G. Pepponi

Intrinsic magnetism and hyperthermia in bioactive Fe-doped hydroxyapatite

The use of magnetic activation has been proposed to answer the growing need for assisted bone and vascular remodeling during template/scaffold regeneration. With this in mind, a synthesis procedure was developed to prepare bioactive (Fe2+/Fe3+)-doped hydroxyapatite (Fe-HA), endowed with superparamagnetic-like properties. This new class of magnetic hydroxyapatites can be potentially employed to develop new magnetic ceramic scaffolds with enhanced regenerative properties for bone surgery; in addition, magnetic Fe-HA can find application in anticancer therapies, to replace the widely used magnetic iron oxide nanoparticles, whose long-term cytotoxicity was recently found to reach harmful levels. An extensive physicochemical, microstructural and magnetic characterization was performed on the obtained Fe-HA powders, and demonstrated that the simultaneous addition of Fe2+ and Fe3+ ions during apatite nucleation under controlled synthesis conditions induces intrinsic magnetization in the final product, minimizing the formation of magnetite as secondary phase. This result potentially opens new perspectives for biodevices aimed at bone regeneration and for anti-cancer therapies based on hyperthermia.

Depth profile characterization of ultra shallow junction implants

A need for analysis techniques, complementary to secondary ion mass spectrometry (SIMS), for depth profiling dopants in silicon for ultra shallow junction (USJ) applications in CMOS technologies has recently emerged following the difficulties SIMS is facing there. Grazing incidence X-ray fluorescence (GIXRF) analysis in the soft X-ray range is a high-potential tool for this purpose. It provides excellent conditions for the excitation of the B-K and the As-Liii,ii shells. The X-ray standing wave (XSW) field associated with GIXRF on flat samples is used here as a tunable sensor to obtain information about the implantation profile because the in-depth changes of the XSW intensity are dependent on the angle of incidence. This technique is very sensitive to near-surface layers and is therefore well suited for the analysis of USJ distributions. Si wafers implanted with either arsenic or boron at different fluences and implantation energies were used to compare SIMS with synchrotron radiation-induced GIXRF analysis. GIXRF measurements were carried out at the laboratory of the Physikalisch-Technische Bundesanstalt (PTB) at the electron storage ring BESSY II using monochromatized undulator radiation of well-known radiant power and spectral purity. The use of an absolutely calibrated energy-dispersive detector for the acquisition of the B-Kα and As-Lα fluorescence radiation enabled the absolute determination of the total retained dose. The concentration profile was obtained by ab initio calculation and comparison with the angular measurements of the X-ray fluorescence.

Analysis of organic contaminants on Si wafers with TXRF- NEXAFS

Abstract Organic contamination is starting to play an important role in the production and quality control of Si wafers. For the traceability of the source of contamination, information on the chemical binding conditions is very valuable. A near edge X-ray absorption fine structure (NEXAFS) investigation is the natural development of total reflection X-ray fluorescence (TXRF) analysis of the wafer surfaces able to solve the problem of speciation. The plane grating monochromator beamline for undulator radiation of the Physikalisch-Technische Bundesanstalt at the electron storage ring BESSY II, which provides photon energies between 30 eV and 1.9 keV for the specimen excitation, is an ideal excitation source for TXRF-NEXAFS experiments that require a high resolving power and a sufficient photon flux for trace analysis of low Z elements. The contaminants have been diluted and deposited as droplets on wafer pieces thoroughly cleaned after the cutting. The K edges of C, N, O have been examined. Some discrepancies have been found in the analysis of the same compounds in two different beamtimes; molecular orientation is pointed to as the cause for the difference in magnitude of the resonances. The unintentional contamination has been identified as mainly composed of aliphatic chains.

Improvement of total reflection X-ray fluorescence analysis of low Z elements on silicon wafer surfaces at the PTB monochromator beamline for undulator radiation at the electron storage ring BESSY II☆

Abstract Several different total reflection X-ray fluorescence (TXRF) experiments were conducted at the plane grating monochromator beamline for undulator radiation of the Physikalisch-Technische Bundesanstalt (PTB) at the electron storage ring BESSY II, which provides photon energies between 0.1 and 1.9 keV for specimen excitation. The lower limits of detection of TXRF analysis were investigated for some low Z elements such as C, N, O, Al, Mg and Na in two different detection geometries for various excitation modes. Compared to ordinary XRF geometries involving large incident angles, the background contributions in TXRF are drastically reduced by the total reflection of the incident beam at the polished surface of a flat specimen carrier such as a silicon wafer. For the sake of an application-oriented TXRF approach, droplet samples on Si wafer surfaces were prepared by Wacker Siltronic and investigated in the TXRF irradiation chamber of the Atominstitut and the ultra-high vacuum TXRF irradiation chamber of the PTB. In the latter, thin C layer depositions on Si wafers were also studied.

Synchrotron radiation induced TXRF

The use of synchrotron radiation (SR) as an excitation source for total reflection X-ray fluorescence analysis (TXRF) offers several advantages over X-ray tube excitation. Detection limits in the fg range can be achieved with efficient excitation for low Z as well as high Z elements due to the features of synchrotron radiation and in particular the high brilliance in a wide spectral range and the linear polarization in the orbital plane. SR-TXRF is especially interesting for samples where only small sample masses are available. Lowest detection limits are typically achieved using multilayer monochromators since they exhibit a bandwidth of about 0.01 ΔE/E. Monochromators with smaller bandwidth like perfect crystals, reduce the intensity, but allow X-ray absorption spectroscopy (XAS) measurements in fluorescence mode for speciation and chemical characterisation at trace levels. SR-TXRF is performed at various synchrotron radiation facilities. An historical overview is presented and recent setups and applications as well as some critical aspects are reviewed.

Analysis of low Z elements on Si wafer surfaces with synchrotron radiation induced total reflection X-ray fluorescence at SSRL, Beamline 3-3: comparison of droplets with spin coated wafers☆

Abstract The unique properties of synchrotron radiation, such as high incident flux combined with low divergence, its linear polarization and energy tunability, make it an ideal excitation source for total reflection X-ray fluorescence (TXRF) spectroscopy in order to non-destructively detect trace impurities of transition metals on Si wafer surfaces. When used with a detector suitable for the determination of low energy radiation this technique can be extended to the detection of low-Z elements, such as Al, Na and Mg. Experiments have been performed at SSRL Beamline 3-3, a bending magnet beamline using monochromatic radiation from a double multilayer monochromator. The wafer was mounted vertically in front of the detector, which was aligned along the linear polarization vector of the incoming synchrotron radiation. This configuration allows the detector to accept a large solid angle as well as to take advantage of the reduced scattered X-ray intensity emitted in the direction of the linear polarization vector. A comparison between droplet samples and spin coated samples was done, in order to compare the capabilities of vapor phase decomposition (VPD-TXRF) with conventional SR-straight-TXRF. Detection limits in the range of 50 fg corresponding to 2E10 atoms/cm2 have been obtained for Na. The spin coated samples, prepared from solutions containing an equal amount of Na, Mg and Al showed an unexpected result when performing a scan of the angle of incidence of the incoming X-rays suggesting a different adsorption behavior of the elements in a multielement solution on the wafer surface. The observation of this behavior is important because the spin coating technique is the standard method for the preparation of surface standards in semiconductor quality control. This effect could be characteristic of the Na, Mg, Al solution used, but the angle dependence of the fluorescence signal of a standard should always be investigated before using the standard for calibration of the apparatus and quantification.

Assessment of chemical species of lead accumulated in tidemarks of human articular cartilage by X-ray absorption near-edge structure analysis.

Lead is a toxic trace element that shows a highly specific accumulation in the transition zone between calcified and non-calcified articular cartilage, the so-called ‘tidemark’. Excellent agreement has been found between XANES spectra of synthetic Pb-doped carbonated hydroxyapatite and spectra obtained in the tidemark region and trabecular bone of normal human samples, confirming that in both tissues Pb is incorporated into the hydroxyapatite crystal structure of bone. During this study the µ-XANES set-up at the SUL-X beamline at ANKA was tested and has proven to be well suited for speciation of lead in human mineralized tissue samples.

Grazing exit versus grazing incidence geometry for x-ray absorption near edge structure analysis of arsenic traces

In the presented study the grazing exit x-ray fluorescence was tested for its applicability to x-ray absorption near edge structure analysis of arsenic in droplet samples. The experimental results have been compared to the findings of former analyses of the same samples using a grazing incidence (GI) setup to compare the performance of both geometries. Furthermore, the investigations were accomplished to gain a better understanding of the so called self-absorption effect, which was observed and investigated in previous studies using a GI geometry. It was suggested that a normal incidence-grazing-exit geometry would not suffer from self-absorption effects in x-ray absorption fine structure (XAFS) analysis due to the minimized path length of the incident beam through the sample. The results proved this assumption and in turn confirmed the occurrence of the self-absorption effect for GI geometry. Due to its lower sensitivity it is difficult to apply the GE geometry to XAFS analysis of trace amounts (few nano...

Grazing incidence x-ray fluorescence and secondary ion mass spectrometry combined approach for the characterization of ultrashallow arsenic distribution in silicon

Dopant depth profiling and dose determination are essential for ultrashallow junction technology development. However they pose a challenge to the widely used dynamic secondary ion mass spectroscopy (SIMS) technique that suffers uncertainties due to an initial transient width comparable to the dopant depth distribution. In this work the authors report on the application of grazing incidence x-ray fluorescence (GIXRF) for arsenic in silicon dose and profile determination and its combination with SIMS in order to try to overcome the limitations of the latter in the topmost few nanometers. A polynomial variation of the sputtering rate is supposed in the first sputtering stage of the SIMS analysis and the parameters that regulate the magnitude of such correction are determined by a least square fitting of the angle dependent fluorescence signal. The total retained fluence was also measured by instrumental neutron activation analysis and synchrotron radiation soft x-ray GIXRF. The comparison among the total re...

Correlation of local structure and electrical activation in arsenic ultrashallow junctions in silicon

The understanding of the behavior of arsenic in highly doped near surface silicon layers is of crucial importance for the formation of N-type ultrashallow junctions in current and future very large scale integrated technology. This is of particular relevance when studying recently developed implantation and annealing methods. Past theoretical as well as experimental investigations have suggested that the increase in As concentration, and therefore the reciprocal proximity of several As atoms, leads to a drastic increase in electrically inactive defects giving only marginal reduction in sheet resistance. Monoclinic SiAs aggregates as well as various arsenic-vacancy clusters contribute to the deactivation of arsenic. This study aims to correlate between the results of electrical activation measurements and x-ray absorption fine structure measurements. Samples were doped with a nominal fluence of 1×1015–3×1015 atoms/cm2, implanted at 2 keV, and annealed by rapid thermal treatments, laser submelt treatments, ...