Investigation of hydrogen concentration and hardness of ion irradiated organically modified silicate thin films

A study of the effects of ion irradiation of organically modified silicate thin films on the loss of hydrogen and increase in hardness is presented. NaOH catalyzed SiNa_wO_xC_yH_z thin films were synthesized by sol–gel processing from tetraethylorthosilicate (TEOS) and methyltriethoxysilane (MTES) precursors and spin-coated onto Si substrates. After drying at 300 °C, the films were irradiated with 125 keV H⁺ or 250 keV N²⁺ at fluences ranging from 1 × 10¹⁴ to 2.5 × 10¹⁶ ions/cm². Elastic Recoil Detection (ERD) was used to investigate resulting hydrogen concentration as a function of ion fluence and irradiating species. Nanoindentation was used to measure the hardness of the irradiated films. FT-IR spectroscopy was also used to examine resulting changes in chemical bonding. The resulting hydrogen loss and increase in hardness are compared to similarly processed acid catalyzed silicate thin films.     

Micro-Raman depth profile investigations of beveled Al+-ion implanted 6H-SiC samples

6H-SiC single crystals were implanted with 450 keV Al⁺-ions to a fluence of 3.4 × 10¹⁵ cm^?2 , and in a separate experiment subjected to multiple Al⁺ implantations with the four energies: 450, 240, 115 and 50 keV and different fluences to obtain rectangular-like depth distributions of Al in SiC. The implantations were performed along [0 0 0 1] channeling and non-channeling (“random”) directions. Subsequently, the samples were annealed for 10 min at 1650 °C in an argon atmosphere. The depth profiles of the implanted Al atoms were obtained by secondary ion mass spectrometry (SIMS). Following implantation and annealing, the samples were beveled by mechanical polishing. Confocal micro-Raman spectroscopic investigations were performed with a 532 nm wavelength laser beam of a 1 μm focus diameter. The technique was used to determine precisely the depth profiles of TO and LO phonon lines intensity in the beveled samples to a depth of about 2000 nm. Micro-Raman spectroscopy was also found to be useful in monitoring very low levels of disorder remaining in the Al⁺ implanted and annealed 6H-SiC samples. The micro-Raman technique combined with sample beveling also made it possible the determination of optical absorption coefficient profiles in implanted subsurface layers.     

Depth-profiling of implanted 28Si by (α,α) and (α,p0) reactions

Silicon nanocrystals enclosed in thin films (Si quantum dots or Si QDs) are regarded to be the cornerstone of future developments in new memory, photovoltaic and optoelectronic products. One way to synthesize these Si QDs is ion implantation in SiO₂ layers followed by thermal annealing post-treatment.Depth-profiling of these implanted Si ions can be performed by reactions induced by α-particles on ²⁸Si. Indeed, for high incident energy, nuclear levels of ³²S and ³¹P can be reached, and cross-sections for (α,α) and (α,p₀) reactions are more intense. This can help to increase the signal for surface silicon, and therefore make distinguishing more easy between implanted Si and Si coming from the SiO₂, even for low fluences.In this work, (α,α) and (α,p₀) reactions are applied to study depth distributions of 70 keV ²⁸Si⁺ ions implanted in 200 nm SiO₂ layers with fluences of 1 × 10¹⁷ and 2 × 10¹⁷ cm^?2. Analysis is performed above E_R = 3864 keV to take advantage of resonances in both (α,α) and (α,p₀) cross-sections. We show how (α,p₀) reactions can complement results provided by resonant backscattering measurements in this complex case.     

Ion beam characterization of Fe-implanted GaN

Fe ion implantation in GaN has been investigated by means of ion beam analysis techniques. Implantations at an energy of 150 keV and fluences ranging from 2 × 10¹⁵ to 1 × 10¹⁶ cm^?2 were done, both at room temperature and at 623 K. Secondary Ions Mass Spectrometry was used to determine the Fe implantation profiles, whereas Rutherford Backscattering in channeling conditions with a 2.2 MeV ⁴He⁺ beam allowed us to follow the damage evolution. Particle Induced X-ray Emission in channeling conditions with a 2 MeV H⁺ beam was employed to study the lattice location of Fe atoms after implantation. The results show that a high fraction of Fe-implanted atoms are located in high symmetry sites in low fluence implanted samples, where the damage level is lower, whereas the fraction of randomly located Fe atoms increases by increasing the fluence and the resulting damage. Moreover, dynamical annealing present in high temperature implantation has been shown to favor the incorporation of Fe atoms in high symmetry sites.     

Ion implantation effects in single crystal Si investigated by Raman spectroscopy

A study of the effects of Ar ion implantation on the structural transformation of single crystal Si investigated by confocal Raman spectroscopy is presented. Implantation was performed at 77 K using 150 keV Ar⁺⁺ with fluences ranging from 2 × 10¹³ to 1 × 10¹⁵ ions/cm². The Raman spectra showed a progression from crystalline to highly disordered structure with increasing fluence. The 520 cm^?1 c-Si peak was seen to decrease in intensity, broaden and exhibit spectral shifts indicating an increase in lattice disorder and changes in the residual stress state. In addition, an amorphous Si band first appeared as a shoulder on the 520 cm^?1 peak and then shifted to lower wavenumbers as a single broadband peak with a spectral center of 465 cm^?1. Additionally, the emergence of the a-Si TA phonon band and the decrease of the c-Si 2TA and 2TO phonon bands also indicated the same structural transition from crystalline to highly disordered. The Raman results were compared to those obtained by channeling RBS.     

Annealing of ion implanted 4H–SiC in the temperature range of 100–800 °C analysed by ion beam techniques

Ion implantation induced damage formation and subsequent annealing in 4H–SiC in the temperature range of 100–800 °C has been investigated. Silicon Carbide was implanted at room temperature with 200 keV ⁴⁰Ar ions with two implantation fluences of 4 × 10¹⁴ and 2 × 10¹⁵ ions/cm². The samples were characterized by Rutherford backscattering and nuclear reaction analysis techniques in channeling mode using 2.00 and 4.30 MeV ⁴He ion beams for damage buildup and recovery in the Si and C sublattices, respectively. At low ion fluence, the restoration of the Si sublattice is evident already at 200 °C and a considerable annealing step occurs between 300 and 400 °C. Similar results have been obtained for the C sublattice using the nuclear resonance reaction for carbon, ¹²C(α,α)¹²C at 4.26 MeV. For samples implanted with the higher ion fluence, no significant recovery is observed at these temperatures.     

Optical contrast formation in amorphous silicon carbide with high-energy focused ion beams

Thin films (d ～ 1 μm) of hydrogenated amorphous silicon carbide (a-Si_1?xC_x:H), deposited by RF reactive magnetron sputtering with different carbon content x, have been implanted with high fluences (Φ = 1016–1017 cm^?2) of high-energy (E = 0.2–1 MeV) He⁺ ions as the implant species. The induced structural modification of the implanted material results in a considerable change of its optical properties, best manifested by a significant shift of the optical absorption edge to lower photon energies as obtained from photo-thermal-deflection spectroscopy (PDS) data. This shift is accompanied by a remarkable increase of the absorption coefficient over one order of magnitude (photo-darkening effect) in the measured photon energy range (0.6–3.8 eV), depending on the ion fluence, energy and carbon content of the films. These effects could be attributed both to additional defect introduction and increased graphitization, as confirmed by Raman spectroscopy and infra-red (IR) optical transmission measurements. The optical contrast thus obtained (between implanted and unimplanted film material) could be made use of in the area of high-density optical data storage using focused high-energy He⁺ ion beams.     

Microstructural modifications induced by swift ions in the NiTi intermetallic compound

The conditions for track formation by irradiation with swift ions, in the shape memory NiTi metallic compound are studied. We observe that tracks are only induced in the monoclinic structure but not in the cubic one and only when the linear rate of energy deposition by electronic excitation ([dE/dx]_e) exceeds 46 keV/nm. We show that the tracks are amorphous in their centre and that a decrease of the monoclinic towards cubic transformation temperature is observed at the periphery of the track region. For [dE/dx]_e=32 keV/nm, no individual tracks can be observed at low fluences, only a monoclinic → cubic structure transformation is observed at high fluences. If [dE/dx] ⩽ 17 keV/nm, swift ions are unable to induce any visible structural modification by electronic excitations. The track formation in this alloy is discussed within the framework of the classical Coulomb explosion and thermal spike models.     

EPR study of defects produced by MeV Ag ion implantation into silicon

The damage produced by implanting (1 1 1) Si wafers with 4 MeV Ag ions at implantation temperatures of 210, 350 and 400 K has been investigated by electron paramagnetic resonance as a function of implantation fluence in the range 5 × 10¹²–2 × 10¹⁵ Ag cm⁻². For each implantation temperature, at low ion fluences the EPR spectra show the presence of the point defect centres Si-P3 (neutral 4-vacancy) and Si-P6 (di-interstitial) as well the so-called Σ defect complexes. As the implantation fluence is raised the population of P3 centres goes through a maximum while the Σ centre resonance is gradually replaced by the spectrum of the well-known Si-D centre of a-Si. For implantation at 210 K the total Σ+D centre concentration increases linearly with implantation fluence up to the point at which an amorphous layer is formed; however raising the implantation temperature causes the dependence of the Σ+D concentration on implantation fluence to become increasingly sublinear with the result that the production of a given level of damage requires a larger implantation fluence. The results are discussed in the context of a previous study of the implantation damage in the same samples by optical reflectivity depth profiling [Mat. Res. Soc. Symp. Proc. 540 (1999) 31].     

Effect of H+ and O+ implantation on electrical properties of SrBi2Ta2O9 ferroelectric thin films

The effect on the crystalline structure and ferroelectric properties of ion implantation in SrBi₂Ta₂O₉(SBT) ferroelectric thin films has been investigated. 25 keV H⁺, 140 keV O⁺ with doses from 1 × 10¹⁴/cm² to 3 × 10¹⁵/cm² were implanted into the Sol–Gel prepared SBT ferroelectric thin films. The X-ray diffraction patterns of SBT films show that no difference appears in the crystalline structure of as-H⁺-implanted SBT films compared with as-grown films, H⁺ and O⁺ co-implanted SBT films show an obvious degradation of crystalline structure. Ferroelectric properties measurements indicate that both remnant polarization and coercive electric field of H⁺ implanted SBT films decrease with increasing the implantation dose. The disappearance of ferroelectricity was found in the H⁺, O⁺ co-implanted SBT films at room temperature. The great recovery of hydrogen-induced degradation in SBT films was obtained with O⁺ implantation using a heat-target-implantation technique.     

Measuring the generation lifetime profile modified by MeV H+ ion implantation in silicon

A silicon wedge mask with thickness varying from approximately 5 μm to a few hundred μm has been used for converting the depth distribution of defect concentration induced by 4 MeV H⁺ ion implantation in silicon to a lateral scale on the surface, i.e. the distance from the edge of the wedge mask. Thus, using proper devices fabricated on bulk Si prior to ion implantation, depth profiles of the generation lifetime of minority charge carriers and of the different defect densities can be measured by the transient capacitance method and by Deep Level Transient Spectroscopy (DLTS), respectively. The distribution of lifetime follows well that of the implantation induced vacancies calculated by the TRIM code in the applied dose range (from 1 × 10¹⁰ to 3 × 10¹¹ H⁺/cm²). The correlation between implantation dose and lifetime decrease is also discussed.     

Microstructure of ion-implanted region in TiNi alloy

TiNi alloy samples implanted with various fluences of 3 MeV Cu²⁺ ions were characterized by transmission electron microscope (TEM) and X-ray diffractometer. Cross-sectional TEM images of the samples showed that amorphous region was seen at the fluence of 10¹⁴ ions cm^?2 in case of ion implantation at 300 K of the substrate temperature, but in case of ion implantation at 100 K it did not appear even at 10¹⁵ ions cm^?2. These results were also confirmed by X-ray diffraction profiles of the same samples. Consequently, the extent of microstructure change of TiNi alloy by ion implantation was different depending on the substrate temperature.     

Characterisation of Ni+ implanted PEEK,PET and PI

Polyimide (PI), polyetheretherketone (PEEK) and polyethyleneterephthalate (PET) were implanted with 40 keV Ni⁺ ions at room temperature at fluences ranging from 1.0 × 10¹⁶ to 1.5 × 10¹⁷ ions cm^?2 and with ion current density varying between 4 and 10 μA cm^?2. The depth profiles of the implanted Ni atoms determined by the RBS technique were compared with those predicted by the SRIM and TRIDYN codes. Hydrogen depletion as a function of the ion fluence was determined by the ERDA technique, and the compositional and structural changes of the polymers were characterised by the UV–vis and XPS methods. The implanted profiles differed significantly from those predicted by the SRIM code while the lower fluences were satisfactorily described by the TRIDYN simulation. A significant hydrogen release from the polymer surface layer was observed along with significant changes in the surface layer composition. The UV–vis results indicated an increase in the concentration and conjugation of double bonds.     

Characterization and qualification of advanced insulators for fusion magnets

Intensive research over the past decades demonstrated that the mechanical material performance of epoxy based glass fiber reinforced plastics, which are normally used by industry as insulating materials in magnet technology, degrades dramatically upon irradiation to fast neutron fluences above 1 × 10²² m^?2 (E > 0.1 MeV). which have to be expected in large fusion devices like ITER. This triggered an insulation development program based on cyanate ester (CE) and blends of CE and epoxies, which are not affected up to twice this fluence level, and therefore appropriate for large fusion magnets like the ITER TF coils. Together with several suppliers resin mixtures with very low viscosity over many hours were developed, which renders them suitable for the impregnation of very large volumes. This paper reports on a qualification program carried out during the past few years to characterize suitable materials, i.e. various boron-free R-glass fiber reinforcements interleaved with polyimide foils embedded in CE/epoxy blends containing 40% of CE, a repair resin, a conductor insulation, and various polyimide/glass fiber bonded tapes. The mechanical properties were assessed at 77 K in tension and in the interlaminar shear mode under static and dynamic load conditions prior to and after reactor irradiation at ~340 K to neutron fluences of up to 2 × 10²² m^?2 (E > 0.1 MeV). i.e. twice the ITER design fluence. The results confirmed that a sustainable solution has become available for this critical magnet component of ITER.     

Tailoring the spring constant of Si nanorod structures using swift heavy ion irradiation

This study reports a post-deposition technique of engineering the mechanical properties of cantilever-like silicon nanorods by using swift heavy ion irradiation. Slanted silicon nanorods grown by glancing angle deposition technique on a patterned Si(1 0 0) substrate are irradiated by 100 MeV Ag⁺⁸ ions at a fluence of 10¹⁴ ions cm^?2. The average spring constant (k) of the nanorods determined by force–distance spectroscopy reduces to 65.6 ± 20.8 Nm^?1 post-irradiation as compared to 174.2 ± 26.5 Nm^?1 for pristine nanorods. Scanning electron micrographs show bending of the Si nanorods after irradiation. Micro-Raman and high-resolution transmission electron microscope studies on pristine and irradiated Si nanorods confirm the transformation of nanocrystalline regions present in pristine nanorods to amorphous phase on irradiation. This structural transformation and bending of the nanorods are responsible for the observed changes in the mechanical properties post-irradiation. The technique offers a simpler possibility of tailoring mechanical properties of nanostructures post-deposition by ion irradiation.     

SHI induced re-crystallization of Ge implanted SiO2 films

Ge nanocrystals embedded in SiO₂ matrix have been synthesized by swift heavy ion irradiation of Ge implanted SiO₂ films. In the present study, 400 keV Ge⁺ ions were implanted into SiO₂ films at dose of 3 × 10¹⁶ ions/cm² at room temperature. The as-implanted samples were irradiated with 150 MeV Ag¹²⁺ ions with various fluences. Similarly 400 keV Ge⁺ ions implanted into Silicon substrate at higher fluence at 573 K have been irradiated with 100 MeV Au⁸⁺ ions at room temperature (RT). These samples were subsequently characterized by XRD and Raman to understand the re-crystallization behavior. The XRD results confirm the presence of Ge crystallites in the irradiated samples. Rutherford backscattering spectrometry (RBS) was used to quantify the concentration of Ge in the SiO₂ matrix. Variation in the nanocrystal size as a function of ion fluence is presented. The basic mechanism of ion beam induced re-crystallization has been discussed.     

Empirical approach to the description of spectral performance degradation of silicon photodiodes used as particle detectors

The spectral deterioration of Hamamatsu S5821 silicon photodiodes for ion types and energies frequently used in Ion Beam Analysis was investigated. Focused proton beams with energies 430 keV and 2 MeV were applied to generate radiation damage via an area selective ion implantation in unbiased diodes at room temperature. The variations of spectroscopic features were measured “in situ” by Ion Beam Induced Current (IBIC) method as a function of fluence, within the 10⁹–5 × 10¹² ion/cm² range and diode bias voltages, between 0 and 100 V.An empirical model has been developed to describe the radiation damage. Equations are derived for the variations of the normalized peak position and peak width. The derived empirical equations are physically correct, as far as they account for the superposition of the influence of charge carrier trapping by native and radiation-induced defects and for the effect of charge carrier velocity saturation with electric field strength, as well.     

Ion implantation into aluminum and copper by a beam of carbon nanoparticles from regenerative sooting discharges

We present a new technique to generate light carbon nanoparticles from regenerative sooting discharges and its use for ion implantation on aluminum and copper surfaces at an energy of 40 keV. Films formed at fluences up to 3 × 10¹⁵ C⁺/cm² for aluminum and 10¹⁶ C⁺/cm² for copper are studied using Raman spectroscopy, X-ray diffraction and atomic force microscopy. Raman spectroscopy reveals the existence of graphite and diamond like structures in all samples. Precipitates of Al₄C₃ of rhombohedral and hexagonal types were found in the nanometer ranges from the X-ray diffraction pattern for aluminum samples and the probable formation of body-centered cubic diamond and hexagonal carbon in copper samples. The average grain sizes of Al₄C₃ were calculated ～40 nm for Al and ～35 nm for Cu. Mass spectra from a graphite hollow cathode duoplasmatron ion source are also presented. Atomic force microscopy images of a Cu sample also support the existence of 46 nm structures. Light carbon nanoparticles are readily available from the ion source in which a special carbonaceous environment creates regenerative soot. Support gas Ar produces more C₃ than Ne.     

Determination of differential cross-sections for the natK(p, p0) and 39K(p, α0) reactions in the backscattering geometry

In the present work, new, differential cross-section values are presented for the ^natK(p, p₀) reaction in the energy range E_lab = 3000–5000 keV (with an energy step of 25 keV) and for detector angles between 140° and 170° (with an angular step of 10°). A qualitative discussion of the observed cross-section variations through the influence of strong, closely spaced resonances in the p + ³⁹K system is also presented. Information has also been extracted concerning the ³⁹K(p,α₀) reaction for E_lab = 4000–5000 keV in the same angular range. As a result, more than ～500 data points will soon be available to the scientific community through IBANDL (Ion Beam Analysis Nuclear Data Library – http://www-nds.iaea.org/ibandl/) and could thus be incorporated in widely used IBA algorithms (e.g. SIMNRA, WINDF, etc.) for potassium depth profiling at relatively high proton beam energies.     

Damage accumulation and annealing in 6H–SiC irradiated with Si+

Damage accumulation and annealing in 6H-silicon carbide (α-SiC) single crystals have been studied in situ using 2.0 MeV He⁺ RBS in a 〈0 0 0 1〉-axial channeling geometry (RBS/C). The damage was induced by 550 keV Si⁺ ion implantation (30° off normal) at a temperature of −110°C, and the damage recovery was investigated by subsequent isochronal annealing (20 min) over the temperature range from −110°C to 900°C. At ion fluences below 7.5 × 10¹³ Si⁺/cm² (0.04 dpa in the damage peak), only point defects appear to be created. Furthermore, the defects on the Si sublattice can be completely recovered by thermal annealing at room temperature (RT), and recovery of defects on the C sublattice is suggested. At higher fluences, amorphization occurs; however, partial damage recovery at RT is still observed, even at a fluence of 6.6 × 10¹⁴ Si⁺/cm² (0.35 dpa in the damage peak) where a buried amorphous layer is produced. At an ion fluence of 6.0 × 10¹⁵ Si⁺/cm² (−90°C), an amorphous layer is created from the surface to a depth of 0.6 μm. Because of recovery processes at the buried crystalline–amorphous interface, the apparent thickness of this amorphous layer decreases slightly (<10%) with increasing temperature over the range from −90°C to 600°C.