Effect of swift heavy ion irradiation on spray deposited CdX (X = S, Te) thin films

Cadmium sulfide and cadmium telluride thin films are irradiated with high energy heavy ion beam to study the irradiation induced effects in these films. The polycrystalline thin film samples deposited by spray pyrolysis are irradiated with 60 MeV Oxygen ions using tandem Pelletron accelerator. The X-ray diffraction patterns exhibit a reduction in peak intensities in both CdS and CdTe films. The grain size decrease with fluence is observed for both CdS and CdTe films, with more decrease for CdTe films. The AFM results support this observation. The films show opposite trend in the variation of electrical resistivity with irradiation fluence. A decrease in resistivity is observed for CdS films due to an increase of carrier concentration arising by the creation of sulfur vacancies during the irradiation. The creation of sulfur vacancies is confirmed by XPS studies. The stoichiometric changes seen from XPS studies support this observation. An enhancement of grain boundary scattering due to the reduction of grain size leads to the increase of electrical resistivity for CdTe films.     

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.     

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.     

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.     

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.     

Ag/Fe:TiO2 nano-catalysts prepared by Fe ion implantation and Ag nanoparticle deposition by electron beam irradiation

TiO₂ nano-catalysts made by the sol-gel method were modified by ion implantation and electron beam irradiation to obtain a more efficient photocatalytic function. The results of photodegradation of methyl orange in aqueous solution demonstrate firstly that the films have a photocatalytic activity which responds to visible light. Secondly, it demonstrates that under ultraviolet excitation the sample with a fluence of 6 × 10¹⁵ ions/cm² and electron beam irradiated with concentration of AgNO₃ aqueous solution at 1 × 10⁻³ M gives a more efficient photodegradation ability than pure TiO₂ film and other Fe-doped films display almost the same photodegradation ability as TiO₂ film. Thirdly it demonstrates that under sunlight, all modified films exhibit more photodegradation activity than TiO₂ film.     

AFM and photoluminescence studies of swift heavy ion induced nanostructured aluminum oxide thin films

E-beam evaporated aluminum oxide films were irradiated with 120 MeV swift Au⁹⁺ ions in order to induced nanostructure formation. Atomic force microscope (AFM) results showed the formation of nanostructures for films irradiated with a fluence of 1 × 10¹³ ions cm⁻². The particle size estimated by section analysis of the irradiated film was in the range 25-30 nm. Glancing angle X-ray diffraction (GAXRD) revealed the amorphous nature of the films. Two strong Photoluminescence (PL) emission bands with peaks at ∼430 nm and ∼645 nm besides a shoulder at ∼540 nm were observed in all irradiated samples. The PL intensity is found to increase with increase of ion fluence.     

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.     

Physical and chemical response of 145 MeV Ne ion irradiated polymethylmethacrylate (PMMA) polymer

Characterization of ion induced modifications in the physical, chemical and structural properties of polymethylmethacrylate (PMMA) polymer induced by 145 MeV Ne⁶⁺ ions has been carried out by FTIR, UV-Visible, Differential scanning calorimetry (DSC) and X-ray diffraction. Heavy ion irradiation was carried out under a vacuum of ∼10⁻⁶ torr at Variable Energy Cyclotron Centre, Kolkata, India using a low beam current (∼15 nA). Ion fluences of 10¹⁰, 10¹¹, 10¹², 10¹³ ions/cm² were used. The optical band gap (E_g), calculated from the absorption edge of the UV-Vis spectra of these films in 200-800 nm region varied from 2.167 eV to 1.512 eV for virgin and irradiated samples. In FTIR spectra appreciable changes have been observed after irradiation, indicating the molecular fragmentation, cross-linking, formation of unsaturated groups and free radicals. DSC thermograms give information about the thermal stability and type of thermal reactions (exothermic/endothermic) on the application of heat to the polymer. XRD analyses show slight shift of peak position and significant changes in peak intensity. XRD results show a decrease of ∼4.12% in crystallite size of irradiated sample at the higher fluence of 10¹² ions/cm².     

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.     

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.     

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.     

Investigations on the effect of 100 MeV Ni ions irradiated chloride vapour phase epitaxy (Cl-VPE) grown GaN epilayers

Gallium nitride (GaN) epilayers have been grown by chloride vapour phase epitaxy (Cl-VPE) technique and the grown GaN layers were irradiated with 100 MeV Ni ions at the fluences of 5 × 10¹² and 2 × 10¹³ ions/cm². The pristine and 100 MeV Ni ions irradiated GaN samples were characterized using X-ray diffraction (XRD), UV-visible transmittance spectrum, photoluminescence (PL) and atomic force microscopy (AFM) analysis. XRD results indicate the presence of gallium oxide phases after Ni ion irradiation, increase in the FWHM and decrease in the intensity of the GaN (0 0 0 2) peak with increasing ion fluences. The UV-visible transmittance spectrum and PL measurements show decrease in the band gap value after irradiation. AFM images show the nanocluster formation upon irradiation and the roughness value of GaN increases with increasing ion fluences.     

Surface modifications and deuterium depth profiles in molybdenum irradiated with low-energy D ions

Depth profiles of deuterium trapped in single crystal Mo, polycrystalline Mo, and molybdenum trioxide film on polycrystalline Mo irradiated with 200 eV D ions have been measured up to a depth of 8 μm using the D(³He,p)⁴He nuclear reaction at a ³He energy varied from 0.69 to 4.0 MeV. For the D ion irradiation at 323 K to the highest ion fluence of 5 × 10²⁴ D/m², the D concentration decreases from several at.% in the near-surface layer to bulk values below 10⁻⁴ at.% for single crystal Mo and about 10⁻² at.% for polycrystalline Mo. The maximum D concentration in molybdenum trioxide film differs little in value from that for polycrystalline Mo. Blister formation at high fluences is observed for polycrystalline Mo and molybdenum trioxide film, but not for single crystal Mo. As the irradiation temperature increases from 323 to 493 K, the D retention in the polycrystalline Mo decreases from about 3 × 10²¹ down to about 2 × 10¹⁸ D/m².     

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.     

Light ion irradiation-induced phase transformation in the monoclinic polymorph of zirconia

Ion irradiation damage experiments were performed at ∼80 K on polycrystalline samples of monoclinic, slightly sub-stoichiometric zirconia (ZrO_1.98). Following irradiation with 150 keV Ne⁺ ions, the monoclinic phase was gradually replaced by a new phase. Transmission electron microscopy (TEM) observations in cross-sectional geometry and electron microdiffraction (μD) measurements revealed that the irradiated layer in a sample irradiated to a fluence of 5 × 10²⁰ Ne/m² is partially transformed to a higher symmetry phase of high crystallinity. This phase transformation is accompanied by reduction of the initial micron-sized, highly-twinned grain distribution, to a nano-phased grain structure. Grazing incidence X-ray diffraction (GIXRD) measurements revealed that the radiation-induced phase is a tetragonal polymorph of zirconia. This was verified by the existence of strong (1 0 1) diffraction maxima and weak (1 0 2) reflections (body-centered cell). Raman spectroscopy (RS) measurements were also performed in an attempt to corroborate GIXRD results obtained from the irradiated material. RS measurements in the confocal geometry agreed with GIXRD measurements, although RS was not as definitive as GIXRD. In addition to RS showing the existence of a band corresponding to a tetragonal structure at 262 cm⁻¹, a new mystery band appeared at 702 cm⁻¹ that increased in intensity as a function of irradiation fluence.     

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.     

Impedance studies on high energy Li irradiated PZT thin films

The ferroelectric Pb(Zr_0.48Ti_0.52)O₃ (PZT) thin films prepared by the pulsed laser deposition technique were studied for their response to high energy lithium ion irradiation through impedance spectroscopy. The Debye peaks, observed in the impedance and modulus plots of irradiated films, shifts towards higher frequencies compared to those of unirradiated films. This is equivalent to the trend observed with increase in temperature in the unirradiated films due to the dielectric relaxation. The irradiated films showed a decrease in the grain resistance compared to the unirradiated films. The activation energy of dielectric relaxation increases from 1.25 eV of unirradiated film to 1.62 eV of irradiated film. The observed modifications in the irradiated film were ascribed to the modifications in the grain structure due to the high value of electronic energy loss.     

Change in magnetic properties of MgB2 thin films after irradiation by 200 MeV Au ion beam

The SHI irradiation induced effects on magnetic properties of MgB₂ thin films are reported. The films having thickness 300-400 nm, prepared by hybrid physical chemical vapor deposition (HPCVD) were irradiated by 200 MeV Au ion beam (S_e ∼ 23 keV/nm) at the fluence 1 × 10¹² ion/cm². Interestingly, increase in the transition temperature T_c from 35.1 K to 36 K resulted after irradiation. Substantial enhancement of critical current density after irradiation was also observed because of the pinning provided by the defects created due to irradiation. The change in surface morphology due to irradiation is also studied.     

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.