The solid film lubrication by carbon ion implantation into α-Al2O3

Improvement in tribological performance by C⁺110 keV implantation can be achieved by having a more graphite-like carbon structure on Al₂O₃. It was shown that fracture toughness and critical peeling load increased for a fluence of 5 × 10¹⁷C⁺/cm² because of residual compression stress and amorphism of surface. The testing in a different implantation dose indicated that the friction and wear mechanism in Optimol fretting wear machine (SRV) was a combination of surface structure and its abrasive wear. Raman shift shows that the amorphous graphite with 5 × 10¹⁷–1 × 10¹⁸ C⁺/cm² implantation dose was formed on Al₂O₃ surface, so that it reduced friction coefficient and wear of Al₂O₃, also it is noticed that the failure of lubrication due to graphite-like film wear is much earlier in the implantation sample with 1 × 10¹⁷C⁺/cm² dose.     

Swift heavy ion induced modifications of optical and microstructural properties of silver–fullerene C60 nanocomposite

In this paper, we study the optical and microstructural properties of silver–fullerene C₆₀ nanocomposite and their modifications induced by swift heavy ion irradiation. Silver nanoparticles embedded in fullerene C₆₀ matrix were synthesized by co-deposition of silver and fullerene C₆₀ by thermal evaporation. The nanocomposite thin films were irradiated by 120 MeV Ag ions at different fluences ranging from 1 × 10¹² to 3 × 10¹³ ions/cm². Optical absorption studies revealed that the surface plasmon resonance of Ag nanoparticles showed a blue shift of ～49 nm with increasing ion fluence up to 3 × 10¹³ ions/cm². Transmission electron microscopy and Rutherford backscattering spectroscopy were used to quantify particle size and metal atomic fraction in the nanocomposite film. Growth of Ag nanoparticles was observed with increasing ion fluence. Raman spectroscopy was used to understand the effect of heavy ion irradiation on fullerene matrix. The blue shift in plasmonic wavelength is explained by the transformation of fullerene C₆₀ matrix into amorphous carbon.     

Self-organized formation of layered carbon–copper nanocomposite films by ion deposition

The quasi-simultaneous deposition of low energy-mass-selected C⁺ and metal⁺ ions leads to the formation of metal–carbon nanocomposites. In the case of C⁺ and Cu⁺ deposition, a homogeneous distribution of small copper clusters in an amorphous carbon matrix is expected. However, at a certain C⁺/Cu⁺ fluence ratio and energy range, alternately metal-rich and metal-deficient layers in an amorphous carbon matrix with periods in the nm range develop have been observed. The metal-rich layers consist of densely distributed crystalline Cu particles while the metal-deficient layers are amorphous and contain only few and small Cu clusters. The formation of multilayers can be described by an interplay of sputtering, surface segregation, ion induced diffusion, and the stability of small clusters against ion bombardment. This formation has been investigated for the a-C:Cu system with respect to the ion energy and the C⁺/Cu⁺ fluence ratio. The sputter coefficient S_M = r_f S_CCu + S_CuCu is the parameter to switch between layer growth (S_M < 1) and homogeneous cluster distribution (S_M > 1).     

Direct measurements of small 14C samples after oxidation in quartz tubes

Small ¹⁴C samples gain importance in environmental research and for dating purposes. However, throughput of such samples is limited by the preparation of graphite targets for accelerator mass spectrometry (AMS) measurements. In our approach, oxidation of samples with copper oxide in quartz tubes was applied to form CO₂ which was measured directly with the gas ion source of the small AMS facility MICADAS. The presented method was designed to meet the requirements for fast and easy handling of small samples (<100 μg carbon). As combustion byproducts are likely to interfere with ionisation processes in the gas ion source, we additionally investigated the effects of several gases on C^? currents.     

Theoretical critical angels of ion channeling in carbon nanotubes

We have developed a mass- and charge-dependent equation to predict theoretical critical angles for ion channeling in carbon nanotubes. We focus M (ion mass) effects how to reduce Ze (ion nucleus charge) effects on Ψ_C (critical angles). As an instance, we give theoretical critical angels of He, Ne, Ar, Kr, Xe and Rn ion channeling in carbon nanotubes. We find that for (10, 10) single-wall carbon nanotubes, Ψ_C(He) ≈ Ψ_C(Ne) ≈ Ψ_C(Ar) ≈ Ψ_C(Kr) ≈ Ψ_C(Xe) ≈ Ψ_C(Rn) ≈ 23.3 (keV/E)^1/2 deg. This is because (Z/M)^1/2 ≈ 0.66 [amu]^?1/2.     

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.     

Formation of complex Al–N–C layer in aluminium by successive carbon and nitrogen implantation

The results of Auger electron spectroscopy and transmission electron microscopy of the surface layer of aluminium after successive implantation by carbon and nitrogen ions are presented in this work. The energy of implanted ions is 40 keV. The implantation dose varies in the range (3.3–6.5) × 10¹⁷ ions/cm². The findings show that successive implantation leads to the formation of two main layers in aluminium. The first layer is AlNC_x (0 < x < 0.5) layer with violated hcp. AlN structure, where carbon atoms form bonds with nitrogen atoms. The second layer contains disoriented Al₄C₃ precipitates and carbon atoms migrated from the first layer. The mechanism of migration is discussed.     

A broad chemical and structural characterization of the damaged region of carbon implanted alumina

As candidate materials for future thermonuclear fusion reactors, isolating ceramics will be submitted to high energy gamma and neutron radiation fluxes together with an intense particle flux. Amorphization cannot be tolerated in ceramics for fusion applications, due to the associated volume change and the deterioration of mechanical properties. Therefore, a comprehensive study was carried out to examine the effects of carbon beam irradiation on polycrystalline aluminium oxide (Al₂O₃), a ceramic component of some diagnostic and plasma heating systems. Complementary techniques have allowed a complete chemical and structural surface analysis of the implanted alumina. Implantation with 75 keV, mono-energetic carbon ions at doses of 1 × 10¹⁷ and 5 × 10¹⁷ ions/cm² was performed on polished and thermally treated ceramic discs. The alumina targets were kept below 120 °C. The structural modifications induced during ion irradiation were studied by the GXRD and TEM techniques. Under these conditions, alumina is readily amorphized by carbon ions, the thickness of the ion-beam induced disordered area increasing with the ion dose. Matrix elements and ion implanted profiles were followed as a function of depth by using ToF-SIMS, indicating the maximum concentration of implanted ions to be in the deeper half of the amorphous region. Ion distribution and chemical modifications caused in the Al₂O₃ substrate by carbon irradiation were corroborated with XPS. The amount of oxygen in the vicinity of the implanted alumina surface was reduced, suggesting that this element was selectively sputtered during carbon irradiation. The intensity of those peaks referring to Al–O bonds diminishes, while contributions of reduced aluminium and metal carbides are found at the maximum of the carbon distribution. TEM observations on low temperature thermally annealed specimens indicate partial recovery of the initial crystalline structure.     

Pulsed repetition rate nanosecond laser heating and ablation of the tokamak graphite tile deposited layers

Laser heating and ablation of the plasma-facing surface of a graphite tile from TEXTOR tokamak that was covered by a deposited carbon layer has been studied. Laser heating measurements were performed with a pulsed nanosecond Nd-YAG laser (2nd harmonic, 10 kHz repetition rate, 100 ns pulse duration). Surface temperature measurements were recorded with a home-made pyrometer having a response time of 15 μs (t_99%). The experimental results are simulated with an analytical model of laser heating of a surface covered by a deposited layer and heated repeatedly by laser pulses. The comparison between experimental and theoretical data of the observed temperature excursions enables us to assess the deposited carbon layer physical parameters (thermal conductivity, porosity, etc.) if the thermal and optical properties of the graphite substrate are known. Laser ablation measurements were performed with two pulsed nanosecond Nd-YAG lasers (20 Hz and 10 kHz repetition rate with 5 ns and 100 ns pulse duration, respectively). For a plasma-facing graphite surface covered by a thick (～30–50 μm) deposited carbon layer, the ablation threshold is 4.5 ± 1 kJ/m² regardless of the pulse duration. The obtained ablation threshold is significantly lower than the one measured for a virgin tokamak graphite sample. The comparison of the experimental results and theoretical data demonstrated that the laser ablation mechanisms for tokamak graphite and thick carbon layers deposited on plasma-facing surface are different.     

An advance process of aluminum rich coating as tritium permeation barrier on 321 steel workpiece

We have proposed an advance three-step process, Al-electroplating in ionic liquid followed by heat treating and selectively oxidation, preparing aluminum rich coating as tritium permeation barrier (TPB). In present work, the advance process was applied to 321 steel workpieces. In the Al-electroplating, pieces were coated by galvanostatic electrodeposition at 20 mA/cm² in aluminum chloride (AlCl₃)–1-ethyl-3-methylimidazolium chloride (EMIC) ionic liquid. The Al coating on those pieces all displayed attractive brightness and well adhered to surface of pieces. Within the aluminizing time from 1 to 30 h, a series of experiments were carried out to aluminize 321 steel pieces with Al 20 μm coating at 700 °C. After heat treated for 8 h, a 30 μm thick aluminized coating on piece appeared homogeneous, free of porosity, and mainly consisted of (Fe, Cr, Ni)Al₂, and then was selectively oxidized in argon gas at 700 °C for 50 h to form Al₂O₃ scale. The finally fabricated aluminum rich coating, without any visible defects, had a double-layered structure consisting of an outer γ-Al₂O₃ layer with thickness of 0.2 μm and inner (Fe, Cr, Ni)Al/(Fe, Cr, Ni)₃Al layer of 50 μm thickness. The deuterium permeation reduction factor, PRF, of piece (Φ 80 × 2, L 150 mm) with such coating increased by 2 orders of magnitude at 600–727 °C. The reproducibility of the process was also showed.     

Soft X-ray fluorescence measurements of irradiated polymer films

Fluorescent soft X-ray carbon Kα emission spectra (XES) have been used to characterize the bonding of carbon atoms in polyimide (PI) and polycarbosilane (PCS) films. The PI films have been irradiated with 40 keV nitrogen or argon ions, at fluences ranging from 1 × 10¹⁴ to 1 × 10¹⁶ cm⁻². The PCS films have been irradiated with 5 × 10¹⁵ carbon ions cm⁻² of 500 keV and/or annealed at 1000°C. We find that the fine structure of the carbon XES of the PI films changes with implanted ion fluence above 1 × 10¹⁴ cm⁻² which we believe is due to the degradation of the PI into amorphous C:N:O. The width of the forbidden band as determined from the high-energy cut-off of the C Kα X-ray excitation decreases with the ion fluence. The bonding configuration of free carbon precipitates embedded in amorphous SiC which are formed in PCS after irradiation with C ions or combined treatments (irradiation and subsequent annealing) is close to either to that in diamond-like films or in silicidated graphite, respectively.     

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.     

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.     

Gaseous radiocarbon measurements of small samples

Radiocarbon dating by means of accelerator mass spectrometry (AMS) is a well-established method for samples containing carbon in the milligram range. However, the measurement of small samples containing less than 50 μg carbon often fails. It is difficult to graphitise these samples and the preparation is prone to contamination. To avoid graphitisation, a solution can be the direct measurement of carbon dioxide. The MICADAS, the smallest accelerator for radiocarbon dating in Zurich, is equipped with a hybrid Cs sputter ion source. It allows the measurement of both, graphite targets and gaseous CO₂ samples, without any rebuilding.This work presents experiences dealing with small samples containing 1-40 μg carbon. 500 unknown samples of different environmental research fields have been measured yet. Most of the samples were measured with the gas ion source. These data are compared with earlier measurements of small graphite samples. The performance of the two different techniques is discussed and main contributions to the blank determined. An analysis of blank and standard data measured within years allowed a quantification of the contamination, which was found to be of the order of 55 ng and 750 ng carbon (50 pMC) for the gaseous and the graphite samples, respectively. For quality control, a number of certified standards were measured using the gas ion source to demonstrate reliability of the data.     

Synthesis of nanostructured multiphase Ti(C,N)/a-C films by a plasma focus device

Nanostructured multiphase Ti(C,N)/a-C films were deposited using a 3.3 kJ pulsed plasma focus device onto silicon (1 0 0) substrates at room temperature. The plasma focus device, fitted with solid titanium anode instead of usual hollow copper anode, was operated with nitrogen and Ar/CH₄ as the filling gas. Films were deposited with different number of shots, at 80 mm from top of the anode and at zero angular position with respect to anode axis. X-ray diffraction results show the diffraction peaks related to different compounds such as TiC₂, TiN, Ti₂CN, Ti and TiC_0.62 confirming the deposition of multiphase titanium carbo-nitride composite films on silicon. X-ray photoelectron spectroscopy confirms the formation of Ti–C, C–N, Ti–N, Ti–O and C–C bonds in the films. Scanning electron microscopy reveals that the nanostructure grains are agglomerates of smaller nanoparticles about 10–20 nm in size. Raman studies verify the formation of multiphase Ti(C,N) and also of amorphous graphite in the films. The maximum microhardness value of the composite film is 14.8 ± 1.3 GPa for 30 shots.     

Preparation of tungsten coatings on graphite by electro-deposition via Na2WO4–WO3 molten salt system

Tungsten coating on graphite substrate is one of the most promising candidate materials as the ITER plasma facing components. In this paper, tungsten coatings on graphite substrates were fabricated by electro-deposition from Na₂WO₄–WO₃ molten salt system at 1173 K in atmosphere. Tungsten coatings with no impurities were successfully deposited on graphite substrates under various pulsed current densities in an hour. By increasing the current density from 60 mA cm⁻² to 120 mA cm⁻² an increase of the average size of tungsten grains, the thickness and the hardness of tungsten coatings occurs. The average size of tungsten grains can reach 7.13 μm, the thickness of tungsten coating was in the range of 28.8–51 μm, and the hardness of coating was higher than 400 HV. No cracks or voids were observed between tungsten coating and graphite substrate. The oxygen content of tungsten coating is about 0.022 wt%.     

129I AMS at 0.5 MV tandem accelerator

The ¹²⁹I measurement program has been established at the 0.5 MV ‘Tandy’ accelerator of the PSI/ETH Zürich AMS facility. This development was made possible by using a SiN window instead of Mylar one in a gas ionization detector. The setting up of the ¹²⁹I measurement at Tandy is simple, the acquired performance is stable and reliable, and the quality of results is equal to or better than at our larger EN-tandem. With this setup, high sample throughput, which is required in many ¹²⁹I studies, can be easily achieved. The measurements are performed in the +3 charge state. At this charge state the major difficulty in the ¹²⁹I⁺³ identification is caused by a highly abundant 43⁺¹ (m = 43, q = +1) molecule interference. This is a positive molecular ion, because its intensity reduces exponentially with an increase in gas stripper pressure. We conclude that this molecule is ²⁷Al¹⁶O⁺ (m/q = 43/1 = 129/3) and comes from the break-up of (Al₂O₃ + Al)^? (m = 129) precursor at the terminal: (Al₂O₃ + Al)^? → ²⁷Al¹⁶O⁺. The expected isobaric interferences ⁴³Ca⁺¹ and ⁸⁶Sr⁺², which also originate from the break-up of molecules in the stripper, were found to be low and do not disturb the ¹²⁹I⁺³ measurements. The best repeatable performance with our standard sample material was achieved at 0.14 μg/cm² Ar gas stripper pressure with machine blanks showing ～6 × 10^?14 normalized ¹²⁹I/I ratio and 9% transmission through the accelerator. However, high ²⁷Al¹⁶O⁺ molecular rates were observed from the user samples, and in order to destroy these molecules we had to increase the stripper pressure to ～0.22 μg/cm². This increase in the stripper pressure degraded the machine blank values to ～9 × 10^?14 and reduced transmission to 8%. Nevertheless, the achieved measurement conditions are sufficient for measurement of nearly all ¹²⁹I samples that have been submitted to PSI/ETH over the last few years.     

Controlling the microstructure of ZnO nanoparticles embedded in Sapphire by Zn ion implantation and subsequent annealing

(0 0 0 1) α-Al₂O₃ single crystals (sapphire) were implanted with Zn ions of 60 keV at a fluence of 1 × 10¹⁷ ions/cm². Transmission electron microscopy and optical absorption spectroscopy studies show the formation of ZnO nanoparticles in the sapphire substrate after the implanted sample was annealed at 700 °C in oxygen ambient. The photoluminescence spectrum of the annealed sample indicates the formation of ZnO nanoparticles with perfect lattice structure. The selected-area electron diffraction pattern proves that the ZnO nanoparticles have the (0 0 0 2) orientation which follows the orientation of Al₂O₃ substrate. The result shows that the crystallographic orientation of nanoparticles obtained through ion implantation is defined by the substrate.     

Photoluminescence induced from hot Ge implantation into SiO2

Up to the present, by using the ion implantation technique, photoluminescence (PL) from Ge nanocrystals (Ge NCs) was obtained by room temperature (RT) Ge implantation into a SiO₂ matrix followed by a high temperature anneal. In this way two PL bands were observed, one at 310 nm and the second, with much higher yield at 390 nm. In the present work we have used another experimental approach. We have performed the Si implantation at high temperature (T_i) and then, we have done a higher temperature anneal (T_a) in order to nucleate the Ge NCs. With this aim we have changed T_i between RT and 600 °C. By performing the implantation at T_i = 350 °C we found a PL yield four times higher than the one obtained from the usual RT implantation at the same fluence. Moreover, by changing the implantation fluence between Φ = 0.25 × 10¹⁶ and 2.2 × 10¹⁶ Ge/cm² we observed that Φ = 0.5 × 10¹⁶ Ge/cm² induces a PL yield three times higher as compared to the usual RT implantation fluence. In conclusion, using a hot Ge implantation plus an optimal Ge atomic concentration, we were able to gain more than one order of magnitude in the 390 nm PL yield as compared with previous ion implantation results.     

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.