted by means of an Si(Li) detector which has a resolution 155 eV at 5.9 keV. The experimental values were compared with the calculated theoretical values for elemental Br and I. Copyright © 2003 John Wiley & Sons, Ltd.     

Application of a pnCCD in X‐ray diffraction: a three‐dimensional X‐ray detector

The first application of a pnCCD detector for X‐ray scattering experiments using white synchrotron radiation at BESSY II is presented. A Cd arachidate multilayer was investigated in reflection geometry within the energy range 7 keV < E < 35 keV. At fixed angle of incidence the two‐dimensional diffraction pattern containing several multilayer Bragg peaks and respective diffuse‐resonant Bragg sheets were observed. Since every pixel of the detector is able to determine the energy of every incoming photon with a resolution ΔE/E? 10^?2, a three‐dimensional dataset is finally obtained. In order to achieve this energy resolution the detector was operated in the so‐called single‐photon‐counting mode. A full dataset was evaluated taking into account all photons recorded within 10⁵ detector frames at a readout rate of 200 Hz. By representing the data in reciprocal‐space coordinates, it becomes obvious that this experiment with the pnCCD detector provides the same information as that obtained by combining a large number of monochromatic scattering experiments using conventional area detectors.