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.     

Grain growth and crack formation in NiO thin films by swift heavy ion irradiation

NiO thin films grown on Si(1 0 0) substrates by electron beam evaporation and sintered at 700 °C, were irradiated by 120 MeV Au⁹⁺ ions. Though irradiation is known to induce lattice disorder and suppression of crystallinity, we observe grain growth at some fluences of irradiation. Associated with the growth of grains, the films develop cracks at a fluence of 3 × 10¹² ions cm⁻². The width of the cracks increased at higher fluences. Swift heavy ion irradiation induced atomic diffusion and strain relaxation in nanoparticle thin films, which are not in thermodynamic equilibrium, seem to be responsible for the observed grain growth. This phenomenon along with the tensile stress induced surface instability lead to crack formation in the NiO thin films.     

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.     

Effect of SHI on dielectric and magnetic properties of metal oxide/PMMA nanocomposites

Magnetic nanoparticles embedded in polymer matrices have excellent potential for electromagnetic device applications like electromagnetic interference suppression, etc. The NiO nanoparticles were synthesized by simple method. These nanoparticles were dispersed in PMMA matrix and films were prepared by casting method with varying concentrations of nickel oxide nanoparticles. These films were irradiated with 50 MeV Li⁺³ ions at a fluence of 5 × 10¹² ions/cm². AC electrical properties of pristine and irradiated samples were studied in wide frequency range. Dependence of dielectric properties on frequency, ion beam fluence and filler concentration was studied. The results reveal the enhancement in dielectric properties after doping nanoparticles and also upon irradiation, which is also corroborated with field-cooled-zero-field-cooled (FC-ZFC) susceptibility measurement in which magnetization is increased upon irradiation. The Fourier transform infrared (FTIR) spectroscopy analysis revealed the change in the intensity of functional groups after irradiation. Average surface roughness observed to change with filler concentration and also with the irradiation fluence as obtained from AFM analysis.     

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.     

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.     

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.     

Fabrication of hollow Ag nanoclusters in silica by irradiation with Ar ions

Ion irradiation is an effective method to control the morphology, size and distribution of metal nanoclusters in substrates. In this work, Ag nanoclusters embedded in silica by 200 keV Ag⁺ ion implantation were irradiated at room temperature with Ar⁺ ions at 200 keV and 500 keV to different fluences. After irradiation, a transmission electron microscopy (TEM) study revealed that nanovoids are formed in the larger Ag nanoclusters. With the increase of fluence and energy of the Ar⁺ ions, the number and average size of the nanovoids grow combining with increases in the average size of the larger Ag nanoclusters within a projected range. During the ion irradiation process, the electronic energy and nuclear energy loss of the Ar⁺ ions determine the size of the hollow Ag nanoclusters and the change of the size and distribution of Ag nanoclusters in silica, leading to changes in the optical absorption spectra.     

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.     

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.     

Electronic and atomic structure modifications of copper nitride films by ion impact and phase separation

We have studied electronic and atomic structure modifications of Cu₃N films under 100 keV Ne and 100 MeV Xe ion impact. Cu₃N films were prepared on R(11-2 surface)-cut-Al₂O₃ substrates at 250 °C by using a RF-magnetron sputter deposition method. X-ray diffraction (XRD) shows that unirradiated films are polycrystalline with (1 0 0) orientation of cubic structure. We find that the electrical resistivity (∼10 Ω cm before ion impact) decreases by more than two orders of magnitude after the Ne impact at a fluence of ∼10¹³ cm⁻², where no Cu phase separation is observed. For further ion impact (larger than ∼10¹⁵ cm⁻²), XRD shows Cu diffraction peak (Cu phase separation), and the resistivity decreases further (three orders of magnitude). Decomposition and phase separation are discussed based on these results, as well as temperature dependence of the resistivity and optical absorption. The results of 100 MeV Xe ion impact are compared with those of Ne ion impact.     

Structural characterization of swift heavy ion irradiated polycarbonate

Makrofol-N polycarbonate thin films were irradiated with copper (50 MeV) and nickel (86 MeV) ions. The modified films were analyzed by UV-VIS, FTIR and XRD techniques. The experimental data was used to evaluate the formation of chromophore groups (conjugated system of bonds), degradation cross-section of the special functional groups, the alkyne formation and the amorphization cross-section. The investigation of UV-VIS spectra shows that the formation of chromophore groups is reduced at larger wavelength, however its value increases with the increase of ion fluence. Degradation cross-section for the different chemical groups present in the polycarbonate chains was evaluated from the FTIR data. It was found that there was an increase of degradation cross-section of chemical groups with the increase of electronic energy loss in polycarbonate. The alkyne and alkene groups were found to be induced due to swift heavy ion irradiation in polycarbonate. The radii of the alkyne production of about 2.74 and 2.90 nm were deduced for nickel (86 MeV) and copper (50 MeV) ions respectively. XRD analysis shows the decrease of the main XRD peak intensity. Progressive amorphization process of Makrofol-N with increasing fluence was traced by XRD measurements.     

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.     

Velocity effect of swift heavy ions in graphite studied by Raman spectroscopy

Highly oriented pyrolytic graphite (HOPG) samples were irradiated with swift heavy ions (Ar, Kr, Bi, U) of fluences between 10¹¹ and 10¹³ ions/cm² in energy range MeV-GeV. The irradiated samples were analyzed by Raman spectroscopy with laser wavelength of 532.2 nm. It is shown that the ratio between the integrated intensities of the disorder-induced D and the original G Raman bands which denotes the degree of the damage induced by ion irradiation increases as a function of ion fluence as well as the electronic energy loss. This agrees with the previous reports. However, quantitative analysis of the peak intensity at a fixed fluence discloses that ion velocity is also a significant parameter in determination of damage. The conclusion is that the extent of discontinuity of ion track may change with ion velocity besides the electronic energy loss. Considering the radial distribution of the energy deposited on the matter being velocity dependent, the energy density which combines the influence of the electronic energy loss and ion velocity may be more suitable for explaining the effect induced by swift heavy ions.     

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.     

Effect of swift heavy ion irradiation on structural, optical and electrical properties of Cd2SnO4 thin films

Transparent conducting cadmium stannate thin films were prepared by spray pyrolysis method on Corning substrate at a temperature of 525 °C. The prepared films are irradiated using 120 MeV swift Ag⁹⁺ ions for the fluence in the range 1 × 10¹² to 1 × 10¹³ ions cm⁻² and the structural, optical and electrical properties were studied. The intensity of the film decreases with increasing ion fluence and amorphization takes place at higher fluence (1 × 10¹³ ions cm⁻²). The transmittance of the films decreases with increasing ion fluence and also the band gap value decreases with increasing ion fluence. The resistivity of the film increased from 2.66 × 10⁻³ Ω cm (pristine) to 5.57 × 10⁻³ Ω cm for the film irradiated with 1 × 10¹³ ions cm⁻². The mobility of the film decreased from 31 to 12 cm²/V s for the film irradiated with the fluence of 1 × 10¹³ ions cm⁻².     

Oxygen defects created in CeO2 irradiated with 200 MeV Au ions

CeO₂ films were irradiated with 200 MeV Au ions in order to investigate the damages created by electronic energy deposition. In the Raman spectra of the ion-irradiated films, a broad band appears at the higher frequency side of the F_2g peak of CeO₂. The band intensity increases as ion fluence increases. Furthermore, the F_2g peak becomes asymmetric with a low-frequency tail. In order to understand the origin of these spectral changes, an unirradiated CeO₂ film was annealed in vacuum at 1000 °C. By comparing the results for the irradiation and for the annealing, it is concluded that the broad band obtained for irradiated samples contains the peak observed for the annealed sample. The F_2g peak becomes asymmetric with a low-frequency tail by the irradiation as well as the annealing. Therefore, the above-mentioned changes in the Raman spectra caused by 200 MeV Au irradiation is closely related to the creation of oxygen vacancies.     

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 swift heavy ion irradiation on nanocrystalline CaS:Bi phosphors: Structural, optical and luminescence studies

Luminescence studies of CaS:Bi nanocrystalline phosphors synthesized by wet chemical co-precipitation method and irradiated with swift heavy ions (i.e. O⁷⁺-ion with 100 MeV and Ag¹⁵⁺-ion with 200 MeV) have been carried out. The samples have been irradiated at different ion fluences in the range 1 × 10¹²-1 × 10¹³ ions/cm². The average grain size of the samples before irradiation was estimated as 35 nm using line broadening of XRD (X-ray diffraction) peaks and TEM (transmission electron microscope) studies. Our results suggest a good structural stability of CaS:Bi against swift heavy ion irradiation. The blue emission band of CaS:Bi³⁺ nanophosphor at 401 nm is from the transition ³P₁ → ¹S₀ of the Bi³⁺. We have observed a decrease in lattice constant (a) and increase of optical energy band gap after ion irradiation. We presume this change due to grain fragmentation by dense electronic excitation induced by swift heavy ion. We have studied the optical and luminescent behavior of the samples by changing the ion energy and also by changing dopant concentration from 0.01 mol% to 0.10 mol%. It has been examined that ion irradiation enhanced the luminescence of the samples.     

Swift heavy ion induced phase transition in CdTe films deposited by spray pyrolysis in presence of electric field

CdTe polycrystalline thin films possessing hexagonal phase regions are obtained by spray deposition in presence of a high electric field. Thin film samples are irradiated with 100 MeV Ag ions using Pelletron accelerator to study the swift heavy ion induced effects. The ion irradiation results in the transformation of the metastable hexagonal regions in the films to stable cubic phase due to the dense electronic excitations induced by beam irradiation. The phase transformation is seen from the X-ray diffraction patterns. The band gap of the CdTe film changes marginally due to ion irradiation induced phase transformation. The value changes from 1.47 eV for the as deposited sample to 1.44 eV for the sample irradiated at the fluence 1×10¹³ ions/cm². The AFM images show a gradual change in the shape of the particles from rod shape to nearly spherical ones after irradiation.