Heating electrons with ion irradiation: A first-principles approach

Using time-dependent density functional theory we calculate from first-principles the rate of energy transfer from a moving charged particle to the electrons in an insulating material. The behavior of the electronic stopping power in LiF (a wide band gap insulator) versus projectile velocity displays an effective threshold velocity of 8.2 Bohr/asec for the proton, consistent with recent experimental observations. The calculated proton/antiproton stopping power ratio is 2.4 at velocities slightly above the threshold (16.5 Bohr/asec) as compared to the experimental value of 2.1. The approximations introduced in this new non-perturbative methodology are discussed, and results on the velocity dependence of the stopping power, the locality of the energy transfer, and other characteristics of the host material are presented.     

Swift heavy ion induced structural modifications in zircon and scheelite phases of ThGeO4

Structural modifications in the zircon and scheelite phases of ThGeO₄ induced by swift heavy ions (93 MeV Ni⁷⁺) at different fluences as well as pressure quenching effects are reported. X-ray diffraction and Raman measurements at room temperature on the irradiated zircon phase of ThGeO₄ indicate the occurrence of stresses that lead to a reduction of the cell volume up to 2% followed by its transformation to a mixture of nano-crystalline and amorphous scheelite phases. Irradiation of the zircon phase at liquid nitrogen temperature induces amorphization at a lower fluence (7.5 × 10¹⁶ ions/m²), as compared to that at room temperature (6 × 10¹⁷ ions/m²). Scheelite type ThGeO₄ irradiated at room temperature undergoes complete amorphization at a lower fluence of 7.5 × 10¹⁶ ions/m² without any volume reduction. The track radii deduced from X-ray diffraction measurements on room temperature irradiated zircon, scheelite and low temperature irradiated zircon phases of ThGeO₄ are, 3.9, 3.5 and 4.5 nm, respectively. X-ray structural investigations on the zircon phase of ThGeO₄ recovered after pressurization to about 3.5 and 9 GPa at ambient temperature show the coexistence of zircon and disordered scheelite phases with a larger fraction of scheelite phase occurring at 9 GPa. On the other hand, the scheelite phase quenched from 9 GPa shows crystalline scheelite phase pattern.     

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.     

Effects of energetic heavy ion irradiation on the structure and magnetic properties of FeRh thin films

Fe-54at.%Rh thin films were irradiated with 10 MeV iodine ions at room temperature. Before and after the irradiations, the changes in magnetic properties and the lattice structure of the samples were studied by means of a SQUID magnetometer and X-ray diffraction. For the low fluence irradiation, the SQUID measurement at 20 K shows that the anti-ferromagnetic region of the thin film is changed into ferromagnetic region by the irradiation. As the film thickness is much smaller than the ion range, we can discuss the relationship between the density of energy deposited by ions and the change in magnetization quantitatively. For the high fluence irradiation, the magnetization of the film is strongly decreased by the irradiation, which can be explained as due to the change in lattice structure from B2 into A1 structure by the irradiation.     

Modeling of ion beam induced damage in Si during channeling Rutherford backscattering spectrometry analysis

We have modeled damage creation by an analyzing beam during channeling Rutherford backscattering spectrometry (RBS) analysis. Based on classic scattering theory and the assumption that only a dechanneled ion beam can cause displacements, a chi-square approach is used to fit the modeled spectra with experimental profiles, to extract the dechanneling cross section and the displacement creation efficiency. The study has shown that, for a 2.0 MeV He beam channeled along a Si(1 0 0) axis, the efficiency of defect creation by dechanneled beams is about 8% of the value predicted from the Kichin-Pease model. This suggests a significant dynamic annealing of point defects. The modeling procedure in this work can be used to predict the displacement creation during channeling RBS analysis.     

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.     

Study on the behavior of oxygen atoms in swift heavy ion irradiated CeO2 by means of synchrotron radiation X-ray photoelectron spectroscopy

To study the effects of swift heavy ion irradiation on cerium dioxide (CeO₂), CeO₂ sintered pellets were irradiated with 200 MeV Xe ions at room temperature. For irradiated and unirradiated samples, the spectra of X-ray photoelectron spectroscopy (XPS) were measured. XPS spectra for the irradiated samples show that the valence state of Ce atoms partly changes from +4 to +3. The amount of Ce³⁺ state was quantitatively obtained as a function of ion-fluence. The relative amount of oxygen atom displacements, which are accompanied by the decrease in Ce valence state, is 3-5%. This value is too large to be explained in terms of elastic interactions between CeO₂ and 200 MeV ions. The experimental result suggests the contribution of 200 MeV Xe induced electronic excitation to the displacements of oxygen atoms.     

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.     

Amorphisation of ZnAl2O4 spinel under heavy ion irradiation

ZnAl₂O₄ spinels have been irradiated with several ions (Ne, S, Kr and Xe) at the IRRSUD beamline of the GANIL facility, in order to determine irradiation conditions (stopping power, fluence) for amorphisation. We observed by transmission electron microscopy (TEM) that with Xe ions at 92 MeV, individual ion tracks are still crystalline, whereas an amorphisation starts below a fluence of 5 × 10¹² cm⁻² up to a total amorphisation between 1 × 10¹³ and 1 × 10¹⁴ cm⁻². The coexistence of amorphous and crystalline domains in the same pristine grain is clearly visible in the TEM images. All the crystalline domains remain close to the same orientation as the original grain. According to TEM and X-ray Diffraction (XRD) results, the stopping power threshold for amorphisation is between 9 and 12 keV nm⁻¹.     

Effects of ion irradiation on the structural transformation of sol-gel derived TEOS/MTES thin films

Ion beam processing of organic/inorganic thin films has been shown to be an effective means in converting polymeric films into their final ceramic-like state. In this study, hybrid sol-gel derived thin films based on TEOS (tetraethylorthosilicate) Si(OC₂H₅)₄ and MTES (methyltriethoxysilane) CH₃Si(OC₂H₅)₃ were prepared and deposited on Si substrates by spin coating. After the films were allowed to air dry, they were heat treated at 300 °C for 10 min. Ion irradiation was performed at room temperature using 125 keV H⁺ and 250 keV N²⁺ ions with fluences ranging from 1 × 10¹⁴ to 5 × 10¹⁶ ions/cm². FT-IR and Raman spectroscopies were used to quantify the chemical structural transformations which occurred including the evolution of the organic components, the cross-linking of silica clusters, and the clustering of carbon.     

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.     

Swift heavy ion irradiation induced modification of the microstructure of NiO thin films

NiO nanoparticle films (200 nm thick) grown on Si substrates by pulsed laser deposition method were irradiated by 200 MeV Ag¹⁵⁺ ions. The films were characterized by glancing angle X-ray diffraction, atomic force microscopy and optical absorption spectroscopy. Though electronic energy loss of 200 MeV Ag ions in NiO matrix was higher than the threshold electronic energy loss for creation of columnar defects, films remained crystalline with the initial fcc structure even up to a fluence of 5 × 10¹³ ions cm⁻², where ion tracks are expected to overlap. Irradiation however modified the microstructure of the NiO films considerably. The grain size decreased with increasing ion fluence, which led to reduced surface roughness and increased optical band gap due to quantum confinement. These results correlate well with variation of the power spectral density exponent with ion fluence, which indicate that at high ion fluences, the evolution of surface morphology is governed by surface diffusion.     

Method to measure composition modifications in polyethylene terephthalate during ion beam irradiation

Matter losses of polyethylene terephthalate (PET, Mylar) films induced by 1600 keV deuteron beams have been investigated in situ simultaneously by nuclear reaction analysis (NRA), deuteron forward elastic scattering (DFES) and hydrogen elastic recoil detection (HERD) in the fluence range from 1 × 10¹⁴ to 9 × 10¹⁶ cm⁻². Volatile degradation products escape from the polymeric film, mostly as hydrogen-, oxygen- and carbon-containing molecules. Appropriate experimental conditions for observing the composition and thickness changes during irradiation are determined. ¹⁶O(d,p₀)¹⁷O, ¹⁶O(d,p₁)¹⁷O and ¹²C(d,p₀)¹³C nuclear reactions were used to monitor the oxygen and carbon content as a function of deuteron fluence. Hydrogen release was determined simultaneously by H(d,d)H DFES and H(d,H)d HERD. Comparisons between NRA, DFES and HERD measurements show that the polymer carbonizes at high fluences because most of the oxygen and hydrogen depletion has already occured below a fluence of 3 × 10¹⁶ cm⁻². Release curves for each element are determined. Experimental results are consistent with the bulk molecular recombination (BMR) model.     

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.     

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.     

Radiation damage in ZnO ion implanted at 15 K

Commercial O-face (0 0 0 1) ZnO single crystals were implanted with 200 keV Ar ions. The ion fluences applied cover a wide range from 5 × 10¹¹ to 7 × 10¹⁶ cm⁻². The implantation and the subsequent damage analysis by Rutherford backscattering spectrometry (RBS) in channelling geometry were performed in a special target chamber at 15 K without changing the target temperature of the sample. To analyse the measured channelling spectra the computer code DICADA was used to calculate the relative concentration of displaced lattice atoms.Four stages of the damage evolution can be identified. At low ion fluences up to about 2 × 10¹³ cm⁻² the defect concentration increases nearly linearly with rising fluence (stage I). There are strong indications that only point defects are produced, the absolute concentration of which is reasonably given by SRIM calculations using displacement energies of E_d(Zn) = 65 eV and E_d(O) = 50 eV. In a second stage the defect concentration remains almost constant at a value of about 0.02, which can be interpreted by a balance between production and recombination of point defects. For ion fluences around 5 × 10¹⁵ cm⁻² a second significant increase of the defect concentration is observed (stage III). Within stage IV at fluences above 10¹⁶ cm⁻² the defect concentration tends again to saturate at a level of about 0.5 which is well below amorphisation. Within stages III and IV the damage formation is strongly governed by the implanted ions and it is appropriate to conclude that the damage consists of a mixture of point defects and dislocation loops.     

A systematic study on analysis-induced radiation damage in silicon during channeling Rutherford backscattering spectrometry analysis

Channeling Rutherford backscattering spectrometry (RBS) is an essential analysis technique in materials science. However, the accuracy of RBS can be significantly affected by disorders in materials induced by the analyzing ion beam even under channeling mode. We have studied RBS analysis-induced radiation damage in silicon. A 140-keV H⁺ ion beam was incident along 〈1 0 0〉 Si axis at room temperature to a fluence ranging from 1.6 × 10¹⁶ cm⁻² to 7.0 × 10¹⁶ cm⁻². The evolution of the aligned yields versus fluences has been examined and found to agree well with a model proposed by us.     

Changes in metal nanoparticle shape and size induced by swift heavy-ion irradiation

Changes in the shape and size of Co, Pt and Au nanoparticles induced by swift heavy-ion irradiation (SHII) have been characterized using a combination of transmission electron microscopy, small-angle X-ray scattering and X-ray absorption near-edge structure. Elemental nanoparticles of diameters 2-15 nm were first formed in amorphous SiO₂ by ion implantation and thermal annealing and then irradiated at room temperature with 27-185 MeV Au ions as a function of fluence. Spherical nanoparticles below a minimum diameter (4-7 nm) remained spherical under SHII but progressively decreased in size as a result of dissolution into the SiO₂ matrix. Spherical nanoparticles above the minimum diameter threshold were transformed to elongated rods aligned with the ion beamdirection. The nanorod width saturated at an electronic energy deposition dependent value, progressively increasing from 4-6 to 7-10 nm (at 5-18 keV/nm, respectively) while the nanorod length exhibited a broad distribution consistent with that of the unirradiated spherical nanoparticles. The threshold diameter for spherical nanoparticle elongation was comparable to the saturation value of nanorod width. We correlate this saturation value with the diameter of the molten track induced in amorphous SiO₂ by SHII. In summary, changes in nanoparticle shape and size are governed to a large extent by the ion irradiation parameters.     

Toward high accuracy in channeling Rutherford backscattering spectrometry analysis

Channeling Rutherford backscattering spectrometry (RBS) has been widely used to quantitatively analyze displacements in monocrystalline solid state thin films. Its accuracy, however, relies on the approach of separating yields contributed by channeled components and by dechanneled components. In this study, efforts have been made to increase accuracy through three major approaches: first, we have considered the stopping power difference between channeled and non-channeled components; second, we have proposed a mathematical formula to describe a smooth transition from single scattering to multiple scattering in describing dechanneling of analyzing beams as a function of displacements; third, we have used an iterative approach to extract yields from dechanneling components without using any predetermined dechanneling cross sections. These novel approaches are expected to increase accuracy in channeling RBS analysis.     

Radiation effects in cubic zirconia: A model system for ceramic oxides

Ceramics are key engineering materials for electronic, space and nuclear industry. Some of them are promising matrices for the immobilization and/or transmutation of radioactive waste. Cubic zirconia is a model system for the study of radiation effects in ceramic oxides. Ion beams are very efficient tools for the simulation of the radiations produced in nuclear reactors or in storage form. In this article, we summarize the work made by combining advanced techniques (RBS/C, XRD, TEM, AFM) to study the structural modifications produced in ion-irradiated cubic zirconia single crystals. Ions with energies in the MeV-GeV range allow exploring the nuclear collision and electronic excitation regimes. At low energy, where ballistic effects dominate, the damage exhibits a peak around the ion projected range; it accumulates with a double-step process by the formation of a dislocation network. At high energy, where electronic excitations are favored, the damage profiles are rather flat up to several micrometers; the damage accumulation is monotonous (one step) and occurs through the creation and overlap of ion tracks. These results may be generalized to many nuclear ceramics.