Ion synthesis of silver nanoparticles in viscous-fluid epoxy resin

A method is described for the ion synthesis of silver nanoparticles in epoxy resin that is in a viscousfluid state (viscosity 30 Pa s) during irradiation. The viscous-fluid or glassy polymer is implanted by 30-keV silver ions at a current density of 4 μA/cm² in the ion beam in the dose range 2.2 × 10¹⁶–7.5 × 10¹⁶ ions/cm². The epoxy layers thus synthesized contain silver nanoparticles, which are studied by transmission electron microscopy and optical absorption spectroscopy. The use of the viscous-fluid state increases the diffusion coefficient of the implanted impurity, which stimulates the nucleation and growth of nanoparticles at low implantation doses and allows a high factor of filling of the polymer with the metal to be achieved.     

The effect of high implant doses and high ion current densities on polyimide film properties

Ar⁺ and Ar²⁺ ions with energies of 40 and 80 keV are implanted into thin polyimide films. The implant doses and the ion current densities are varied in a wide range between 2.5×10¹⁴ and 1.5×10¹⁷ cm⁻² and between 1 and 16 μA/cm², respectively. The effect of the implantation parameters on the electrical, paramagnetic, and optical properties of the ion-modified near-surface polymer layer is studied. It is shown that the radiation-stimulated thermolysis of polyimide and its chemical constitution are responsible for a monotonic growth of the electrical conductivity of the layer with increasing ion current at a given implant dose. When the ion current density is fixed, the conductivity grows stepwise with implant dose, whereas the concentration of paramagnetic centers and the optical transmission of the modified layer decrease. The dependences observed are treated within a model of the structural reconfiguration of the polymer carbonized phase formed during the implantation.     

Experimental study of laser induced decomposition based processing of a brittle plastic,CR-39 (allyl diglycol carbonate)

A cw CO₂ laser, coupled with an astigmatism free beam focussing mirrors arrangement is used for processing a brittle plastic, CR-39 without producing cracks, vents or chips. The processing is based on the formation of volatile products of laser-induced decomposition in the plastic. Threshold fluence for the decomposition (found to be independent of the power density and beam residence time) in CR-39 at=10.6m is determined to be 25 J cm^–2 and the decomposition threshold power density for cw irradiation 2.1±0.5 W cm^–2. The depth and width of the tapered laser processed region are observed to increase with power density and beam residence time. The widths attain a steady state value of 1 mm at beam residence time above 65 ms, for a fixed power density (2.5×10⁴ W cm^–2) and sheet thickness (250 m). Taper angle of the edges decreases with increasing power density and/or beam residence time. The heat affected zone (measured in crossed polarisers) around the processed region is found to extend with increasing beam residence time but remains unaffected on changing power density. The results are discussed in terms of the optical and thermophysical properties of CR-39 and the parameters of the interacting laser beam.     

AC electrical properties of proton irradiated EVA films

MeV ions passing through polymeric films modify their electrical, optical and thermal properties and these changes are related to changes in the chemical structure of the polymers. Ethylene vinyl acetate (EVA) films were irradiated with 3 MeV proton beam at different fluences of 10¹³, 10¹⁴ and 10¹⁵ ions/cm². AC electrical properties of pristine and irradiated samples were studied in the frequency range 100 Hz to 100 kHz by means of an LCR meter. There is an exponential increase in conductivity with log frequency and conductivity increases as fluence increases. The dielectric loss/constant is observed to change with the fluence. FTIR spectra reveals significant change in intensities of functional groups at a fluence of 10¹⁵ ions/cm² due to scissioning of polymer chains.     

Li3+ ion irradiation effects on ionic conduction in P(VDF–HFP)–(PC + DEC)–LiClO4 gel polymer electrolyte system

Swift heavy ion irradiation of P(VDF–HFP)–(PC + DEC)–LiClO₄ gel polymer electrolyte system with 48 MeV Li³⁺ ions having five different fluences was investigated with a view to increase the Li⁺ ion diffusivity in the electrolyte. Irradiation with swift heavy ion (SHI) shows enhancement of conductivity at lower fluences and decrease in conductivity at higher fluences with respect to unirradiated polymer electrolyte films. Maximum room temperature (303 K) ionic conductivity is found to be 2.2 × 10^− 2 S/cm after irradiation with fluence of 10¹¹ ions/cm². This interesting result could be ascribed to the fluence-dependent change in porosity and to the fact that for a particular ion beam with a given energy higher fluence provides critical activation energy for cross-linking and crystallization to occur, which results in the decrease in ionic conductivity. The XRD results show decrease in the degree of crystallinity upon ion irradiation at low fluences (≤ 10¹¹ ions/cm²) and increase in crystallinity at high fluences (> 10¹¹ ions/cm²). The scanning electron micrographs (SEM) exhibit increased porosity of the polymer electrolyte films after low fluence ion irradiation.     

Surface modification of poly(propylene carbonate) by oxygen ion implantation

Poly(propylene carbonate) (PPC) was implanted by oxygen ion with energy of 40 keV. The influence of experimental parameters was investigated by varying ion fluence from 1 × 10¹² to 1 × 10¹⁵ ions/cm². XPS, SEM, surface roughness, wettability, hardness, and modulus were employed to investigate structure and properties of the as-implanted PPC samples. Eight chemical groups, i.e., carbon, CH, COC, CO, OCO, CO, , and groups were observed on surfaces of the as-implanted samples. The species and relative intensities of the chemical groups changed with increasing ion fluence. SEM images displayed that irradiation damage was related strongly with ion fluence. Both surface-recovering and shrunken behavior were observed on surface of the PPC sample implanted with fluence of 1 × 10¹⁵ ions/cm². As increasing ion fluence, the surface roughness of the as-implanted PPC samples increased firstly, reached the maximum value of 159 nm, and finally decreased down the minimum value. The water droplet contact angle of the as-implanted PPC samples changed gradually with fluence, and reached the minimum value of 70° with fluence of 1 × 10¹⁵ ions/cm². The hardness and modulus of the as-implanted PPC samples increased with increasing ion fluence, and reached their corresponding maximum values with fluence of 1 × 10¹⁵ ions/cm². The experimental results revealed that oxygen ion fluence closely affected surface chemical group, morphology, surface roughness, wettability, and mechanical properties of the as-implanted PPC samples.     

Structural features of aluminium alloy 1441 irradiated by Ar+ ions

Using electron microscopy it was found that irradiation of clad cold-worked specimens made of commercial aluminium-lithium alloy 1441 by the Ar ⁺ ions of energy 40 keV at low doses of irradiation (10¹⁵ cm⁻², irradiation time 1 s, T < 70 °C) and ion-current density of about 100 μA/cm² results in the transformation of the cellular structure formed in the alloy under deformation. As the dose of irradiation is increased up to 10¹⁶ cm⁻², a transition from a cellular to a subgrain structure close to a polygonal one is observed. The efficiency of the process is increased with ion-current density. Furthermore, under ion irradiation at increased ion-current densities, the β′(Al ₃ Zr) and Al ₈ Fe ₂ Si particles present in the deformed alloy dissolve, and disperse particles of a new Al ₂ LiMg phase of platelet shape are formed. The changes in the dislocation structure and phase composition in alloy 1441 are observed several seconds after irradiation not only in the surface layer adjacent to the ion incorporation band but also through the thickness of the specimen tens of thousands times greater than ion projective ranges. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 73–81, February, 2007.     

Effects of irradiation parameters on metal surface erosion by pulsed ion beams

Potential application of high-power ion beams of submicrosecond and microsecond durations with the initial particle energy from 50 to 1000 keV and power density 10⁷–10⁹ W/cm² to ensure metal surface erosion are investigated. Evaporation is treated as a major erosion mechanism and the erosion coefficient is taken as an efficiency indicator. Dependences of the erosion coefficients of several metals on beam parameters obtained via calculations using a technique based on the solution of thermal conductivity equation with phase transitions are presented. The ion species, their initial energy, current pulse duration and power density are used as the beam parameters controlling the result of irradiation. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 49–54, August, 2007.     

Excimer-laser-induced permanent electrical conductivity in solid C60 films

After being irradiated in air by a XeCI (308 nm) excimer laser, the electrical conductivity of solid thin-film C₆₀ has been improved by more than six orders of magnitudes. The products resulting from laser irradiation of C₆₀ films have been investigated by Raman scattering and the onset of conductivity can be attributed to laser-induced oxygenation and disintegration of the fullerene. Irradiated by 40 ns laser pulses with different fluence, products with different microstructure were observed. At lower fluence, the Raman features of microcrystalline graphite and fullerene polymer were observed. At a fluence just below the ablation threshold (36 mJ/cm²), the fullerene molecules in the film were disintegrated completely and transformed to amorphous graphite.     

Effect of Ar bombardment on the electrical and optical properties of low-density polyethylene films

The influence of low-energy Ar ion beam irradiation on both electrical and optical properties of low-density polyethylene (LDPE) films is presented. The polymer films were bombarded with 320 keV Ar ions with fuences up to 1×10¹⁵ cm^?2. Electrical properties of LDPE films were measured and the effect of ion bombardment on the DC conductivity, dielectric constant and loss was studied. Optically, the energy gap, the Urbach’s energy and the number of carbon atoms in a cluster were estimated for all polymer samples using the UV–Vis spectrophotometry technique. The obtained results showed slight enhancement in the conductivity and dielectric parameters due to the increase in ion fluence. Meanwhile, the energy gap and the Urbach’s energy values showed significant decrease by increasing the Ar ion fluence. It was found that the ion bombardment induced chain scission in the polymer chain causing some carbonization. An increase in the number of carbon atoms per cluster was also observed.     

The fluence effect in hydrogen-ion cleaving of silicon at the sub-100-nm scale

The implementation at the sub-100-nm scale of ion cleaving requires ion beams of 5 keV/amu or less. The blistering efficiency in 5-keV H-ion-implanted and annealed Si has been found to peak and vanish in a narrow range of ion fluence of (1.5–3.5)×10¹⁶H/cm². In order to understand this effect, the defect profiles in 5-keV H-irradiated Si were studied by Rutherford backscattering/channelling, while the Si-H bonding configurations during annealing were investigated by Raman scattering spectroscopy. Three types of defects play major roles: the broad-band monohydride multivacancy complexes, the fully or partially passivated monovacancy VH_n, and H-terminated internal surfaces Si(100):H. Blister absence at high fluence is characterised by the persistence up to 550 °C of the Si(100):H structures, which are blister embryos that failed to coalesce and grow. Radiation-induced stresses and fracture toughening may play roles in inhibiting cleavage at high fluence; however, widening towards the surface of the zone of high H and defect concentration is the likely major factor. PACS 61.82.Fk; 82.80.Gk; 61.85.+p     

Study on the effect of Ar9+ ion irradiation of Zr–2.5 wt.% Nb alloy pressure tube

Response of Zr–2.5 wt.% Nb alloy pressure tube, used in PHWR nuclear reactors, to 315 keV Ar⁹⁺ ion irradiation at room temperature was investigated in the fluence range of 3.1?×?10¹⁵–4.17?×?10¹⁶ Ar⁹⁺?cm^?2. Changes in microstructural parameters, viz., the size of coherently scattering domains, microstrain and dislocation density, upon irradiation were ascertained through grazing incidence X-ray diffraction. In general, a decrease in domain size was observed with fluence with a corresponding increase in microstrain and dislocation density. Residual stress measurement showed the development of compressive stresses in place of tensile after irradiation. Transmission electron microscopy showed the formation of dislocation loops of ?a?-type and ?c?-type during irradiation. The hardness of irradiated samples, probed through nanoindentation technique, was found to be higher in comparison with unirradiated samples. The above findings have been rationalised on the basis of the defects generated during the Ar⁹⁺ ion irradiation.     

Ar irradiation of Si nanocrystal-doped SiO2: Evolution of photoluminescence

We report the evolution of photoluminescence (PL) of Si nanocrystals (nc-Si) embedded in a matrix of SiO₂ during Ar⁺ ion bombardment. The integrated intensity of nc-Si PL falls down drastically before the Ar⁺ ion fluence of 10¹⁵ ions cm⁻², and then decreases slowly with the increasing ion fluence. At the meantime, the PL peak position blueshifts steadily before the fluence of 10¹⁵ ions cm⁻², and then changes in an oscillatory manner. Also it is found that the nc-Si PL of the Ar⁺-irradiated sample can be partly recovered after annealing at 800 °C in nitrogen, but can be almost totally recovered after annealing in oxygen. The results confirm that the ion irradiation-induced defects are made up of oxygen vacancies, which absorb light strongly. The oscillatory peak shift of nc-Si can be related to a size-distance distribution of nc-Si in SiO₂.     

Optical properties of ZnO and Al2O3 implanted with silver ions

ZnO and Al₂O₃ samples implanted with 30-keV silver ions with fluences in the interval (0.25–1.00) × 10¹⁷ ions/cm² are studied by the method of optical photometry in the visible part of the spectrum. The optical transmission spectra of the implanted samples exhibit a selective band associated with surface plasmon resonance absorption of silver nanoparticles. The intensity of this band nonmonotonically depends on the implantation fluence. The silver ion depth distribution in the samples is calculated. It is shown that the non-monotonicity observed in experiments is due to an increase in the substrate sputtering ratio with increasing implantation fluence. It is found that vacuum thermal annealing of the implanted Al₂O₃ layers up to 700°C causes a considerable narrowing of the plasmon absorption bandwidth without a tangible change in its intensity. At higher annealing temperatures, the plasmon absorption band broadens and its intensity drops. Annealing of the ZnO films under such conditions causes their complete vaporization.     

Enhancement in electrochemical properties of ionic liquid-based nanocomposite polymer electrolytes by 100 MeV Si9+ swift heavy ion irradiation

Swift heavy ion (SHI) irradiation has been used as a tool to enhance the electrochemical properties of ionic liquid-based nanocomposite polymer electrolytes dispersed with dedoped polyaniline (PAni) nanorods; 100 MeV Si⁹⁺ ions with four different fluences of 5?×?10¹⁰, 1?×?10¹¹, 5?×?10¹¹, and 1?×?10¹² ions cm^?2 have been used as SHI. XRD results depict that with increasing ion fluence, crystallinity decreases due to chain scission up to fluence of 5?×?10¹¹ ions cm^?2, and at higher fluence, crystallinity increases due to cross-linking of polymer chains. Ionic conductivity, electrochemical stability, and dielectric properties are enhanced with increasing ion fluence attaining maximum value at the fluence of 5?×?10¹¹ ions cm^?2 and subsequently decrease. Optimum ionic conductivity of 1.5?×?10^?2 S cm^?1 and electrochemical stability up to 6.3 V have been obtained at the fluence of 5?×?10¹¹ ions cm^?2. Ac conductivity studies show that ion conduction takes place through hopping of ions from one coordination site to the other. On SHI irradiation, amorphicity of the polymer matrix increases resulting in increased segmental motion which facilitates ion hopping leading to an increase in ionic conductivity. Thermogravimetric analysis (TGA) measurements show that SHI-irradiated nanocomposite polymer electrolytes are thermally stable up to 240–260 °C.     

Recombination measurements at low energies with Ar16+ and Ar18+ ions in a dense, cold electron target

Recombination of multiply charged ions with electrons at very low relative energies has become a major topic of interest, due to the observation of rates which are enhanced beyond the expectations for radiative recombination. We present results for Ar¹⁶⁺ and Ar¹⁸⁺ ions from systematic measurements along the argon isonuclear sequence using a high density cold electron beam target (n_e = 7 × 10⁹ cm^-3) at the UNILAC of GSI. The transverse and longitudinal temperatures of the electron beam were determined from DR resonance features observed with metastable Ar¹⁶⁺ (2³S) ions. The rate at E_rel = 0 for radiative recombination of completely stripped Ar¹⁸⁺ calculated with electron beam temperatures kT_∥ = 0.002 eV, kT_⊥ = 0.2 eV amounts to α = 10^-9 cm³ s^-1. This is exceeded by nearly a factor of 10 by the rate measured in experiments with Ar¹⁸⁺ ions. This revised version was published online in August 2006 with corrections to the Cover Date.     

Effect of Ar+ irradiation on the electrical conductivity of BaCe0.9Y0.1O3−δ

The effects of 10 keV Ar⁺ ion irradiation on the electrical characteristics of BaCe_0.9Y_0.1O_2.95 subject to fluences of 0, 1.0 × 10¹⁷, 5.0 × 10¹⁷ and 1.0 × 10¹⁸ ions/cm² at room temperature, has been investigated using elastic recoil detection analysis (ERDA), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and alternating current (AC) impedance measurements. It was confirmed from the ERDA results that the hydrogen concentration near the surface increased with increase of Ar⁺ ion fluence. This increase may be associated with the increasing quantities of hydrogen generated by interaction between oxygen vacancies, formed by irradiation, and H₂O from exposure to air. SEM images showed clearly that the number of surface defects due to modification increased with increasing fluence. In addition, the size of the defects showed a tendency to increase with increasing fluence. From the results of XPS analyses, providing information on the electronic states on the surface, it was evident that with increase in the Ar⁺ ion fluence, the quantity of excess oxygen, such as hydroxide, increased in the oxygen 1s XPS spectrum. In addition, it was indirectly found, from decomposition of the Ce 3d, spectrum that the concentration of oxygen vacancies increased with fluence, since the percentage of Ce³⁺ also increased. Accordingly, the surface modification led to the formation of more oxygen vacancies and a greater hydrogen concentration on the surface, since the H₂O interacted with some of them. From the results of the DC conductivity and AC impedance measurements, the proton conductivity was shown to predominate over the temperature range from 473 K to 823 K. It was concluded that the increase in these protons and vacancies generated from surface modification contributed to the increase of proton conductivity.     

Chemical reaction of sputtered Cu film with PI modified by low energy reactive atomic beam

Polyimide (PMDA-ODA) surface was irradiated by low energy reactive atomic beam with energy 160-180 eV to enhance the adhesion with metal Cu film. O₂⁺ and N₂⁺ ions were irradiated at the fluence from 5 × 10¹⁵ to 1 × 10¹⁸ cm⁻². Wetting angle 78° of distilled deionized (DI) water for bare PI was greatly reduced down to 2-4° after critical ion flounce, and the surface energy was increased from 37 to 81.2 erg/cm. From the analysis of O 1s core-level XPS spectra, such improvement seemed to result from the increment of hydrophilic carbonyl oxygen content on modified PI surface. To see more carefully correlation of the peel strength with interfacial reaction between Cu and PI, flexible copper clad laminate with Cu (9 μm)/Cu (200 nm) on modified PI substrate (25 μm) was fabricated by successive sputtering and electroplating. Firstly, peel strength was measured by using t-test and it was largely increased from 0.2 to 0.5 kgf/cm for Ar⁺ only irradiated PI to 0.72-0.8 kgf/cm for O₂⁺ or N₂O⁺ irradiated PI. Chemical reaction at the interface was reasoned by analyzing C 1s, O 1s, N 1s, and Cu 2p core-level X-ray photoelectron spectroscopy over the as-cleaved Cu-side and PI side surface through depth profiling. From the C 1s spectra of cleaved Cu-side, by the electron transfer from Cu to carbonyl oxygen, carbonyl carbon atom became less positive and as a result shifted to lower binding energy not reaching the binding energy of C₂ and C₃. The binding energy shift of the peak C₄ as small as 1.7 eV indicates that carbonyl oxygen atoms were not completely broken. From the analysis of the O 1s spectra, it was found that new peak at 530.5 eV (O₃) was occurred and the increased area of the peak O₃ was almost the same with reduced area of the peak carbonyl oxygen peak O₁. Since there was no change in the relative intensity of ether oxygen (O₂) to carbonyl oxygen (O₁), and thus O₃ was believed to result from Cu oxide formation via a local bonding of Cu with carbonyl oxygen atoms. Moreover, from X-ray induced Auger emission spectra Cu LMM which was very sensitive to chemical bonding, Cu oxide or CuOC complex formation instead of CuNO complex was clearly identified by the observation of the peak at 570 eV at higher 2 eV than that of metal Cu. In conclusion, when Cu atoms were sputtered on modified PI by low energy ion beam irradiation, it can be suggested that two Cu atoms locally reacted with carbonyl oxygen in PMDA units and formed Cu⁺O⁻C complex linkage without being broken from carbon atoms and thus the chemically bound Cu was in the form of Cu₂O.     

Erosion of the GaAs target under irradiation by a high-power pulsed ion beam

The results of examination of the GaAs-target erosion under irradiation by a high-power pulsed ion beam are reported. In the experiments, use was made of a high-power pulsed ion source with the following parameters: ion energy — 250 keV, target current density — 350 A/cm², pulse duration — 80 ns, target energy density — up to 7 J/cm². The target erosion coefficient and its dependence on the number of successive pulses are measured. It is found that the surface roughness parameter is increased with the number of successive beam pulses. A regular structure of surface relief is observed to form in the case where the number of pulses > 20–40. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 66–70, January, 2007.