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.     

Effects of ion irradiation on the mechanical properties of SiNawOxCyHz sol-gel derived thin films

A study of the effects of ion irradiation of hybrid organic/inorganic modified silicate thin films on their mechanical properties 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. Nanoindentation was used to characterize the films. Changes in hardness and reduced elastic modulus were examined as a function of ion fluence and irradiating species. The resulting increases in hardness and reduced elastic modulus are compared to similarly processed acid catalyzed silicate thin films.     

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.     

Effect of 200 MeV Ag ion irradiation on structural and electrical transport properties of Fe3O4 thin films

Thin films of Fe₃O₄ have been deposited on single crystal MgO(1 0 0) and Si(1 0 0) substrates using pulsed laser deposition. Films grown on MgO substrate are epitaxial with c-axis orientation whereas, films on Si substrate are highly 〈1 1 1〉 oriented. Film thicknesses are 150 nm. These films have been irradiated with 200 MeV Ag ions. We study the effect of the irradiation on structural and electrical transport properties of these films. The fluence value of irradiation has been varied in the range of 5 × 10¹⁰ ions/cm² to 1 × 10¹² ions/cm². We compare the irradiation induced modifications on various physical properties between the c-axis oriented epitaxial film and non epitaxial but 〈1 1 1〉 oriented film. The pristine film on Si substrate shows Verwey transition (T_V) close to 125 K, which is higher than generally observed in single crystals (121 K). After the irradiation with the 5 × 10¹⁰ ions/cm² fluence value, T_V shifts to 122 K, closer to the single crystal value. However, with the higher fluence (1 × 10¹² ions/cm²) irradiation, T_V again shifts to 125 K.     

Structural studies of Ge nanocrystals embedded in SiO2 matrix

Germanium nanoparticles embedded in SiO₂ matrix were prepared by atom beam sputtering on a p-type Si substrate. The as-deposited films were annealed at temperatures of 973 and 1073 K under Ar + H₂ atmosphere. The as-deposited and annealed films were characterized by Raman, X-ray diffraction and Fourier transform infrared spectroscopy (FTIR). Rutherford backscattering spectrometry was used to quantify the concentration of Ge in the SiO₂ matrix of the composite thin films. The formation of Ge nanoparticles were observed from the enhanced intensity of the Ge mode in the Raman spectra as a function of annealing, the appearance of Ge(3 1 1) peaks in the X-ray diffraction data and the Ge vibrational mode in the FTIR spectra. We have irradiated the films using 100 MeV Au⁸⁺ ions with a fluence of 1 × 10¹³ ions/cm² and subsequently studied them by Raman and FTIR. The results are compared with the ones obtained by annealing.     

Post-annealing temperature dependence of blistering in high-fluence ion-implanted H in Si 〈1 0 0〉

This study examined the influence of post-annealing temperature on blister formation and growth in ion-implanted H in Si 〈1 0 0〉. Ion energy levels of 40 and 100 keV and fluences of 2 × 10¹⁶ and 5 × 10¹⁶ cm⁻² were investigated. Post-annealing treatments were performed using the furnace annealing (FA) method with temperatures ranging from 200 to 600 °C for a duration of 1 h. Raman scattering spectroscopy (RSS), optical microscopy (OM), secondary ion mass spectrometry (SIMS), atomic force microscopy (AFM), and cross-sectional transmission electron microscopy (XTEM) were employed to explore the mechanisms behind the smart cut technique. The results revealed that variations among the transformation of the VH₃ (or V₂H₆) defect complex phase into the Si(1 0 0):H bonding configuration phase (RSS results), the appearance of optically detectable blisters and craters (OM results), the average depth of craters (AFM results), the trapping of hydrogen atoms and gettering of oxygen atoms (SIMS results), and the damaged microstructures (XTEM results) against post-annealing temperature were in close correspondence. It was also found that the optimal post-annealing temperature for blister formation and growth was 550 °C.     

Flux dependent MeV ion induced modification of nano-Ag/Si system

Thin films of Ag (1.5 nm thick) are grown on Si (1 1 1) substrates using evaporation method in high vacuum condition and due to non-wetting nature of silver, isolated islands of mean size ≈12.0 nm have been formed on the surface. Au²⁺ (1.5 MeV) ions have been used to irradiate the above systems at various fluences (5 × 10¹³-1 × 10¹⁵ cm⁻²) at an impact angle of 5° and at a flux of 6.3 × 10¹² cm⁻² s⁻¹ (corresponding to a beam current density of 2.0 μA cm⁻² for Au²⁺ ions). Ion beam induced embedding is observed to begin at a fluence of 1 × 10¹⁴ cm⁻² for this high flux whereas low flux irradiations (current density ≈ 0.02 μA cm⁻²) of Au²⁺ ions under similar irradiation conditions did not yield embedding (impact angle 5°). High resolution transmission electron microscopy measurement showed no mixing in the form of silicide formation. These results are compared with high flux modifications in Au/Si system.     

Sputtering of cryogenic films of hydrogen by keV ions: Thickness dependence and surface morphology

The sputtering yield induced by keV hydrogen ions measured at CERN and at Risø National Laboratory for solid H₂ and D₂ at temperatures below 4.2 K decreases with increasing film thickness from about 100 × 10¹⁵ molecules/cm². For a film thickness comparable to or larger than the ion range the data from Risø show a slight increase, whereas the yield from CERN continues to decrease up to very large film thicknesses, i.e. one order of magnitude larger than the ion range. The different behavior of the yield is discussed in terms of the probable growth modes of the films. The films produced at the Risø setup are quench-condensed films, while those produced at CERN are supposed to grow with large hydrogen aggregates on top of a thin bottom layer.     

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.     

Swift heavy ion irradiation induced texturing in NiO thin films

NiO thin films grown on Si(1 0 0) substrate by electron beam evaporation and sintered at 500 and 700 °C were irradiated with 120 MeV Au⁹⁺ ions. The FCC structure of the sintered films was retained up to the highest fluence (3 × 10¹³ ions cm⁻²) of irradiation. In the low fluence (?1 × 10¹³ ions cm⁻²) regime however, the evolution of the XRD pattern with fluence showed a wide variation, critically depending upon their initial microstructure. Though irradiation is known to induce disorder in the structure, we observe improvement in crystallization and texturing at intermediate fluences of irradiation.     

Desorption of gold nanoclusters from gold nanodispersed targets by 200 keV Au5 polyatomic ions in the elastic stopping mode: Experiment and molecular-dynamics simulation

Au nanoislet targets (∅ 2-60 nm) were bombarded by 200 keV polyatomic ions (40 keV/atom), which deposit their energy mainly in the nuclear stopping mode: ∑(dE/dx)_n = 30 keV/nm and ∑(dE/dx)_e = 2 keV/nm. The matter desorbed in the form of nanoclusters was registered by TEM. The total transfer of matter was determined by neutron-activation analysis. The total yield of the ejected gold reached high values of up to 2.6 × 10⁴ atoms per Au₅ ion. The major part (2 × 10⁴ atoms per ion Au₅) of the emission is in the form of nanoclusters. The results are compared with the data of similar experiments with 1 MeV Au₅ (200 keV/atom) and other projectiles. The analysis of the experimental data and the comparison to molecular-dynamics simulation results of the desorption process show that the desorption of Au nanoislets is induced by their melting, build-up of pressure and thermal expansion.     

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.     

Effect of swift heavy ion irradiation on the surface morphology of highly c-axis oriented LSMO thin films grown by pulsed laser deposition

A detailed investigation of the surface morphology of the pristine and swift heavy ion (SHI) irradiated La_0.7Sr_0.3MnO₃ (LSMO) thin film using atomic force microscope (AFM) is presented. Highly c-axis oriented LSMO thin films were grown on LaAlO₃ (1 0 0) (LAO) substrates by the pulsed laser deposition (PLD) technique. The films were annealed at 800 °C for 12 h in air (pristine films) and subsequently, irradiated with SHI of oxygen and silver. The incident fluence was varied from 1 × 10¹² to 1 × 10¹⁴ ions/cm² and 1 × 10¹¹ to 1 × 10¹² ions/cm² for oxygen and silver ions, respectively. X-ray diffraction (XRD) studies reveal that the irradiated films are strained. From the AFM images, various details pertaining to the surface morphology such as rms roughness (σ), the surface rms roughness averaged over an infinite large image (σ_∞), fractal dimension (D_F) and the lateral coherence length (ξ) were estimated using the length dependent variance measurements. In case of irradiated films, the surface morphology shows drastic modifications, which is dependent on the nature of ions and the incident fluence. However, the surface is found to remain self-affine in each case. In case of oxygen ion irradiated films both, σ_∞ and D_F are observed to increase with fluence up to a dose value of 1 × 10¹³ ions/cm². With further increase in dose value both σ_∞ and D_F decreases. In case of silver ion irradiated films, σ_∞ and D_F decrease with increase in fluence value in the range studied.     

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.     

Electronic stopping dependence of ion beam induced modifications in GaN

We report here Swift heavy ion induced effects in GaN samples grown by metal organic chemical vapor deposition (MOCVD) technique. These samples were irradiated with 80 MeV Ni and 100 MeV Ag ions at a fixed fluence of 1 × 10¹³ ions/cm². Ion species and energies are chosen such that the difference in their electronic energy loss (S_e) would be 8 keV/nm. Effects of Ag on structural and optical properties over Ni ions have been discussed extensively. We employed different characterization techniques like High Resolution X-ray Diffraction (HRXRD) and Raman Spectroscopy for defect density calculations and for vibrational modes, respectively. Defect densities are calculated and compared using Williamson-Hall method from HRXRD. Change of strain and vibrational modes with S_e has been discussed.     

Mixing of Cr and Si atoms induced by noble gas ions irradiation of Cr/Si bilayers

Cr/Si bilayers were irradiated at room temperature with 120 keV Ar, 140 keV Kr and 350 keV Xe ions to fluences ranging from 10¹⁵ to 2 × 10¹⁶ ions/cm². The thickness of Cr layer evaporated on Si substrate was about 400 Å. Rutherford backscattering spectrometry (RBS) was used to investigate the atomic mixing induced at the Cr-Si interface as function of the incident ion mass and fluence. We observed that for the samples irradiated with Ar ions, RBS yields from both Cr layer and Si substrate are the same as before the irradiation. There is no mixing of Cr and Si atoms, even at the fluence of 2 × 10¹⁶ ions/cm². For the samples irradiated with Kr ions, a slight broadening of the Cr and Si interfacial edges was produced from the fluence of 5 × 10¹⁵ ions/cm². The broadening of the Cr and Si interfacial edges is more pronounced with Xe ions particularly to the fluence of 10¹⁶ ions/cm². The interface broadening was found to depend linearly on the ion fluence and suggests that the mixing is like a diffusion controlled process. The experimental mixing rates were determined and compared with values predicted by ballistic and thermal spike models. Our experimental data were well reproduced by the thermal spikes model.     

Implantation of anatase thin film with 100 keV Fe ions: Damage formation and magnetic behaviour

We have investigated the damage morphology and magnetic properties of titanium dioxide thin films following implantation with Fe ions. The titanium dioxide films, having a polycrystalline anatase structure, were implanted with 100 keV ⁵⁶Fe⁺ ions to a total fluence of 1.3 × 10¹⁶ ions/cm². The ion bombardment leads to an amorphized surface with no indication of the presence of secondary phases or Fe clusters. The ion-beam induced damage manifested itself by a marked change in surface morphology and film thickness. A room temperature ferromagnetic behaviour was observed by SQUID in the implanted sample. It is believed that the ion-beam induced damage and defects in the polycrystalline anatase film were partly responsible for the observed magnetic response.     

Raman investigation of incident N-, Xe-ions induced effects in ZnO thin films

Highly c-axis orientation ZnO thin films with hundreds nanometers in thickness have been deposited on (1 0 0) Si substrate by RF magnetron sputtering. These films are implanted at room temperature by 80 keV N-ions with fluences from 5.0 × 10¹⁴ to 1.0 × 10¹⁷ ions/cm², implanted by 400 keV Xe-ions with 2.0 × 10¹⁴ to 2.0 × 10¹⁶ ions/cm², irradiated by 3.64 MeV Xe-ions with 1.0 × 10¹² to 1.0 × 10¹⁵ ions/cm², or irradiated by 308 MeV Xe-ions with 1.0 × 10¹² to 5.0 × 10¹⁴ ions/cm², respectively. Then the ZnO films are investigated using a Raman spectroscopy. The obtained Raman spectra show that a new Raman peak located at about 578 cm⁻¹ relating to simple defects or disorder phase appears in all ZnO films after ion implantation/irradiation, a new Raman peak at about 275 cm^-1 owing to N-activated zinc-like vibrations is observed in the N-implanted samples. Moreover, a new Raman peak at about 475 cm⁻¹ is only seen in the samples after 400 keV and 3.64 MeV Xe-ions bombardment. The area intensity of these peaks increases with increasing ion fluence. The effects of ion fluence, element chemical activity, atom displacements induced by nuclear collisions as well as energy deposition on the damage process of ZnO films under ion implantation/irradiation are discussed briefly.     

Studies on the high electronic energy deposition in polyaniline thin films

We report here the physico-chemical changes brought about by high electronic energy deposition of gold ions in HCl doped polyaniline (PANI) thin films. PANI thin films were synthesized by in situ polymerization technique. The as-synthesized PANI thin films of thickness 160 nm were irradiated using Au⁷⁺ ion of 100 MeV energy at different fluences, namely, 5 × 10¹¹ ions/cm² and 5 × 10¹² ions/cm², respectively. A significant change was seen after irradiation in electrical and photo conductivity, which may be related to increased carrier concentration, and structural modifications in the polymer film. In addition, the high electronic energy deposition showed other effects like cross-linking of polymer chains, bond breaking and creation of defect sites. AFM observations revealed mountainous type features in all (before and after irradiation) PANI samples. The average size (diameter) and density of such mountainous clusters were found to be related with the ion fluence. The AFM profiles also showed change in the surface roughness of the films with respect to irradiation, which is one of the peculiarity of the high electronic energy deposition technique.     

Formation of silicon hydride using hyperthermal negative hydrogen ions (H) extracted from an argon-seeded hydrogen sheet plasma source

An E × B probe (a modified Wien filter) is constructed to function both as a mass spectrometer and ion implanter. The device, given the acronym EXBII selects negative hydrogen ions (H⁻) from a premixed 10% argon-seeded hydrogen sheet plasma. With a vacuum background of 1.0 × 10⁻⁶ Torr, H⁻ extraction ensues at a total gas feed of 1.8 mTorr, 0.5 A plasma discharge. The EXBII is positioned 3 cm distance from the sheet core as this is the region densely populated by cold electrons (T_e ∼ 2 eV, N_e ∼ 3.4 × 10¹¹ cm⁻³) best suited for H⁻ formation. The extracted H⁻ ions of flux density ∼0.26 A/m² are segregated, accelerated to hyperthermal range (<100 eV) and subsequently deposited into a palladium-coated 1.1 × 1.1 cm², n-type Si (1 0 0) substrate held at the rear end of the EXBII, placed in lieu of its Faraday cup. The palladium membrane plays the role of a catalyst initiating the reaction between Si atoms and H⁻ ions simultaneously capping the sample from oxidation and other undesirable adsorbents. AFM and FTIR characterization tests confirm the formation of SiH₂. Absorbance peaks between 900-970 cm⁻¹ (bending modes) and 2050-2260 cm⁻¹ (stretching modes) are observed in the FTIR spectra of the processed samples. It is found that varying hydrogen exposure time results in the shifting of wavenumbers which may be interpreted as changes in the frequencies of vibration for SiH₂. These are manifestations of chemical changes accompanying alterations in the force constant of the molecule. The sample with longer exposure time exhibits an additional peak at 2036 cm⁻¹ which are hydrides of nano-crystalline silicon.