EDXRF analysis of Marajoara pubic covers

This work evaluated the elemental composition of decorated pottery pubic covers (tangas) from the Marajoara culture of Marajó Island (at the mouth of the Amazon River, Brazil) using EDXRF technique. The XRF system used in this work consists in a Si(Li) detector from ORTEC, with resolution of 180 eV, at 5.9 keV, and a mini X-ray tube with Mo anode. The elements identified in the samples were: S, Cl, K, Ca, Ti, Mn, Fe, Cu, Zn, Ga, Rb, Sr, Y, Zr and Pb. Principal components analysis (PCA) was used to evaluated the provenance of the samples.     

Use of silicon drift detectors for the detection of medium-light elements in PIXE

In order to fully exploit in PIXE the superior performance of silicon drift detectors especially for the detection of low- and medium-energy X-rays, avoiding in particular the negative effects of backscattered particles, we developed a custom spectrometer based on a 10 mm² chip with a thermoelectric Peltier cooler and home-designed front-end electronics, coupled to a weakly focusing polycapillary lens.This paper briefly describes the detector + lens assembly and reports the results of first tests carried out at an external beam line of the LABEC laboratory in Florence. Excellent energy resolution is achieved under real operating conditions in a PIXE run (measured FWHM at 1 keV is 81 eV with a count-rate of 480 cps) and also the lineshapes are very good (FW1/10M over FWHM ratio is 2.1). As a whole, our preliminary tests gave encouraging results and also helped to point out some aspects which it is worthwhile to investigate further (e.g. how X-ray peak intensity ratios may be affected by inaccurate lens alignment), in order to profit fully from such a good performance of the spectrometer.     

A systematic study on MOS type radiation sensors

Radiation sensors based on metal oxide semiconductor (MOS) structure are useful because of their superior sensitivity as well as excellent compatibility with the existing microelectronic technology. In this paper, a systematic study of MOS capacitors built on p- and n-type Si substrates with different SiO₂ thicknesses (10 nm, 50 nm, 100 nm and 240 nm) is presented. MOS device response to gamma radiation up to 256 Gray have been studied from the sensor application point of view. Variation of the radiation induced device response with oxide thickness, substrate type, applied bias and post annealing have been measured and discussed. Radiation induced charge in MOS devices is shown to be a strong function of the oxide thickness as expected. Application of a positive bias to the gate is found to enhance the device sensitivity for both n- and p-type devices. This is explained in terms of the involvement of the interface states in the sensing process. Devices have also been studied after repeated cycles of irradiation and annealing treatment under hydrogen atmosphere. Each cycle consists of gamma irradiation with 60 Gray dose and an anneal at 200 °C for 30 min. The charging-discharging mechanism during these cycles is discussed.     

Synchrotron X-ray induced damage in polymer (PS) thin films

Thin polystyrene (PS) films (M_w = 234,000) are spin coated on silicon substrates with a Chromium (Cr) layer as a sandwiched metallic layer that produces photoelectrons (by synchrotron X-rays). Earlier studies on synchrotron radiation damage in PS films, without metallic layer, have shown a decrease in interfacial roughness and a slight increase in thickness, at temperatures below T_g [A.G. Richter, R. Guico, K. Shull, J. Wang, Macromolecules 39 (2006) 1545]. Similar trend is observed in the presence of a thin layer of Cr film (∼2.5 nm). For the sample with a thick Cr layer the opposite effect was observed for X-ray radiation damage. For the 50 nm thick Cr film system thickness of the polystyrene film decreased by ≈4.4% which amount to a loss of about 0.021 nm³ per incident photon in the fluence range studied (6.8 × 10⁹ photons mm⁻² to 1 × 10¹⁴ photons mm⁻²). Interfacial roughness also increased from about 1.0 nm to 2.1 nm in the process. These effects are explained by invoking the presence of more number of X-ray induced photoelectrons and secondary electrons for 50 nm thick Cr film case compared to 2.5 nm thin film case.     

The interdiffusion and solid-state reaction of low-energy copper ions implanted in silicon

At room temperature, single-crystal silicon was implanted with Cu⁺ ions at an energy of 80 keV using two doses of 5 × 10¹⁵ and 1 × 10¹⁷ Cu⁺ cm⁻². The samples were heat treated by conventional thermal annealing at different temperatures: 200 °C, 230 °C, 350 °C, 450 °C and 500 °C. The interdiffusion and solid-state reactions between the as-implanted samples and the as-annealed samples were investigated by means of Rutherford backscattering spectrometry (RBS) and X-ray diffraction (XRD). After annealing at 230 °C, the XRD results of the samples (subject to two different doses) showed formation of Cu₃Si. According to RBS, the interdiffusion between Cu and Si atoms after annealing was very insignificant. The reason may be that the formation of Cu₃Si after annealing at 230 °C suppressed further interdiffusion between Si and Cu atoms.     

Sub-surface retention of Pb atoms in silicon after low-energy ion implantation and electron beam annealing

Low-energy Pb ion implantation into (1 0 0) Si and subsequent high-vacuum electron beam annealing was used to study the potential of sub-surface retention of Pb atoms after applying a high temperature annealing process. 7 keV Pb⁺ ions were implanted into p-type (1 0 0) Si at room temperature with a fluence of 4 × 10¹⁵ ions cm⁻². The implantation results in a Pb depth distribution that has a calculated Pb peak concentration of 23.9 at.% at a depth of 8.0 nm. The Pb implanted Si substrates were annealed with a high-current 20 keV electron beam at 200-700 °C for 15 s. The Pb loss by out-diffusion was measured with RBS. Key results are: (i) minimal Pb loss in samples annealed up to 400 °C, (ii) emerging out-diffusion above 400 °C, (iii) retention of Pb atoms in the near-surface region in samples annealed up to 700 °C. Comparison of the RBS data with the calculated evaporation rate of Pb under similar conditions reveals two distinctive temperature ranges in which the measured Pb loss of the implanted samples disagrees with the calculated Pb loss: (1) Pb atoms diffused out of the samples at a higher rate in the temperature range up to 400 °C and (2) the Pb atoms diffused out of the samples at a much slower rate above 450 °C. Both phenomena are attributed to the ion implantation process.     

An energy dispersive micro X-ray diffractometer based on a combined system of polycapillary optics

An energy dispersive micro X-ray diffractometer based on a combined system of two polycapillary X-ray lenses is designed. The polycapillary X-ray lens in the excitation channel is either a polycapillary parallel X-ray lens (PPXRL) or a slightly focusing polycapillary X-ray lens (SFPXRL). The polycapillary X-ray lens in the detection channel is a PPXRL. At 6.4 keV and 2θ = 141.5°, the total resolution of the diffractometer based on a SFPXRL in the excitation channel and a PPXRL in the detection channel in Δd/d is 4.8%.     

Effects of the behaviour of the proton-induced isotopes production on the analysis of ancient alloys

The present work concerns non-destructive ion beam analysis carried out by means of proton-beam-induced nuclear reactions in the 10-30 MeV energy range. We focused our attention on the yield distribution of the isotopes produced in the internal region of a metal alloy. This distribution, which defines the analytical region, displays, at incident energy of about 20 MeV in a bronze based alloy, a bell-shaped curve centred at about 600 μm with an average width of about 400 μm. By changing the incident proton energy it is possible to displace the above region in the interior of the metal body. It should be pointed out that if we neglect to take into account the correct behaviour of the isotope yield distribution in samples with surface inhomogeneities we can obtain erroneous analytical results. We describe some experiments based on proton activation analysis (PAA) carried out at the INFN-Laboratori Nazionali del Sud (LNS) in Catania where we verified the bell-shape of the radioactive isotope distribution. The resulting formulas are given for quantitative analysis.It is straightforward that, by choosing the appropriate incident proton energy, it is possible to confine the whole analytical region to the interior of the body, thus eliminating any influence of surface effects. We have called this particular approach deep proton activation analysis (DPAA). Examples of its use on archaeological artefacts are given.     

HRBS/channeling studies of ultra-thin ITO films on Si

High-resolution Rutherford backscattering spectroscopy (HRBS)/channeling techniques have been utilized for a detailed characterization of ultra-thin indium tin oxide (ITO) films and to probe the nature of the interface between the ITO film and the Si(0 0 1) substrate. Channeling studies provide a direct measure of the lattice strain distribution in the crystalline Si substrate in the case of amorphous over layers. The measurements on DC magnetron sputtered ITO films have been carried out using the recently installed HRBS facility at the Centre for Ion Beam Applications (CIBA). The thickness of the ultra-thin (∼9.8 nm) ITO films was calculated from the HRBS spectra having an energy resolution of about 1.4 keV at the superimposed leading (In + Sn) edge of the ITO film. The films were near stoichiometric and the interface between ITO film and Si was found to include a thin SiO_x transition layer. The backscattering yields from (In + Sn) of ITO were equal in random and channeling directions, thereby revealing the non-crystalline nature of the film. Angular scans of HRBS spectra around the off-normal [1 1 1] axis clearly showed a shift in the channeling minimum indicative of compressive strain of the Si lattice at the SiO_x/Si interface. The observed strain was about 0.8% near the interface and decreased to values below our detection limits at a depth of ∼3 nm from the SiO_x/Si interface.     

Xenon-ion irradiation of Co/Si bilayers: Effects of interface structure and ion energy

Heavy-ion irradiation of ferromagnetic thin layers changes their micromagnetic and microstructural properties, due to the production of defects, relaxation or build-up of stress, or changes of grain size. When the ion range exceeds the layer thickness, ion mixing processes take place, leading to the formation of silicide phases. The present study deals with Co(30 or 55 nm)/Si bilayers irradiated at room temperature with 100- or 200 keV Xe ions to fluences of up to 15 × 10¹⁵/cm². The Si(1 0 0) wafers were either crystalline or pre-amorphized by 1 keV Ar⁺ implantation. Rutherford backscattering spectroscopy, in-plane magneto-optical Kerr effect, and X-ray diffraction served to analyse the samples before and after irradiation. The results will be compared with those obtained for other heavy-ions for Co/Si bilayers and in similar studies on Fe/Si bilayers.     

Search for short-time phase effects in the electronic damage evolution - A case study with silicon

This work focusses on the production and decay properties of inner-shell vacancies and valence-band excitations induced by swift highly charged ions interacting with amorphous and crystalline Si. High resolution electron spectra have been taken for fast heavy ions at 1.78-5 MeV/u as well as for electrons of similar velocity incident on atomically clean Si targets of well defined phase. Various Auger-electron structures are analyzed concerning their width, their intensity and exact peak position. All measured peaks show a small shift towards lower energy when the charge of the projectile is increased. This finding is an indication for a nuclear-track potential inside the ion track. A detailed analysis of the Auger-electron spectra for amorphous Si and crystalline Si(1 1 1) 7 × 7 points to a small but significant phase effect in the short-time dynamics of ion tracks.     

Ionization in symmetric and nearly symmetric low energy ion-surface collisions

Multiply charged ions are emitted following bombardment of Al(1 0 0) and Si(1 1 1) by low energy Si⁺ and P⁺ ions. The ion formation is attributed to inner-shell electron promotion during a hard collision between symmetric or nearly symmetric atomic species, followed by Auger decay outside the surface. The relative yield of triply charged Si ions for Si⁺ → Si(1 1 1) is much smaller than that of triply charged Al ions in direct recoil Si⁺ → Al(1 0 0) experiments. This difference can be explained by assuming that only one 2p hole is produced in a Si atom during the symmetric collision, whereas a double 2p hole is also produced in the Al atom following the nearly symmetric Si-Al collision. Further evidence is provided by the complimentary experiment P⁺ → Si(1 1 1), where Si³⁺ regains its intensity and Si⁴⁺ emerges as a result of a double 2p hole decay with shake-off.     

Determination of uranium content in Th, U mixed oxides using EDXRF

An energy dispersive X-ray fluorescence (EDXRF) technique has been developed for the determination of U content in the range 2-80% in mixed oxides of thorium and uranium. The experimental parameters for XRF measurements were optimized using 1 cm diameter pellets made from 1:1 mixture of thorium-uranium mixed oxide standards and cellulose. Calibration plots were established using both L_α as well as L_β peaks of uranium. The reproducibility of the determination was evaluated to be better than 3% for L_α peak, while for L_β peak, it was better than 4%. The measured values of the uranium concentration in the synthetic samples were found to be in good agreement with the added values. Simultaneously Th was also determined using its L_α peak. The present method will be useful for fast routine measurements of mixed oxide samples of Th and U, without the need for dissolution.     

Resonant Rutherford backscattering spectrometry for carbon diffusion in silicon

300 keV C⁺ ion implantation onto Si(1 0 0) wafers was carried out at temperatures of 400, 500, 550, 600, 650 and 700 °C. Depth profile of C was determined by resonant Rutherford backscattering spectrometry (RRBS) measurements using ¹²C(α,α)¹²C resonant reaction with the α-particle energy of 4.27 MeV. The concentration of the implanted carbon at the surface as a function of inverse of implantation temperature shows an Arrhenius behaviour. The activation energy for diffusion of carbon in Si was measured and found to be 0.434 eV, which is smaller than the activation energy (0.88 eV) for the C diffusion in Si in equilibrium condition. The possible mechanism of C diffusion in Si during irradiation conditions existing in our experiments where large concentration of vacancies and interstitials are produced is discussed and we find that the C diffusion during irradiation conditions could be due to the drag the carbon towards the surface by the vacancy flux.     

Behavior of crystalline silicon under huge electronic excitations: A transient thermal spike description

Recent experimental works devoted to the phenomena of mixing observed at metallic multilayers Ni/Si irradiated by swift heavy ions irradiations make it necessary to revisit the insensibility of crystalline Si under huge electronic excitations. Knowing that Ni is an insensitive material, such observed mixing would exist only if Si is a sensitive material. In order to extend the study of swift heavy ion effects to semiconductor materials, the experimental results obtained in bulk silicon have been analyzed within the framework of the inelastic thermal spike model. Provided the quenching of a boiling (or vapor) phase is taken as the criterion of amorphization, the calculations with an electron-phonon coupling constant g(300 K) = 1.8 × 10¹² W/cm³/K and an electronic diffusivity D_e(300 K) = 80 cm²/s nicely reproduce the size of observed amorphous tracks as well as the electronic energy loss threshold value for their creation, assuming that they result from the quenching of the appearance of a boiling phase along the ion path. Using these parameters for Si in the case of a Ni/Si multilayer, the mixing observed experimentally can be well simulated by the inelastic thermal spike model extended to multilayers, assuming that this occurs in the molten phase created at the Ni interface by energy transfer from Si.     

Characterization of the interaction layer grown by interdiffusion between U-7wt%Mo and Al A356 alloy at 550 and 340 °C

U(Mo) alloys are under study to get a low-enriched U fuel for research and test reactors. Qualification experiments of dispersion fuel elements have shown that the interaction layer between the U(Mo) particles and the Al matrix behaves unsatisfactorily. The addition of Si to Al seems to be a good solution. The goal of this work is to identify the phases constituting the interaction layer for out-of-pile interdiffusion couples U(Mo)/Al(Si). Samples γU-7wt%Mo/Al A356 alloy (7.1 wt%Si) made by Friction Stir Welding were annealed at 550 and 340 °C. Results from metallography, microanalysis and X-ray diffraction, indicate that the interaction layer at 550 °C is formed by the phases U(Al,Si)₃, U₃Si₅ and Al₂₀Mo₂ U, while at 340 °C it is formed by U(Al,Si)₃ and U₃Si₅. X-ray diffraction with synchrotron radiation showed that the Si-rich phase, previously reported in the interaction layer at 550 °C near U(Mo) alloy, is U₃Si₅.     

Effects of ion irradiation on the structural transformation of sol-gel derived TEOS/MTES thin films

Ion beam processing of organic/inorganic thin films has been shown to be an effective means in converting polymeric films into their final ceramic-like state. In this study, hybrid sol-gel derived thin films based on TEOS (tetraethylorthosilicate) Si(OC₂H₅)₄ and MTES (methyltriethoxysilane) CH₃Si(OC₂H₅)₃ were prepared and deposited on Si substrates by spin coating. After the films were allowed to air dry, they were heat treated at 300 °C for 10 min. Ion irradiation was performed at room temperature using 125 keV H⁺ and 250 keV N²⁺ ions with fluences ranging from 1 × 10¹⁴ to 5 × 10¹⁶ ions/cm². FT-IR and Raman spectroscopies were used to quantify the chemical structural transformations which occurred including the evolution of the organic components, the cross-linking of silica clusters, and the clustering of carbon.     

Adhesion of proton beam written high aspect ratio hydrogen silsesquioxane (HSQ) nanostructures on different metallic substrates

Hydrogen silsesquioxane (HSQ) behaves as a negative resist under MeV proton beam exposure. HSQ is a high-resolution resist suitable for production of tall (<1.5 μm) high aspect ratio nanostructures with dimensions down to 22 nm. High aspect ratio HSQ structures can be used in many applications, e.g. nanofluidics, biomedical research, etc. Isolated HSQ nanostructures, however, tend to detach from substrates during the development process due to the weak adhesive forces between the resist and the substrate material. Larger proton fluences were observed to promote the adhesion. To determine an optimal substrate material and the proton irradiation doses for HSQ structures, a series of 2 μm long and 60-600 nm wide free-standing lines were written with varying fluences of 2 MeV protons in 1.2 μm thick HSQ resist spun on Ti/Si, Cr/Si and Au/Cr/Si substrates. The results indicate that the Ti/Si substrate is superior in terms of adhesion, while Au/Si is the worst. Cr/Si is not suitable as a substrate for HSQ resist because debris was formed around the structures, presumably due to a chemical reaction between the resist and Cr.     

Surface roughness of ion-bombarded Si(1 0 0) surfaces: Roughening and smoothing with the same roughness exponent

We have carried out scanning tunneling microscopy experiments under ultrahigh vacuum condition to study the roughness of pristine as well as ion-bombarded Si(1 0 0) surfaces and of ultrathin Ge films deposited on them. One half of a Si(1 0 0) sample (with native oxide layer) was irradiated at room temperature using 45 keV Si⁻ ions at a fluence of 4 × 10¹⁵ ions/cm² while the other half was masked. STM measurements were then carried out on the unirradiated as well as the irradiated half of the sample. Root-mean-square (rms) roughness of both the halves of the sample has been measured as a function of STM scan size. Below a length scale of ∼30 nm we observe surface smoothing and surface roughening is observed for length scales above this value. However, the surface is self-affine up to length scales of ∼200 nm and the observed roughness exponent of 0.46 ± 0.04 is comparable to earlier cases of ion sputtering studies where only roughening [J. Krim, I. Heyvart, D.V. Haesendonck, Y. Bruynseraede, Phys. Rev. Lett. 70 (1993) 57] or only smoothing [D.K. Goswami, B.N. Dev, Phys. Rev. B 68 (2003) 033401] was observed. Preliminary results involving morphology for Ge deposition on clean ion-irradiated and pristine Si(1 0 0) surfaces are presented.     

SIMS study of effect of Cr adhesion layer on the thermal stability of silver selenide thin films on Si

Effect of heat treatment on silver selenide films grown from diffusion-reaction of Ag and Se films on Cr-buffered Si substrates was investigated up to 400 °C. X-ray diffraction (XRD), Scanning electron microscopy (SEM), Secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS) were used to characterize the films. XRD patterns of the films showed stress assisted change in preferential orientation of the films upon annealing: the films annealed at 200 °C exhibited a strong orientation along (2 0 0) plane, which changed to (0 1 3) after annealing at 300 and 400 °C. Dynamic SIMS measurements showed that Cr is confined to the interface and that there is no diffusion of Cr into silver selenide.