Electron irradiation-induced change of structure and damage mechanisms in multi-walled carbon nanotubes

Owing to their unique structure and excellent electrical property, carbon nanotubes(CNTs) as an ideal candidate for making future electronic components have great application potentiality. In order to meet the requirements for space application in electronic components, it is necessary to study structural changes and damage mechanisms of multi-walled carbon nanotubes(MWCNTs), caused by the irradiations of 70 and 110 ke V electrons. In the paper, the changes of structure and damage mechanisms in the irradiated MWCNTs, induced by the irradiations of 70 and 110 ke V electrons, are investigated.The changes in surface morphology and structure of the irradiated MWCNT film are characterized using scanning electron microscopy(SEM), x-ray photoelectron spectroscopy(XPS), Raman spectroscopy, x-ray diffraction analysis(XRD), and electron paramagnetic resonance(EPR) spectroscopy. It is found that the MWCNTs show different behaviors in structural changes after 70 and 110 ke V electron irradiation due to different damage mechanisms. SEM results reveal that the irradiation of 70 ke V electrons does not change surface morphology of the MWCNT film, while the irradiation of 110 ke V electrons with a high fluence of 5 × 1015cm-2leads to evident morphological changes, such as the formation of a rough surface, the entanglement of nanotubes and the shrinkage of nanotubes. Based on Raman spectroscopy, XPS, and XRD analyses, it is confirmed that the irradiation of 70 ke V electrons increases the interlayer spacing of the MWCNTs and disorders their structure through electronic excitations and ionization effects, while the irradiation of 110 ke V electrons obviously reduces the interlayer spacing of the MWCNTs and improves their graphitic order through knock-on atom displacements. The improvement of the irradiated MWCNTs by 110 ke V electrons is attributed to the restructuring of defect sites induced by knock-on atom displacements. EPR spectroscopic analyses reveal that the MWCNTs exposed to both70 ke V electrons and 110 ke V electrons suffer ionization damage to some extent.     

Structural and optical investigation of nonpolar a-plane GaN grown by metal-organic chemical vapour deposition on r-plane sapphire by neutron irradiation

Nonpolar (1120) a-plane GaN films are grown by metal-organic chemical vapour deposition (MOCVD) on r-plane (1102) sapphire.The samples are irradiated with neutrons under a dose of 1 × 10 15 cm 2.The surface morphology,the crystal defects and the optical properties of the samples before and after irradiation are analysed using atomic force microscopy (AFM),high resolution X-ray diffraction (HRXRD) and photoluminescence (PL).The AFM result shows deteriorated sample surface after the irradiation.Careful fitting of the XRD rocking curve is carried out to obtain the Lorentzian weight fraction.Broadening due to Lorentzian type is more obvious in the as-grown sample compared with that of the irradiated sample,indicating that more point defects appear in the irradiated sample.The variations of line width and intensity of the PL band edge emission peak are consistent with the XRD results.The activation energy decreases from 82.5 meV to 29.9 meV after irradiation by neutron.     

Femtosecond laser-induced long-lasting phosphorescence in Pr^3＋-doped ZnO-B2O3-SiO2 glass

This paper studies the phenomenon of long-lasting phosphorescence induced by a femtosecond laser in Pr3 -doped ZnO-B2O3-SiO2 glass. With the glass irradiated by a focused femtosecond laser for a short time, the emission of strong reddish long-lasting phosphorescence from the irradiated part of the glass can be observed. The emission peaks are located at 495 and 603 nm in wavelength, showing that the long-lasting phosphorescence originates from the emission of Pr^3 . The intensity of the phosphorescence decreases in inverse proportion to time after the removal of the laser. By analysing the absorption and electron spin resonance spectra of the glass, we find that colour-centres are induced in the glass matrix after the irradiation of the femtosecond laser. A possible mechanism has been provided to account for the generation of long-lasting phosphorescence.     

Study of the microstructural transformations of borate glass and barium metaborate crystals induced by femtosecond laser

This paper describes the microstructural transformations of borate glass and barium metaborate crystals induced by femtosecond laser. Such structural transformations were verified by Raman spectroscopy. The borate glass is transformed into low temperature (LT) phase of barium metaborate (BaB_2O_4) crystals after being irradiated for 10 min by a femtosecond laser. In addition, after 20 min of irradiation, high temperature (HT) phase of BaB_2O_4 crystals is also produced. Further studies demonstrate that LT phase BaB_2O_4 crystals are formed in the HT phase BaB_2O_4 crystals after femtosecond laser irradiation for 10 s.     

Effect of Chemicals on Chemical Mechanical Polishing of Glass Substrates

We investigate the effect of chemicals on chemical mechanical polishing （CMP） of glass substrates. Ceria slurry in an ultra-low concentration of 0.25 wt. % is used and characterized by scanning electron microscopy. Three typical molecules, i.e. acetic acid, citric acid and sodium acrylic polymer, are adopted to investigate the effect on CMP performance in terms of material removal rate （MRR） and surface quality. The addition of sodium acrylic polymer shows the highest MRR as well as the best surface by atomic force microscopy after CMP, while the addition of citric acid shows the worst performance. These results reveal a mechanism that a long-chain molecule without any branches rather than small molecules and common molecules with ramose abundant-electron groups is better for the dispersion of the slurry and thus better for the CMP process.     

Radiation resistance property of barium gallo-germanate glass doped by Nb2O5

Effects of Nb₂O₅dopant on the radiation response of barium gallo-germanate(BGG)glass are studied mainly by electron paramagnetic resonance and absorption spectroscopy.Owing to the Nb⁵⁺$Nb³⁺interconversion in doped samples,formations of Ge-related non-bridging oxygen hole center and Ge-related electron center defects after g-ray irradiation are inhibited.Thereby,Nb₂O₅dopant can enhance radiation resistance of BGG glass,and 1.0%Nb2O5 concentration is the best.     

Structural modification in swift heavy ion irradiated muscovite mica

Two-layer monoclinic(2 M) muscovite mica sheets with a thickness of 12 μm are irradiated with Sn ions at room temperature with electronic energy loss( dE/dx)_e of 14.7 keV/nm. The ion fluence is varied between 1×10~(11) and1×10~(13) ions/cm~2. Structural transition in irradiated mica is investigated by x-ray diffraction(XRD). The main diffraction peaks shift to the high angles, and the inter-planar distance decreases due to swift heavy ion(SHI) irradiation. Dehydration takes place in mica during SHI irradiation and mica with one-layer monoclinic(1 M) structure is thought to be generated in 2 M mica after SHI irradiation. In addition, micro stress and damage cross section in irradiated mica are analyzed according to XRD data. High resolution transmission electron microscopy(HRTEM) is used on the irradiated mica to obtain the detailed information about the latent tracks and structural modifications directly. The latent track in mica presents an amorphous zone surrounded by strain contrast shell, which is associated with the residual stress in irradiated mica.     

Effect of vacancy defect clusters on the optical property of the aluminium filter used for the space solar telescope

We investigate the microstructures of the pure aluminium foil and filter used on the space solar telescope, irradiated by photons with different doses. The vacancy defect clusters induced by proton irradiation in both samples are characterized by transmission electron microscopy, and the density and the size distribution of vacancy defect clusters are determined. Their transmittances are measured before and after irradiating the samples by protons with energy E=100~keV and dose φ =6× 10¹¹/mm². Our experimental results show that the density and the size of vacancy defect clusters increase with the increase of irradiation doses in the irradiated pure aluminium foils. As irradiation dose increases, vacancies incline to form larger defect clusters. In the irradiated filter, a large number of banded void defects are observed at the agglomerate boundary, which results in the degradation of the optical and mechanical performances of the filter after proton irradiation.     

Structural Change in Au^3＋-Doped BK7 Glass Irradiated by Femtosecond Laser

We report on structural change in an Au^3＋-doped BK7 glass irradiated by an infrared femtosecond laser at 800 nm. A grating structure is inscribed in the glass sample. The glass sample is then annealed at various temperatures. Structural change of the grating is observed by an optical microscope. Absorption spectra indicate that colour centres are induced after the laser irradiation, and they decrease with increasing annealing temperature. Au nanoparticles are precipitated at high temperatures （≥ 600℃）. The mechanisms of the phenomena are discussed.     

Femtosecond Laser Induced Optical Waveguides and Micro—mirrors Inside Glasses

Optical Waveguides and micro-mirrors have been successfully induced inside fused silica glass and k9 glass,respectively,by focusing a 800nm femtosecond(fs)pulsed laser with a repetition rate of 1kHz,The change of refractive index was determined to be 0.001-0.008 in the fused silica glass and 0.006 in the k9 glass.The refractive index change is dependent on both the dose of irradiation and the power density of the fs pulsed laser,Photoluminescence was observed in the irradiated region,and was attributed to the defects induced by fs laser irradiation.We discuss the relationship between the optical property and the luminescent propert property of the irradiated region.     

硼硅酸盐玻璃的电子辐照效应

在高放废物长期地质处置过程中,作为第一层工程屏障的固化体玻璃会受到持续的电子辐照,研究其电子辐照效应对高放废物的长期安全处置具有重要的意义。在透射电子显微镜(TEM)上对硼硅酸盐玻璃样品进行原位电子辐照实验。在电子束的作用下,两种硼硅酸盐玻璃均很快发生相分离现象,这主要是由于电离作用导致Na的迁移或逃逸引起网络体结构重组的结果。引入简单的结构模型解释了两种不同组分硼硅酸盐玻璃相分离的不同,结果表明,相分离的不同与玻璃组分中Na成分的多少密切相关。     

分子动力学模拟钠硼硅酸盐玻璃电子辐照诱导的结构演化效应

钠硼硅酸盐玻璃作为高放射废物玻璃固化体的候选材料之一,已有大量实验对该类玻璃开展了电子或重离子的辐照效应研究.然而,在理论计算与模拟方面的工作却很少,目前主要集中于重离子的辐照效应,对电子的辐照效应的模拟尚未见报道.本文利用分子动力学工具提出一种新的方法,以实现对电子辐照诱导的玻璃结构演化进行模拟.该方法基于实验中玻璃的结构变化特点,即实验中的拉曼结果已经证实:在大剂量的电子辐照后的玻璃中存在分子氧的事实,由于这些分子氧不会与其他粒子发生相互作用,因而可以通过从体系中逐步地移除一定数量氧原子的方式,以达到模拟大剂量电子辐照的情形,进而得到电子辐照后的玻璃的结构信息.模拟结果显示:随着移除氧原子的数量增加,玻璃中的Si—O—Si平均键角逐渐减小;而且玻璃中的小环数量会因氧的逐渐减少而逐渐增加;玻璃中部分[BO4]结构会转变为[BO3]结构,最终这种转变会达到饱和;大量移除氧之后,玻璃中的钠元素也出现明显的相分离.这些模拟辐照的玻璃结构特性能较好地与实验中的硼硅酸盐玻璃电子辐照诱导的结构变化符合.因此,本文提出的方法有望为通过分子动力学模拟硼硅酸盐玻璃的电子辐照效应提供新思路.     

Irradiated rare‐earth‐doped powellite single crystal probed by confocal Raman mapping and transmission electron microscopy

The irradiation‐induced damages and structure modifications of rare earths doped powellite single crystal have been precisely studied using optical and electron microscopy techniques, including optical interferometry, confocal micro‐Raman spectroscopy and transmission electron microscopy. The surface of powellite crystal pops out anisotropically after exposing under Ar ion beam, with a saturation swelling value of 2.0% along a‐axis and 1.3% along the c‐axis of powellite at high dose. Raman mapping on focused ion‐beam sections (5 × 3 µm²) perpendicular to the irradiated surface reveals that irradiation damage induces orientation‐dependent compressive stresses in powellite. However, no significant anisotropic effect has been found on the irradiation‐induced structural disorder in powellite. At low dose (0.012 dpa), the main irradiation‐induced defects created in powellite crystal are small defect clusters. By comparison, the dominant kinds of defects in high‐dose (5.0 dpa) sample are dislocations loops and networks. Copyright © 2014 John Wiley & Sons, Ltd.     

Study of irradiation conditions and thermodynamics of optical glass in the problem of modification of materials by femtosecond laser pulses

The local heating of glass by a focused femtosecond laser pulse and cooling of an irradiated region are numerically modeled. The structural modifications that change the optical properties of glass are assumed to occur within a bulk region whose temperature after irradiation exceeds the glass transition temperature. The shape of the modified region obtained from the calculations coincides with that known from experimental data available. The size of this region is determined by the spatiotemporal dynamics of the laser beam under multiphoton absorption conditions. The heating of glass is maximal in front of a thin lens used for the beam focusing.     

Effects of atomic oxygen irradiation on the surface properties of phenolphthalein poly(ether sulfone)

To study the effects of low earth orbit environment on the surface properties of polymers, phenolphthalein poly(ether sulfone) (PES-C) blocks were irradiated by atomic oxygen in a ground-based simulation system. The surface properties of the pristine and irradiated blocks were studied by attenuated total-reflection FTIR (FTIR-ATR), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM). It was found that atomic oxygen irradiation induced the destruction of PES-C molecular chains, including the scission and oxidation of PES-C molecular chains, as evidenced by FTIR and XPS results. The scission of PES-C molecular chains decreased the relative concentration of C in the surface, while the oxidation increased the relative concentration of O in the surface. The changes in surface chemical structure and composition also changed the surface morphology of the block, which shifted from smooth structure before irradiation to “carpet-like” structure after irradiation.     

强流脉冲电子束辐照诱发纯钼表面的损伤效应及结构缺陷

利用强流脉冲电子束（HCPEB）装置对纯钼表面进行辐照处理,并利用X射线衍射仪,扫描电子显微镜（SEM）、透射电子显微镜（TEM）详细分析了辐照表面的微观结构和损伤效应. 1次HCPEB辐照后,纯钼表层积聚了极大的残余应力,多次辐照后表面未融化区域出现大量绝热剪切带,且局部区域发生开裂. 微观结构分析显示,辐照后材料表面形成发散状的位错组态和大量空位簇缺陷;绝热剪切带内部是尺寸为1 μm 左右等轴状的再结晶晶粒. 剪切带造成的材料表面局部软化以及间隙原子偏聚于晶界是材料发生开裂的主要原因. 另外,表面熔化区域可形成尺寸为20 nm左右的纳米晶. 关键词： 强流脉冲电子束 纯钼 绝热剪切带 空位簇缺陷     

强流脉冲电子束作用下金属锆的微观结构与应力状态

利用强流脉冲电子束 (HCPEB) 技术对金属纯锆进行表面处理, 采用X射线衍射, 扫描电子显微镜及透射电子显微镜详细分析了辐照诱发的表层微观结构和缺陷. X射线分析结果表明, HCPEB辐照后在材料表层诱发幅值为GPa量级的压应力, 并形成{0002}, {1012}, {1120}及{1013}织构. 表层微观结构观察表明, 与其他金属材料不同, HCPEB辐照在材料表层诱发的熔坑数量极少, 多次轰击甚至几乎没有表面熔坑的形成. 此外, 在快速的加热和冷却状态下, 在表面熔化层形成大量的超细晶粒结构, 同时诱发马氏体相变和强烈的塑性变形. 1次HCPEB辐照后表层内形成的变形微结构以位错为主, 孪晶数量较少; 5 次辐照样品的位错密度迅速增高, 孪晶数量也显著增加; 10次辐照后样品中的变形微结构以变形孪晶为主, 且出现二次孪晶现象. 表层晶粒内部变形的晶体学特征不仅决定了表层的织构演化行为, 而且还起到细化晶粒的作用, 为纯锆及锆合金表面强化提供了一条有效的途径. 关键词： 强流脉冲电子束 纯锆 微观结构 应力状态     

Morphological and structural modifications induced in a-Si1−x C x :H films by excimer laser annealing

Hydrogenated amorphous silicon carbon films of different carbon content deposited by plasma enhanced chemical vapour deposition on Corning glass and crystalline silicon substrates have been irradiated by an excimer (KrF) laser. The properties of these samples were investigated by X-ray diffraction, field emission scanning electron microscopy and Fourier transform infrared spectroscopy before and after laser treatment, in order to understand the role of the carbon content as well as the substrate in the structural modifications. It has been demonstrated that the changes induced in the films by the laser treatment are independent of the substrate but depend on the carbon content which facilitates the crystallization process.     

Optical three-dimensional shape analysis of metallic nanoparticles after laser-induced deformation

The 3D shape of Ag nanoparticles in glass irradiated by fs laser pulses is investigated by optical spectroscopy. It is shown that in general spheroids are produced with their symmetry axis oriented along the direction of the linear laser polarization. Depending on the actual irradiation conditions, oblate or prolate spheroids are obtained. The halo of small Ag clusters and Ag ions around the reshaped particles causes a redshift of the surface plasmon resonances via refractive index increase.     

Solid-state NMR characterization of a controlled-pore glass and of the effects of electron irradiation

Controlled-pore glasses (CPGs) are silica-based materials which provide an adequate model system for a better understanding of the radiation chemistry of glasses, especially under nanoscopic confinement. This paper presents a characterization of a nanoporous CPG before and after electron irradiation using multinuclear solid-state magnetic resonance (NMR). 1H MAS NMR has been used for studying the surface proton sites and it is observed that the irradiation leads to a dehydration of the material. Accordingly, concerning the silicon sites near the surface, the observed variation of the Q4, Q3 and Q2 species from 1H-29Si CPMAS spectra shows an increase of the surface polymerization under irradiation, implying in majority a Q2 to Q3/Q4 conversion mechanism. Similarly, 1H-17 O CPMAS measurements exhibit an increase of Si-O-Si groups at the expenses of Si-OH groups. In addition, modifications of the environment of the residual boron atoms are also put in evidence from 11B MAS and MQMAS NMR These data show that MAS NMR methods provide sensitive tools for the characterization of these porous glasses and of the tiny modifications occurring under electron irradiation.