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.     

Laser-joined Al2O3 and ZrO2 ceramics for high-temperature applications

A laser process is presented that has been specially developed for joining oxide ceramics such as zirconium oxide (ZrO₂) and aluminium oxide (Al₂O₃). It details, by way of example, the design of the laser process applied for to producing both Al₂O₃-Al₂O₃ and ZrO₂-ZrO₂ joints using siliceous glasses as fillers.The heat source used was a continuous wave diode laser with a wavelength range of 808-1010 nm. Glasses of the SiO₂-Al₂O₃-B₂O₃-MeO system were developed as high-temperature resistant brazing fillers whose expansion coefficients, in particular, were optimally adapted to those of the ceramics to be joined. Specially designed measuring devices help to determine both the temperature-dependent emission coefficients and the synchronously determined proportions of reflection and transmission.The glass-ceramic joints produced are free from gas inclusions and macroscopic defects and exhibit a homogenous structure. The average strength values achieved were 158 MPa for the Al₂O₃ system and 190 MPa for the ZrO₂ system, respectively.     

Strain enhancement in Si induced by direct bonding of a LaAlO3 film to a Si substrate

The depth profiles of lattice strain near the interface regions of LaAlO₃/Si and the SiO₂ interfacial layer/Si were investigated by the ion channeling technique using high-resolution Rutherford backscattering spectroscopy (HRBS). In the case of the LaAlO₃/Si stack, horizontal tensile strain in the Si near the interface was clearly observed. However, this strain was relaxed by formation of the interfacial layer through annealing in an oxygen ambient. These results suggest that the strain in Si induced by a dielectric strongly depends on the material in contact with Si.     

The lattice parameter of cubic ZrO2 formed on zirconium

The simultaneous presence of cubic and monoclinic ZrO₂ and αZr reflections in selected area electron diffraction patterns taken from an oxide grown on αZr(0001) allowed the determination of a new cubic ZrO₂ lattice parameter of a = 0.5135 ± 0.0005 nm.     

The phase state at high temperatures in the MOX-SiO2 system

Influence of impurity Si on microstructure in a plutonium and uranium mixed oxide (MOX), which is used for fast breeder reactor fuel, was investigated, and phase state in 25% SiO₂ - (U_0.7Pu_0.3)O₂ was observed as a function of oxygen chemical potential. Compounds composed of Pu and Si with other elements were observed at grain boundaries of the MOX parent phase in the specimens after annealing. These compounds were not observed in the grain interior and the MOX phase was not affected significantly by impurity Si. It was found that the compounds tended to form more observably with decreasing O/M ratio and with increasing annealing temperatures.     

Electrical properties changes induced by electron radiation at TiO2/Si interface

TiO₂/Si structures were fabricated by electron beam evaporation, and exposed to electron beam irradiation to investigate their electrical properties using the high frequency capacitance-voltage measurements. It was found that samples annealed in oxygen became more radiation resistant than un-annealed samples, which can be explained by the Ti valence variations induced by radiation. The samples were characterized by X-ray diffraction to show the Ti₂O₃ crystalline phase transformed to anatase-crystalline phase after oxygen annealing.     

Gettering layer for oxygen accumulation in the initial stage of SIMOX processing

A cavity layer or nano-bubble layer introduced by He implantation before the oxygen implantation collects the implanted oxygen and increases the oxygen concentration. The average size and density of the oxygen precipitates formed in the initial stage of the separation-by-implanted-oxygen (SIMOX) process is conform with the size and density of the cavities pre-formed by He implantation and annealing. The gettering ability of the cavity layer for oxygen is directly related to the area of the internal surface of the cavities. A nano-bubble layer accumulates oxygen in a very narrow range occurring between the damage maximum, D_P, and the mean projected ion range, R_P. Such a nano-bubble layer is most efficient in oxygen gettering due to their larger area of the internal surface and the small size of the oxide precipitates initially formed at the bubbles.     

Synthesis of nanodimensional TiO2 thin films using energetic ion beam

Nanophases of TiO₂ are achieved by irradiating polycrystalline thin films of TiO₂ by 100 MeV Au ion beam at varying fluence. The surface morphology of pristine and irradiated films is studied by atomic force microscopy (AFM). Phase of the film before and after irradiation is identified by glancing angle X-ray diffraction (GAXRD). The blue shift observed in UV-vis absorption edge of the irradiated films indicates nanostructure formation. Electron spin resonance (ESR) studies are carried out to identify defects created by the irradiation. The nanocrystallisation induced by SHI irradiation in polycrystalline thin films is studied.     

Radiation effect on the photoluminescence properties of Si/SiO2 thin films

Silicon ions were implanted into SiO₂ thin films with various doses and energies. For the films implanted with various ion doses the photoluminescence (PL) intensity of 470 nm firstly increased with the increase of Si ion dose, which is similar to the variation trend of displacement per atom (DPA) number during ion radiation. Further increasing Si ion dose the PL intensity of 470 nm decreased gradually since the neutral oxygen vacancy centers were destroyed. For the samples implanted with different energy the variation trend of PL intensity for 470 nm peak is similar to the result of DPA under different radiation energy according to SRIM2006 simulation. With the increase of radiation energy a new PL peak at 550 nm appeared because of the variation of defect type. Combining with the simulation results and PL spectra the radiation effect on Si/SiO₂ thin films were proposed.     

Study on effects of swift heavy ion irradiation on the crystal structure in CeO2 doped with Gd2O3

To simulate the effects of Gd₂O₃-doping and high-energy fission products in UO₂, Gd₂O₃-doped CeO₂ pellets were irradiated with 200-MeV Xe¹⁴⁺ ions. Doping and irradiation effects were analyzed using X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS). The lattice constant of CeO₂ decreases and the local structure is disordered with increased doping levels. However, the irradiation induces an expansion of the lattice and a disordering of atomic arrangement near the Gd atoms. The effects of the irradiation become more pronounced with increasing Gd₂O₃-dopant levels. Our results are compared with those of a study involving Er₂O₃-doped CeO₂.     

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.     

Positron annihilation on the surfaces of SiO2 films thermally grown on single crystal of Cz-Si

Two-detector coincidence system and mono-energetic slow positron beam has been applied to measure the Doppler broadening spectra for single crystals of SiO₂, SiO₂ films with different thickness thermally grown on single crystal of Cz-Si, and single crystal of Si without oxide film. Oxygen is recognized as a peak at about 11.85 × 10⁻³m₀c on the ratio curves. The S parameters decrease with the increase of positron implantation energy for the single crystal of SiO₂ and Si without oxide film. However, for the thermally grown SiO₂-Si sample, the S parameters in near surface of the sample increase with positron implantation energy. It is due to the formation of silicon oxide at the surface, which lead to lower S value. S and W parameters vary with positron implantation depth indicate that the SiO₂-Si system consist of a surface layer, a SiO₂ layer, a SiO₂-Si interface layer and a semi-infinite Si substrate.     

Defect volumes of BO2 doped Y2O3 (B = Ti, Zr, Hf and Ce)

Atomistic simulations have been employed to study the effect of BO₂ (fluorite) incorporation into the bixbyite oxide Y₂O₃. The energetically preferred defect mechanism and the associated lattice parameter changes that occur from BO₂ doping have been predicted. The addition of Group IV elements into Y₂O₃ can follow three different mechanisms. The energetically favourable method is through a mediated reaction for ZrO₂ and HfO₂ while for TiO₂ and CeO₂, reducing B⁴⁺ to B³⁺ provides the lowest energy reaction. ZrO₂ and HfO₂ doping results in the lowest volume changes.     

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.     

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.     

Radiation damage effects in layered thin film MgO/HfO2 structures

In this report, we present a study of a thin film tri-layer structure, HfO₂/MgO/HfO₂, irradiated at room temperature with 10 MeV Au ions over a wide fluence range from 5 × 10¹³ to 3.7 × 10¹⁶ Au/cm². The tri-layer structure is a model representation for the microstructure in a composite dispersion nuclear fuel or waste form. Microstructural and chemical composition changes were examined by transmission and scanning transmission electron microscopy (TEM & STEM) combined with energy dispersive X-ray spectroscopy (EDXS), grazing incidence X-ray diffraction (GIXRD) and Rutherford backscattering spectroscopy (RBS) techniques. The microstructural evolution in the HfO₂/MgO/HfO₂ trilayer was similar to the radiation damage behavior of the individual HfO₂ and MgO constituents. For instance, we observed an absence of amorphization in both the MgO and HfO₂ layers and a phase transformation of HfO₂ from the monoclinic to the tetragonal HfO₂ polymorph. In addition, we observed the formation of void-type defects at one of the MgO/HfO₂ interfaces. Such voids are not characteristic to either bulk material (MgO or HfO₂) exposed to ion irradiation.     

Effects of swift heavy ion irradiation on the structure of Er2O3-doped CeO2

In order to simulate the effects of burnable poison doping on the fission fragment damage of UO₂ nuclear fuels, Er₂O₃-doped CeO₂ pellets were irradiated with 200 MeV Xe¹⁴⁺ ions. The irradiation effect was measured by means of X-ray diffraction (XRD). The expansion of lattice and the disordering of atomic arrangement due to the irradiation become more remarkable with increasing the concentration of the Er₂O₃ dopant.     

Mechanism of elongation of gold or silver nanoparticles in silica by irradiation with swift heavy ions

It has been reported that elongated Au nanoparticles oriented parallel to one another can be synthesized in SiO₂ by ion irradiation. Our aim was to elucidate the mechanism of this elongation. We prepared Au and Ag nanoparticles with a diameter of 20 nm in an SiO₂ matrix. It was found that Au nanoparticles showed greater elongated with a higher flux of ion beam and with thicker SiO₂ films. In contrast, Ag nanoparticles split into two or more shorter nanorods aligned end to end in the direction parallel to the ion beam. These experimental results are discussed in the framework of a thermal spike model of Au and Ag nanorods embedded in SiO₂. The lattice temperature exceeds the melting temperatures of SiO₂, Au and Ag for 100 ns after one 110 MeV Br¹⁰⁺ ion has passed through the middle of an Au or Ag nanorod.     

Eutectic crystallization in the FeO1.5-UO2+x-ZrO2 system

Results of the investigation of the FeO_1.5-UO_2+x-ZrO₂ system in air are presented. The eutectic position and the content of the phases crystallized at this point have been determined. The temperature and the composition of the ternary eutectic are 1323 ± 7 °С and 67.4 ± 1.0 FeO_1.5, 30.5 ± 1.0 UO_2+x, 2.1 ± 0.2 ZrO₂ mol.%, respectively. The solubilities of FeO_1.5 and ZrO₂ in the UO_2+x(FeO_1.5, ZrO₂) solid solution correspond to respectively 3.2 and 1.1 mol.%. The solubilities of UO₂ and ZrO₂ in FeO_1.5 are not significant. The existence of a solid solution on the basis of U(Zr)FeO₄ compound is found. The ZrO₂ solubility in this solid solution is 7.0 mol.%.     

Chlorination of UO2, PuO2 and rare earth oxides using ZrCl4 in LiCl-KCl eutectic melt

A new chlorination method using ZrCl₄ in a molten salt bath has been investigated for the pyrometallurgical reprocessing of nuclear fuels. ZrCl₄ has a high reactivity with oxygen but is not corrosive to refractory metals such as steel. Rare earth oxides (La₂O₃, CeO₂, Nd₂O₃ and Y₂O₃) and actinide oxides (UO₂ and PuO₂) were allowed to react with ZrCl₄ in a LiCl-KCl eutectic salt at 773 K to give a metal chloride solution and a precipitate of ZrO₂. An addition of zirconium metal as a reductant was effective in chlorinating the dioxides. When the oxides were in powder form, the reaction was observed to progress rapidly. Cyclic voltammetry provided a convenient way of establishing when the reaction was completed. It was demonstrated that the ZrCl₄ chlorination method, free from corrosive gas, was very simple and useful.