Ion irradiation effects on surface mechanical behavior and shrinkage of hybrid sol-gel derived silicate thin films

A study of the effects of ion irradiation on the surface mechanical behavior and shrinkage of organic/inorganic modified silicate thin films was performed. The films were synthesized by sol-gel processing from tetraethylorthosilicate (TEOS) and methyltriethoxysilane (MTES) precursors and spin-coated onto Si substrates. The sol viscosity and the spin velocity were adjusted so that the films produced had a final thickness ranging from 580 to 710 nm after heat treatment. The ion species and incident energies used were selected such that the projected ion range was greater than the film thickness, resulting in fully irradiated films. After heat treatment at 300 °C for 10 min, the films were irradiated with 125 keV H⁺, 250 keV N²⁺ and 2 MeV Cu⁺ ions with fluences ranging from 1 × 10¹⁴ to 1 × 10¹⁶ ions/cm². Both hardness and reduced elastic modulus were seen to exhibit a monotonic increase with fluence for all three ion species. Also, H loss was found to increase monotonically with increase in fluence, while the film thickness was found to decrease with increase in fluence.     

Structural characterization of buried nitride layers formed by nitrogen ion implantation in silicon

The synthesis of buried silicon nitride insulating layers was carried out by SIMNI (separation by implanted nitrogen) process using implantation of 140 keV nitrogen (¹⁴N⁺) ions at fluence of 1.0 × 10¹⁷, 2.5 × 10¹⁷ and 5.0 × 10¹⁷ cm⁻² into 〈1 1 1〉 single crystal silicon substrates held at elevated temperature (410 °C). The structures of ion-beam synthesized buried silicon nitride layers were studied by X-ray diffraction (XRD) technique. The XRD studies reveal the formation of hexagonal silicon nitride (Si₃N₄) structure at all fluences. The concentration of the silicon nitride phase was found to be dependent on the ion fluence. The intensity and full width at half maximum (FWHM) of XRD peak were found to increase with increase in ion fluence. The Raman spectra for samples implanted with different ion fluences show crystalline silicon (c-Si) substrate peak at wavenumber 520 cm⁻¹. The intensity of the silicon peak was found to decrease with increase in ion fluence.     

Electronic excitations induced modifications of structural and optical properties of ZnO-porous silicon nanocomposites

The influence of swift heavy ion (SHI) irradiation on structural and photoluminescence (PL) properties of ZnO nanocrystallites deposited into porous silicon (PS) templates by the sol-gel process was studied. The ZnO/PS nanocomposites were irradiated using 120 MeV Au ions at different fluences varying from 1 × 10¹² to 1 × 10¹³ ions/cm². The intensity of the X-ray diffraction peaks is suppressed at the high fluence, without evolution of any new peak. The PL emission from PS around 700 nm is found to decrease with increase in ion fluence, while the PL emission from deep level defects of ZnO nanocrystallites is increased with ion fluence. At the highest fluence, the observation of drastic increase in PL emission due to donor/acceptor defects in the region 400-600 nm and suppressions of XRD peaks could be attributed to the defects induced structural modifications of ZnO nanocrystallites.     

Photoluminescence and photoluminescence excitation studies in 80 MeV Ni ion irradiated MOCVD grown GaN

We report damage creation and annihilation under energetic ion bombardment at a fixed fluence. MOCVD grown GaN thin films were irradiated with 80 MeV Ni ions at a fluence of 1 × 10¹³ ions/cm². Irradiated GaN thin films were subjected to rapid thermal annealing for 60 s in nitrogen atmosphere to anneal out the defects. The effects of defects on luminescence were explored with photoluminescence measurements. Room temperature photoluminescence spectra from pristine sample revealed presence of band to band transition besides unwanted yellow luminescence. Irradiated GaN does not show any band to band transition but there is a strong peak at 450 nm which is attributed to ion induced defect blue luminescence. However, irradiated and subsequently annealed samples show improved band to band transitions and a significant decrease in yellow luminescence intensity due to annihilation of defects which were created during irradiation. Irradiation induced effects on yellow and blue emissions are discussed.     

Ion-irradiation-induced athermal annealing of helium bubbles in SiC

We have compared the microstructural evolution of helium bubbles under ion irradiation and high temperature annealing. 4H-SiC was irradiated first by 140 keV He ions to a fluence of 1.0 × 10¹⁷ cm⁻² and then annealed at 1200 K for 30 min. Then, the samples were either irradiated by 2 MeV He ions to a fluence of 3.0 × 10¹⁶ cm⁻² at room temperature or annealed additionally at 1200 K for 30 min. Before and after 2 MeV He ion irradiation, significant microstructural changes were observed, similar to effects of high temperature annealing. Thus, the study provides evidence of ion-irradiation-induced athermal annealing on defect Ostwald ripening process and bubble evolution. Possible mechanisms are discussed.     

Thickness and MeV Si ions bombardment effects on the thermoelectric properties of Ce3Sb10 thin films

The three single layer Ce₃Sb₁₀ thin films were grown on silicon dioxide and quartz (suprasil) substrates with thicknesses of 297, 269 and 70 nm using ion beam assisted deposition (IBAD) technique. The high-energy cross plane Si ion bombardments with constant energy of 5 MeV have been performed with varying fluence from 1 × 10¹², 1 × 10¹³, 1 × 10¹⁴, 1 × 10¹⁵ ions/cm². The Si ions bombardment modified the thermoelectric properties of films as expected. The fluence and temperature dependence of cross plane thermoelectric parameters that are Seebeck coefficient, electrical and thermal conductivities were determined to evaluate the dimensionless figure of merit, ZT. Rutherford backscattering spectrometry (RBS) enabled us to determine the elemental composition of the deposited materials and layer thickness of each film.     

Structural and optical study of irradiation effect in GaN epilayers induced by 308 MeV Xe ions

Wurtzite GaN epilayers irradiated at room temperature with 308 MeV ¹²⁹Xe³⁵⁺ ions to fluences of 1 × 10¹³ and 3 × 10¹³ cm⁻² have been studied by contact mode atomic force microscopy (AFM), high-resolution X-ray diffraction (HRXRD), micro-Raman scattering and photoluminescence (PL) spectroscopy. The AFM images showed that the surface of GaN films was etched efficiently due to the Xe ion irradiation. The initial step-terrace structure on GaN surface was eliminated completely at a fluence of 3 × 10¹³ cm⁻². HRXRD and Raman results indicated that the Xe ion irradiation led to a homogenous lattice expansion throughout the entire ∼3 μm-thick GaN films. The lattice expansion as well as the biaxial compressive stress of the films was increasing with the increase of ion fluence. PL measurements showed that a dominant yellow luminescence band in the as-grown GaN films disappeared, but a blue and a green luminescence bands were produced after irradiation. Based on these results, the strong electronic excitation effect of 308 MeV Xe ions in GaN is discussed.     

Swift heavy ion induced modifications of fullerene C70 thin films

Modifications of the C₇₀ molecule (fullerene) under swift heavy ion irradiation are investigated. C₇₀ thin films were irradiated with 120 MeV Au ions at fluences from 1 × 10¹² to 3 × 10¹³ ions/cm². The energetic ion impacts lead to the destruction of the C₇₀ molecule. To investigate the stability of C₇₀ fullerene, the damage cross-section and radius of the damaged cylindrical zones are evaluated by fitting the evanescence of C₇₀ vibration modes recorded by Raman spectroscopy. Conductivity measurements together with Raman and optical absorption studies revealed that an irradiation fluence of 3 × 10¹³ ions/cm² results in complete amorphization of the carbon structure of the fullerene molecules.     

Effect of thermal spike energy created in CuFe2O4 by 150 MeV Ni swift heavy ion irradiation

Effects of 150 MeV Ni¹¹⁺ swift heavy ion (SHI) irradiation on copper ferrite nanoparticles have been studied at the fluences of 1 × 10¹¹, 1 × 10¹², 1 × 10¹³, 1 × 10¹⁴ and 5 × 10¹⁴ ions/cm². The XRD pattern shows the irradiation fluence dependant preferential orientation. Scanning electron microscope analysis displays fine blocks of material for pristine while partial agglomeration on irradiation. Notably, a large number of holes are present at the fluence of 5 × 10¹⁴ ions/cm². The magnetization measurements performed in these samples exposes that the coercivity and remanence magnetization value increases due to the magnetocrystalline anisotropy up to the fluence of 1 × 10¹³ ions/cm². At 1 × 10¹⁴ ions/cm² fluence, the induced thermal energy overcomes the magnetocrystalline anisotropy constant and causes a decrease in coercivity and remanence values. The saturation magnetization decreases up to the fluence of 1 × 10¹³ ions/cm² and then it increases for further irradiation. The change of crystalline orientation observed from XRD, the creation of holes from SEM and the change in magnetic properties are discussed on the basis of electro-phonon coupling and it invokes the thermal spike theory.     

Irradiation effect of carbon negative-ion implantation on polytetrafluoroethylene for controlling cell-adhesion property

We have investigated the irradiation effect of negative-ion implantation on the changes of physical surface property of polytetrafluoroethylene (PTFE) for controlling the adhesion property of stem cells. Carbon negative ions were implanted into PTFE sheets at fluences of 1 × 10¹⁴-1 × 10¹⁶ ions/cm² and energies of 5-20 keV. Wettability and atomic bonding state including the ion-induced functional groups on the modified surfaces were investigated by water contact angle measurement and XPS analysis, respectively. An initial value of water contact angles on PTFE decreased from 104° to 88° with an increase in ion influence to 1 × 10¹⁶ ions/cm², corresponding to the peak shifting of XPS C1s spectra from 292.5 eV to 285 eV with long tail on the left peak-side. The change of peak position was due to decrease of C-F₂ bonds and increase of C-C bonds with the formation of hydrophilic oxygen functional groups of OH and CO bonds after the ion implantation. After culturing rat mesenchymal stem cells (MSC) for 4 days, the cell-adhesion properties on the C⁻-patterned PTFE were observed by fluorescent microscopy with staining the cell nuclei and their actin filament (F-actin). The clear adhesion patterning of MSCs on the PTFE was obtained at energies of 5-10 keV and a fluence of 1 × 10¹⁵ ions/cm². While the sparse patterns and the uncontrollable patterns were found at a low fluence of 3 × 10¹⁴ ions/cm² and a high fluence of 3 × 10¹⁵ ions/cm², respectively. As a result, we could improve the surface wettability of PTFE to control the cell-adhesion property by carbon negative-ion implantation.     

Study of 200 MeV Ag ion induced amorphisation in nickel ferrite thin films

Thin films of nickel ferrite of thickness ∼100 and 150 nm were deposited by pulsed laser deposition. The films were irradiated with a 200 MeV Ag¹⁵⁺ beam of three fluences 1 × 10¹², 2 × 10¹² and 4 × 10¹² ions/cm². X-ray diffraction showed a decrease in the intensity of peaks indicating progressive amorphisation with increased irradiation fluence. Fourier transform infra-red and Raman spectra of pristine and irradiated films were also recorded which showed a degradation of the crystallinity of the samples after irradiation. The damage cross section of the infra-red bands was determined. It was found that the two bands at 557 and 614 cm⁻¹ did not show similar behaviour with fluence.     

Tailoring optical and electrical properties of MgO thin films by 1.5 MeV H implantation to fluences

Thin films of magnesia (MgO) with (1 0 0) dominant orientations were implanted with 1.5 MeV H⁺ ions at room temperature to various fluences of 10¹³, 10¹⁴ and 10¹⁵ ions/cm². X-ray analysis unambiguously showed crystallinity even after a peak damage fluence of 10¹⁵ ions/cm². Rutherford backscattering spectrometry combined with ion channeling (RBS/C) was used to analyze radiation damages and defect distributions. Optical absorption band observed at 5.7 eV in implanted films was assigned to the anion vacancies and the defect was completely disappeared on annealing at 450 °C. Number of F-type defects estimated was 9.42 × 10¹⁵ cm⁻² for the film implanted with 10¹⁵ ions/cm². DC electrical conductivity of 4.02 × 10⁻⁴ S cm⁻¹ was observed in the implanted region which was three orders higher than the as-deposited films. In unison, film surface was modified as a result of the formation of aggregates caused by the atomic mixing of native matrix atoms (Mg and O) and precipitated hydrogen.     

Ferroelectricity in Li-implanted ZnO thin films

ZnO:Li thin films were prepared by implantation of ZnO with a Li ion fluence 5 × 10¹⁶ ions/cm² at implantation energies of 50, 100, 200 keV. Ferroelectric characterization of the implanted samples revealed a clear hysteresis in the polarization-field curves. The origin of the ferroelectricity can be attributed to an off-center dipole caused by the large difference in ionic radii between the host Zn (0.74 Å) and the dopant Li (0.60 Å). ZnO:Li films which were implanted at 200 keV and annealed at a temperature of 700 ^°C exhibited a well-defined polarization hysteresis loop, with a remanent polarization of 0.8 μC/cm² and coercive field of 8.2 kV/cm, at room temperature. The dielectric phase transition was observed in the temperature range from 340 to 360 K. It is concluded that this novel ferroelectric phase transition in ZnO:Li results from the small structural distortion induced along the c-axis.     

Morphological change in FePt nanogranular thin films induced by swift heavy ion irradiation

We have investigated morphology change of FePt nanogranular films (FePt)₄₇(Al₂O₃)₅₃ under irradiation with 210 MeV Xe ions. Here, electron tomography technique was extensively employed to clarify three-dimensional (3D) structure in irradiated specimens, in addition to conventional transmission electron microscopy (TEM) techniques such as bright-field observation and scanning TEM energy dispersive X-ray spectroscopy (STEM-EDX) analysis. The ion irradiation induces the coarsening of FePt nanoparticles with elongation along the beam direction. Electron tomography 3D reconstructed images clearly demonstrated that when the fluence achieves 5.0 × 10¹⁴ ions/cm², well-coarsened FePt balls have been formed on the irradiated surface, and the particles in the film interior have been deformed into rods along the ion trajectory. The alloy particles become inhomogeneous in composition after prolonged irradiation up to 1.0 × 10¹⁵ Xe ions/cm². The particle center is enriched with Pt, while Fe is slightly redistributed to the periphery.     

Defects creation in sapphire by swift heavy ions: A fluence depending process

Single crystals of sapphire (α-Al₂O₃) were irradiated at GANIL with 0.7 MeV/amu xenon ions corresponding to an electronic stopping power of 21 keV/nm. Several fluences were applied between 5 × 10¹¹ and 2 × 10¹⁴ ions/cm². Irradiated samples were characterized using optical absorption spectroscopy. This technique exhibited the characteristic bands associated with F and F⁺ centers defects. The F centers density was found to increase with the fluence following two different kinetics: a rapid increase for fluences less than 10¹³ ions/cm² and then, a slow increase for higher fluences. For fluences less than 10¹³ ions/cm², results are in good agreement with those obtained by Canut et al. [B. Canut, A. Benyagoub, G. Marest, A. Meftah, N. Moncoffre, S.M.M. Ramos, F. Studer, P. Thévenard, M. Toulemonde, Phys. Rev. B 51 (1995) 12194]. In the fluences range: 10¹³-10¹⁴ ions/cm², the F centers defects creation process is found to be different from the one evidenced for fluences less than 10¹³ ions/cm².     

Effect of swift heavy ion irradiation on structure, optical, and gas sensing properties of SnO2 thin films

Swift heavy ion irradiation has been successfully used to modify the structural, optical, and gas sensing properties of SnO₂ thin films. The SnO₂ thin films prepared by sol-gel process were irradiated with 75 MeV Ni⁺ beam at fluences ranging from 1 × 10¹¹ ion/cm² to 3 × 10¹³ ion/cm². Structural characterization with glancing angle X-ray diffraction shows an enhancement of crystallinity and systematic change of stress in the SnO₂ lattice up to a threshold value of 1 × 10¹³ ions/cm², but decrease in crystallinity at highest fluence of 3 × 10¹³ ions/cm². Microstructure investigation of the irradiated films by transmission electron microscopy supports the XRD observations. Optical properties studied by absorption and PL spectroscopies reveal a red shift of the band gap from 3.75 eV to 3.1 eV, and a broad yellow luminescence, respectively, with increase in ion fluence. Gas response of the irradiated SnO₂ films shows increase of resistance on exposure to ammonia (NH₃), indicating p-type conductivity resulting from ion irradiation.     

Evidence of nanostructure formation in Ge oxide by crystallization induced by swift heavy ion irradiation

Ge oxide films were irradiated with 150 MeV Ag ions at fluences varying between 10¹² and 10¹⁴ ions/cm². The irradiation-induced changes were monitored by FT-IR spectroscopy, atomic force microscopy, X-ray diffraction and photoluminescence spectroscopy. The FT-IR spectra indicate stoichiometric changes and an increase in Ge content on irradiation. X-ray diffraction shows a crystallization of the irradiated films and presence of both Ge and GeO₂ phases. The Ge nanocrystal size, as calculated from Scherrer’s formula, was around 30 nm. The morphological changes, observed in atomic force microscopy, also indicate formation of nanostructures upon ion irradiation and a uniform growth is observed for a fluence of 1 × 10¹⁴ ions/cm².     

Ion bombardment induced changes in the optical and electrical properties of polycarbonate

The changes in the optical and electrical properties of polycarbonate (PC) films, bombarded with He and Ar ion beams, have been studied. The PC films were divided into two groups where the first group was bombarded with 130 keV He ions of fluences ranged from 1 × 10¹⁴ cm⁻² to 2 × 10¹⁶ cm⁻², while the second one was bombarded with 320 keV Ar of fluences (1 × 10¹³ cm⁻² and 1 × 10¹⁵ cm⁻²). The surface morphology of the unirradiated and irradiated PC films was studied using scanning electron microscopy (SEM) technique. The optical properties of the two groups have been carried out using UV-Vis spectrophotometer and the direct current (DC) electrical conductivity was also performed. The obtained results showed a decrease in the optical energy gap, the optical activation energy and the electrical activation energy with increasing the fluence of both He and Ar ions. Meanwhile, an increase in the DC conductivity was obtained with increasing the fluence of the ions. The bombardment of the PC films with He and Ar ion beams induced formation of carbon clusters near the polymer surface and, also, resulted in scission in the polymer chains.     

Sputtering and crystalline structure modification of bismuth thin films deposited onto silicon substrates under the impact of 20-160 keV Ar ions

The sputtering of bismuth thin films induced by 20-160 keV Ar⁺ ions has been studied using Rutherford backscattering spectrometry, scanning electron microscopy and X-ray energy dispersive and diffraction spectroscopy. These techniques revealed increasing modifications of the Bi film surfaces with increasing both ion beam energy and fluence up to their complete deterioration under irradiation conditions E = 160 keV and φ = 1.5 × 10¹⁶ cm⁻², leaving isolated islands of preferred (0 1 2) orientation on the Si substrate. The observed surface morphology and crystalline structure evolutions are likely due to a complex interplay of interaction mechanisms involving both elastic nuclear collisions and inelastic electronic ones. The measured Bi sputtering yields versus Ar⁺ ion fluence for a fixed ion energy exhibit a significant depression at very low φ-values followed by a steady state regime above ∼2.0 × 10¹⁴ cm⁻². Measured sputtering yields versus Ar⁺ ion energy with fixing ion fluence to 1.2 × 10¹⁶ cm⁻² in the upper part of the yield saturation regime are also reported. Their comparison to theoretical model and SRIM 2008 Monte Carlo simulation predictions is discussed.     

Anisotropic deformation of polystyrene particles by MeV Au ion irradiation

MeV Au irradiation leads to a shape change of polystyrene (PS) and SiO₂ particles from spherical to ellipsoidal, with an aspect ratio that can be precisely controlled by the ion fluence. Sub-micrometer PS and SiO₂ particles were deposited on copper substrates and irradiated with Au ions at 230 K, using an ion energy and fluence ranging from 2 to 10 MeV and 1 × 10¹⁴ ions/cm² to 1 × 10¹⁵ ions/cm². The mechanisms of anisotropic deformation of PS and SiO₂ particles are different because of their distinct physical and chemical properties. At the start of irradiation, the volume of PS particles decrease, then the aspect ratio increases with fluence, whereas for SiO₂ particles the volume remains constant.