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.     

氦-3对Zr0.85Ti0.15Co合金吸氚特性影响研究

通过铀床向Zr_0.85Ti_0.15Co床转移氚过程中,研究氦-3对Zr_0.85Ti_0.15Co合金吸氚特性的影响,并结合Ortman模型分析氦-3影响机理。结果表明：氦-3对床体的屏蔽效应明显影响粉末的吸附性能,但屏蔽效应并不能完全抑制Zr_0.85Ti_0.15Co的吸氚反应,覆盖现象严重时其仍能在较低的速率持续吸氚直至吸附完全;氦-3浓度较低时,吸氚完成时间主要由氦-3浓度影响,而氦-3浓度较高时,主要由初始氚分压影响;氦-3对Zr_0.85Ti_0.15Co吸氚的屏蔽过程分为整体流阶段和扩散散流阶段,Ortman模型可较好的预测整体流阶段的氦-3屏蔽压强。     

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.     

热-水-力-化学耦合作用下Ca0.86Nd0.14Ti0.86Al0.14SiO5固溶体的化学稳定性

以CaCO₃、Nd₂O₃、TiO₂、SiO₂、Al₂O₃为原料,用固相法制备掺钕榍石固溶体（Ca_0.86Nd_0.14Ti_0.86Al_0.14SiO₅）。采用PCT法进行浸泡实验,借助X射线衍射（XRD）、扫描电镜（SEM）、电感耦合等离子体发射光谱（ICP-OES）等分析手段,研究掺钕榍石固溶体在热 水 力 化学（THMC）耦合作用下的化学稳定性。结果表明,在pH值为5～9、温度150～200 ℃、压强0.476～1.554 MPa的耦合作用下,Ca_0.86Nd_0.14Ti_0.86Al_0.14SiO₅固溶体具有良好的化学稳定性;pH值、温度（压力）对Ca_0.86Nd_0.14Ti_0.86Al_0.14SiO₅固溶体中Si⁴⁺、Al³⁺、Nd³⁺的归一化浸出率无明显影响;Ca²⁺在200 ℃（1 554 MPa）时的抗浸出性能较150 ℃时的好;在浸泡初期（1～21 d）Ca²⁺在pH值为9时的抗浸出性能优于pH值为5和7时的,浸泡后期（28、42 d）3种溶液中固溶体的Ca²⁺抗浸出性能趋于一致;Ti⁴⁺在pH值为9时的抗浸出性能较pH值为5和7时的好。     

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.     

13C呼吸试剂D-木糖-U-13C5的合成

以D-葡萄糖-U-¹³C₆为起始原料,采用减碳法经双丙酮保护、选择性酸水解、氧化、还原和碱水解五步合成D-木糖-U-¹³C₅,总产率为38.6%（以D-葡萄糖-U-¹³C₆计）。对每步产物使用相应的气相色谱（GC）、气质联用仪（GC-MS）、液相色谱（HPLC）和液质联用仪（LC-MS）进行表征。分析结果表明,每步反应中的产物均为目的产物,同位素丰度和纯度都符合要求,最后一步的产物为D-木糖-U-¹³C₅,其¹³C丰度为99.1 % ,化学纯度为99.9%,符合¹³C呼吸试验的要求。     

烧绿石(La1-yNdy)2Zr2O7模拟固化241Am的晶体结构稳定性研究

为研究²⁴¹Am在La₂Zr₂O₇烧绿石中的固化行为及其对烧绿石晶体结构稳定性的影响,实验选用Nd作为²⁴¹Am的模拟物,采用Sol-喷雾热解法合成了(La_1-yNd_y)₂Zr₂O₇（0.0≤y≤1.0）系列样品,并借助X射线衍射和振动光谱手段对样品的晶体结构稳定性进行了研究。实验结果表明：随着Nd掺杂量的增加,O48f位置参数x_48f和I₍₁₁₁₎ /I₍₂₂₂₎均呈规律性增大,Raman谱逐渐展宽,IR谱发生蓝移,所有结果均证实用Nd不断替换La将导致烧绿石晶体结构有序化程度逐渐降低。另外,实验发现掺杂量y≈0.8是烧绿石晶体结构发生几何相变的逾渗阈值,超过该阈值有序的烧绿石结构将发生突变进而加速向无序萤石结构转变,该实验结果可为(La_1-yAm_y)2Zr2O7固溶体的结构稳定性研究提供参考。     

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.     

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.