Ion irradiation induced nanocrystal formation in amorphous Zr55Cu30Al10Ni5 alloy

Ion irradiation can be used to induce partial crystallization in metallic glasses to improve their surface properties. We investigated the microstructural changes in ribbon Zr₅₅Cu₃₀Al₁₀Ni₅ metallic glass after 1 MeV Cu-ion irradiation at room temperature, to a fluence of 1.0 × 10¹⁶ cm⁻². In contrast to a recent report by others that there was no irradiation induced crystallization in the same alloy [S. Nagata, S. Higashi, B. Tsuchiya, K. Toh, T. Shikama, K. Takahiro, K. Ozaki, K. Kawatusra, S. Yamamoto, A. Inouye, Nucl. Instr. and Meth. B 257 (2007) 420], we have observed nanocrystals in the as-irradiated samples. Two groups of nanocrystals, one with diameters of 5–10 nm and another with diameters of 50–100 nm are observed by using high resolution transmission electron microscopy. Experimentally measured planar spacings (d-values) agree with the expectations for Cu₁₀Zr₇, NiZr₂ and CuZr₂ phases. We further discussed the possibility to form a substitutional intermetallic (Ni_xCu_1−x)Zr₂ phase.     

Structural changes in anatase TiO2 thin films irradiated with high-energy heavy ions

In order to investigate possible structural changes due to high-density electronic excitation, anatase TiO₂ thin film specimens were irradiated with 230 MeV ¹³⁶Xe¹⁵⁺ ions and 200 MeV ¹⁹⁷Au¹³⁺ ions. X-ray diffraction (XRD) patterns were measured before and after irradiation. The intensity of the XRD peak assigned to the (0 0 4) planes of anatase TiO₂ decreases in an exponential manner as a function of ion-fluence. This result can be explained by the formation of the cylindrical damaged regions (i.e. ion tracks) with diameters of 9.6 and 16.3 nm for 230 MeV Xe and for 200 MeV Au ion irradiations, respectively. The difference in the track diameter between Xe ion irradiation and Au ion irradiation can be attributed to the difference in the electronic stopping power (and to the ion-velocity effect, if any). For 200 MeV Au ion irradiation, splitting of the (0 0 4) peak is observed. The original (0 0 4) TiO₂ peak remains in the same position, but the new peak shifts to higher angles as fluence increases.     

Swift heavy ion irradiation-induced microstructure modification of two delta-phase oxides: Sc4Zr3O12 and Lu4Zr3O12

Swift gold ions (185 MeV) were used to systematically investigate the radiation damage response of delta phase compounds Sc₄Zr₃O₁₂ and Lu₄Zr₃O₁₂ in the electronic energy loss regime. Ion irradiation-induced microstructural modifications were examined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). XRD investigations indicate a phase transformation from ordered rhombohedral to disordered fluorite (O-D) in both compounds, with the Sc compound transforming at a higher ion fluence compared with the Lu compound. This result is consistent with our previous study on Sc₄Zr₃O₁₂ and Lu₄Zr₃O₁₂ under displacive radiation environment in which the nuclear energy loss is dominant. High resolution TEM revealed that individual ion tracks maintain crystalline structure, while the core region experiences an O-D phase transformation. TEM observations also suggest that for the doses in which the tracks overlap, the O-D phase transformation occurs across the entire ion range.     

Damage evolution in Au-implanted Ho2Ti2O7 titanate pyrochlore

Damage evolution at room temperature in Ho₂Ti₂O₇ single crystals is studied under 1 MeV Au²⁺ ion irradiation by Rutherford backscattering spectroscopy along the 〈0 0 1〉 direction. For a better determination of ion-induced disorder profile, an iterative procedure and a Monte Carlo code (McChasy) were used to analyze ion channeling spectra. A disorder accumulation model, with contributions from the amorphous fraction and the crystalline disorder, is fit to the Ho damage accumulation data. The damage evolution behavior indicates that the relative disorder on the Ho sublattice follows a nonlinear dependence on dose and that defect-stimulated amorphization is the primary amorphization mechanism. Similar irradiation behavior previously was observed in Sm₂Ti₂O₇. A slower damage accumulation rate for Ho₂Ti₂O₇, as compared with damage evolution in Sm₂Ti₂O₇, is mainly attributed to a lower effective cross section for defect-stimulated amorphization.     

Influence of UV irradiation and RTA process on optical properties of Si implanted SiO2

Si ion implantation was widely used to synthesize specimens of SiO₂ containing supersaturated Si and subsequent high temperature annealing induces the formation of embedded luminescent Si nanocrystals. In this work, the potentialities of excimer UV-light (172 nm, 7.2 eV) irradiation and rapid thermal annealing (RTA) to enhance the photoluminescence and to achieve low temperature formation of Si nanocrystals have been investigated. The Si ions were introduced at acceleration energy of 180 keV to fluence of 7.5 × 10¹⁶ ions/cm². The implanted samples were subsequently irradiated with an excimer-UV lamp. After the process, the samples were rapidly thermal annealed before furnace annealing (FA). Photoluminescence spectra were measured at various stages at the process. We found that the luminescence intensity is strongly enhanced with excimer-UV irradiation and RTA. Moreover, effective visible photoluminescence which is not observed with a simple FA treatment, is found to be observed even after FA at 900 °C, only for specimens treated with excimer-UV lamp and RTA. Based on our experimental results, we discuss the effects of excimer-UV lamp irradiation and RTA process on Si nanocrystals related photoluminescence.     

Heavy-ion-induced luminescence of amorphous SiO2 during nanoparticle formation

Silica glass was implanted with negative 60 keV Cu ions at an ion flux from 5 to 75 μA/cm² up to a fluence of 1 × 10¹⁷ ions/cm² at initial sample temperatures of 300, 573 and 773 K. Spectra of ion-induced photon emission (IIPE) were collected in situ in the range from 250 to 850 nm. Optical absorption spectra of implanted specimens were ex situ measured in the range from 190 to 2500 nm.

IIPE spectra showed a broad band centered around 560 nm (2.2 eV) that was assigned to Cu⁺ solutes. The band appeared at the onset of irradiation, increased in intensity up to a fluence of about 5 × 10¹⁵ ions/cm² and then gradually decreased indicating three stage of the ion beam synthesis of nanoclusters: accumulation of implants, nucleation and growth nanoclusters. The IIPE intensity normalized on the ion flux is independent on the ion flux below 20 μA/cm²at higher fluences. The intensity of the band increased with increasing samples temperature, when optical absorption spectra reveal the increase of Cu nanoparticles size.     

Radiation damage induced by 5 keV Si ion implantation in strained-Si/Si0.8Ge0.2

The damage distributions induced by ultra low energy ion implantation (5 keV Si⁺) in both strained-Si/Si_0.8Ge_0.2 and normal Si are measured using high-resolution RBS/channeling with a depth resolution better than 1 nm. Ion implantation was performed at room temperature over the fluence range from 2 × 10¹³ to 1 × 10¹⁵ ions/cm². Our HRBS results show that the radiation damage induced in the strained Si is slightly larger than that in the normal Si at fluences from 1 × 10¹⁴ to 4 × 10¹⁴ ions/cm² while the amorphous width is almost the same in both strained and normal Si.     

Thermoluminescence properties of nanocrystalline K2Ca2(SO4)3:Eu irradiated with gamma rays and proton beam

Thermoluminescence properties of nanocrystalline K₂Ca₂(SO₄)₃:Eu prepared by ball milling technique have been studied and the nanophosphor’s suitability as an effective gamma radiation and proton beam dosimeter material has been examined. It is found that the nanophosphor is suitable for dosimetry over a very wide range of doses ∼1 Gy to 1 kGy for gamma radiation. And for proton beam the same nanophosphor shows a more or less linear response for the dose range 0.1-100 Gy. A comparative study of this nanophosphor with its corresponding microcrystalline form (prepared by solid-state diffusion method) as well as the nanocrystalline form prepared by (the more conventional) co-precipitation technique has shown that the nanophosphor prepared by the ball milling technique is in almost all respects better than the other two forms reported earlier.     

XRD investigation of ion irradiated Ti3Si0.90Al0.10C2

Ti₃SiC₂ is one of the most promising materials belonging to M_n+1AX_n phases, which exhibit good damage tolerance, thermal stability and mechanical properties.Recently, in the frame of research on future gas cooled fast nuclear reactors, Ti₃SiC₂ has been considered as an innovative candidate material, which could be incorporated in some core components such as fuel cladding. At the present time, however, very few data are available concerning the behaviour of this material after irradiation. In this work, Ti₃Si_0.90Al_0.10C₂ samples were irradiated with high energy Kr and Xe ions and characterized by X-ray diffraction. Patterns were analysed in terms of change in peak intensity, peak position and width. Rietveld refinements were also performed. Increase in micro-strains and lattice parameter with irradiation dose was highlighted. The formation of β-Ti₃SiC₂, which has never been observed by experimental XRD on non irradiated material, was proposed for the highly irradiated samples. A partial recovery of the microstructure with temperature was found.     

Structure and morphology of ion irradiated Au nanocrystals in SiO2

We have investigated the effect of ion irradiation on the structure and morphology of Au nanocrystals (NCs) fabricated by ion beam synthesis in a thin SiO₂ layer on a Si substrate. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements show a significant drop in the average Au–Au coordination, as well as a loss of medium and long range order with increasing irradiation dose. Small angle X-ray scattering (SAXS) measurements reveal a concomitant reduction in average NC size. These observations are a consequence of structural disorder and collisional mixing induced by the irradiation. The observed reduction in average Au–Au coordination by EXAFS differs significantly from that estimated from the average NC sizes evaluated using SAXS. This behavior can be explained by the dissolution of Au NCs into the SiO₂ matrix. A significant bond-length contraction indicates that part of this material forms small Au clusters (dimers, trimers, etc.) during irradiation that cannot be detected by SAXS. Combining the results from SAXS and EXAFS measurements, we estimate the volume fraction of such clusters.     

Ion beam analysis of a structural phase transition in porous TiO2/V2O5 ceramics with rough surfaces

TiO₂/V₂O₅ based ceramic materials applied in catalysis were investigated. Structural properties like the grain diameter of these pressed ceramic powders were analysed by means of Rutherford backscattering (RBS) making use of an analytic model to describe the energy spectra of porous rough samples. Grain diameters of these samples were deduced as function of process temperature and chemical composition and related to a phase transition from the TiO₂-Anatase/V₂O₅-Shcherbinaite to Rutile solid solution (Rutile-ss) structure. RBS data were compared to results of scanning electron microscopy (SEM). The activation energy for the sintering at the phase transition was estimated to 5.4 eV.     

The fabrication of planar waveguides on Bi12TiO20 crystals by oxygen and helium ion implantation

We report the first fabrication and characterization of optical planar waveguides in Bi₁₂TiO₂₀ crystals by ion implantation. For comparison we selected O²⁺ and He⁺ as our implanted ions. The loss value of the oxygen-implanted planar waveguide is reduced to 1.24 dB/cm after annealing at 260 °C for 30 min. The guided-mode profiles are successfully modeled through numerical simulations.     

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.     

Ion beam enhanced etching of LiNbO3

Single crystals of z- and x-cut LiNbO₃ were irradiated at room temperature and 15 K using He⁺- and Ar⁺-ions with energies of 40 and 350 keV and ion fluences between 5 × 10¹² and 5 × 10¹⁶ cm⁻². The damage formation investigated with Rutherford backscattering spectrometry (RBS) channeling analysis depends on the irradiation temperature as well as the ion species. For instance, He⁺-irradiation of z-cut material at 300 K provokes complete amorphization at 2.0 dpa (displacements per target atom). In contrast, 0.4 dpa is sufficient to amorphize the LiNbO₃ in the case of Ar⁺-irradiation. Irradiation at 15 K reduces the number of displacements per atom necessary for amorphization. To study the etching behavior, 400 nm thick amorphous layers were generated via multiple irradiation with He⁺- and Ar⁺-ions of different energies and fluences. Etching was performed in a 3.6% hydrofluoric (HF) solution at 40 °C. Although the etching rate of the perfect crystal is negligible, that of the amorphized regions amounts to 80 nm min⁻¹. The influence of the ion species, the fluence, the irradiation temperature and subsequent thermal treatment on damage and etching of LiNbO₃ are discussed.     

Bulk-compositional changes of Ni2Al3 and NiAl3 during ion etching

Bulk-compositional changes of Ni₂Al₃ and NiAl₃ in a Ni-50 wt% Al alloy during ion etching have been investigated by transmission electron microscopy and energy dispersive X-ray spectroscopic analyses. After etching with 7, 5 and 3 keV Ar⁺ ions for 15, 24 and 100 h nickel contents in both Ni₂Al₃ and NiAl₃ exceeded greatly those in the initial compounds and increased with the decrement of the sputtering energy. After 100 h etching with 3 keV Ar⁺ ions the compositions of these two compounds reached a similar value, about Ni_80-83Al_12-15Fe_3-4Cr_1-2 (at%). A synergistic action of preferential sputtering, radiation-induced segregation and radiation-enhanced diffusion enables the altered-layers at the top and bottom of the film extend through the whole film. The bulk-compositional changes are proposed to occur in the unsteady-state sputtering regime of ion etching and caused by an insufficient supply of matter in a thin film.     

Effects of MeV Si ions bombardment on the thermoelectric generator from SiO2/SiO2 + Cu and SiO2/SiO2 + Au nanolayered multilayer films

The defects and disorder in the thin films caused by MeV ions bombardment and the grain boundaries of these nanoscale clusters increase phonon scattering and increase the chance of an inelastic interaction and phonon annihilation. We prepared the thermoelectric generator devices from 100 alternating layers of SiO₂/SiO₂ + Cu multi-nano layered superlattice films at the total thickness of 382 nm and 50 alternating layers of SiO₂/SiO₂ + Au multi-nano layered superlattice films at the total thickness of 147 nm using the physical vapor deposition (PVD). Rutherford Backscattering Spectrometry (RBS) and RUMP simulation have been used to determine the stoichiometry of the elements of SiO₂, Cu and Au in the multilayer films and the thickness of the grown multi-layer films. The 5 MeV Si ions bombardments have been performed using the AAMU-Center for Irradiation of Materials (CIM) Pelletron ion beam accelerator to make quantum (nano) dots and/or quantum (quantum) clusters in the multilayered superlattice thin films to decrease the cross plane thermal conductivity, increase the cross plane Seebeck coefficient and cross plane electrical conductivity. To characterize the thermoelectric generator devices before and after Si ion bombardments we have measured Seebeck coefficient, cross-plane electrical conductivity, and thermal conductivity in the cross-plane geometry for different fluences.     

Localised modifications of anatase TiO2 thin films by a Focused Ion Beam

A Focused Ion Beam (FIB) has been used to implant micrometer-sized areas of polycrystalline anatase TiO₂ thin films with Ga⁺ ions using fluencies from 10¹⁵ to 10¹⁷ ions/cm². The evolution of the surface morphology was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). In addition, the chemical modifications of the surface were followed by X-ray photoelectron spectroscopy (XPS). The implanted areas show a noticeable change in surface morphology as compared to the as-deposited surface. The surface loses its grainy morphology to gradually become a smooth surface with a RMS roughness of less than 1 nm for the highest ion fluence used. The surface recession or depth of the irradiated area increases with ion fluence, but the rate with which the depth increases changes at around 5 × 10¹⁶ ions/cm². Comparison with implantation of a pre-irradiated surface indicates that the initial surface morphology may have a large effect on the surface recession rate. Detailed analysis of the XPS spectra shows that the oxidation state of Ti and O apparently does not change, whereas the implanted gallium exists in an oxidation state related to Ga₂O₃.     

Drastic reduction of leakage current in ferroelectric Bi3.15Nd0.85Ti3O12 films by ionizing radiation

Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) ferroelectric thin films were grown on Pt/Ti/SiO₂/Si substrates by a sol-gel method. The samples were exposed to different dosage of ionizing radiation. Distortions in the crystalline structure, changes in the surface roughness and decrease in the remnant polarization were observed after radiation. For films subjected to 100 Mrad radiation, decrease in the leakage current up to four orders of magnitude was also observed, which can be explained by the increased grain boundary barrier height. Our results suggest that ionizing radiation could be an effective tool in modifying the properties of ferroelectric thin film for use in non-volatile memory devices.