原位动态电子显微学研究进展

随着电镜内原位技术的不断成熟和发展,透射电子显微镜不再仅仅是材料结构表征的工具,还是实现高精度纳米加工、性能测试等的重要手段。这不但丰富了纳米尺度下开展实验研究的方法,也拓宽了透射电子显微镜的应用范围,为纳米科学与技术的迅速发展提供了新的契机。本文侧重作者所在研究小组的研究工作,以"将纳米实验室建在透射电子显微镜里"的构想为主线,从材料的原位生长、结构加工、性能表征和器件构建等四个方面综述了近年来基于透射电子显微镜的代表性原位实验研究进展。     

原位透射电子显微学进展及应用

文章简要介绍了近年来原位透射电子显微学的进展,并指出,原位透射电子显微技术的发展使得在纳米、原子层次观察样品在力、热、电、磁作用下以及化学反应过程中的微结构演化成为可能。通过研究物质在外界环境作用下的微结构演化规律,揭示其原子结构与物理化学性质的相关性,指导其设计合成和微结构调控,促进新物质的探索和深层次物质结构研究,为解决凝聚态物理学中的具体问题提供了直接、准确和详细的方法。     

用于Raman光谱与微纳米结构同步检测的Raman-AFM系统研究

研究和发展了一种将微区拉曼(Raman)光谱检测与原子力显微镜(AFM)微纳米扫描成像相结合的新型Raman-AFM技术。设计了Raman光谱与AFM扫描成像的原位检测探头;研制出相应的Raman-AFM系统;利用该系统,对ZnO纳米颗粒和TiO2纳米薄膜开展了微区Raman光谱与微纳米结构的检测实验。研究表明,所获得的Raman光谱检测结果与理论值良好吻合,同时,AFM扫描检测得到的图像很好地表征了样品的微纳米结构,从而实现了微区Raman光谱与AFM图像的原位及同步检测,验证了这一技术的可行性,为Raman光谱技术与微纳米技术领域的实际应用提供了技术基础。     

现代透射电子显微技术在多铁材料研究中的应用

文章简要介绍了材料科学研究中被广泛应用的透射电子显微(TEM)技术及其在多铁材料研究中的应用,并给出了几个典型案例:利用球差矫正原子分辨扫描透射电子显微术(STEM),并和电子能量损失谱(EELS)相结合,分析多铁异质结界面处的原子分布、离子价态和化学键的变化;结合球差矫正原子分辨透射电子显微图像(HRTEM)和STEM图像,分析多铁材料中的局域对称性破缺和电极化特性;利用原位变温及电/磁场加载技术,研究多铁材料中的结构相变和电畴/磁畴的动态演变特性。文章特别指出,现代透射电子显微学是全面分析理解多铁材料局域微结构,探讨多铁耦合机制及其物理根源的有效手段。     

纳米材料的同步辐射研究

近年来,科学家们在纳米材料的生长及应用研究等诸多方面取得了巨大的进展.然而,由于受到表征手段的限制,纳米科技领域的许多关键科学问题至今仍未得到清楚的解答.同步辐射具有多种独特优点,随着国内第三代同步辐射光源的逐步发展,基于同步辐射的各种实验技术将为实时、原位、动态地表征纳米结构提供功能强大的研究平台.文章简单介绍了基于同步辐射的一些新型纳米结构表征技术,并根据作者的研究举例说明了同步辐射技术在纳米材料研究方面的一些优势.     

纳米材料及HfO_2基存储器件的原位电子显微学研究

总结了我们将原位技术和透射电子显微学分析方法相结合,针对纳米材料和器件的结构、形貌、成分以及电势分布等物理性质的动态行为所开展的综合物性表征和分析工作.主要成果有:揭示了C_(60)纳米晶须在焦耳热作用下的结构相变路径;观察到了电荷俘获存储器中的电荷存储位置以及栅极电压诱导的氧空位缺陷;研究了阻变存储器中氧空位通道的形成过程以及导电通道的开关机理.这些成果不但有助于深入理解纳米材料和器件相关功能的物理机理,改善其工作性能,更展示了透射电子显微学在微电子领域强大的研究能力.     

金属铁纳米粒子的液相制备表面修饰及其结构表征

报道在知性剂存大的条件下于乙醇／水的简单液相体系中以ＫＢＨ４还原制备金属铁纳米粒子,然后再用含镍盐修饰溶液进行原位粒子的表面修饰,并通过Ｘ射线衍射（ＸＲＤ）、光电子能谱分析（ＸＰＳ）、透射电子显微分析（ＴＥＭ）、选区电子衍射（ＥＤ）表征和讨论所得产物粒子的形貌结构特征和粒子大小。结果表明,初始生成的金属铁纳米粒子与修饰溶液的电化学反应形成以金属纳米铁核为中心的具有较好稳定性的多层复合结构。     

基于聚焦离子束纳米剪纸/折纸形变的三维微纳制造技术及其光学应用

高精度的三维微纳制造技术是现代光电子学和微纳光子学发展的重要基础之一,是实现下一代微纳光子集成器件的重要前提.纳米尺度的剪纸和折纸技术由于能够实现丰富的三维形变,正发展成为一门新兴的研究领域.本文系统地介绍了一种新型的片上三维微纳加工方法—基于聚焦离子束的纳米剪纸/折纸技术.该技术利用聚焦离子束辐照具有不同拓扑形貌的自支撑膜片,可实现优于50 nm精度、前所未见的三维形状变换,包括片上、实时的多向折叠、弯曲、扭曲等形变.提出了"树型"纳米剪纸和"闭环"纳米剪纸两种类型的加工方法,并针对不同类型的工艺特性和优缺点进行分析对比.利用全局扫描纳米剪纸技术制备的闭环纳米结构实现了独特的光学效应,包括超光学手性、超构表面衍射、相位和偏振调控以及光子自旋霍尔效应等.研究结果表明,纳米剪纸/折纸形变技术在保持结构复杂性和功能性的同时,可实现高精度、原位、片上、一步成型的三维微纳加工,可望为三维微纳光子器件的设计、制备和应用提供一类新的设计方法和技术途径,乃至为相关微纳光学、微电子、微机电系统、生物医学等领域的发展提供新颖的加工平台.     

室温离子液体中超声辐照制备氧化锌纳米棒的研究

离子液体与超声技术结合在纳米材料的制备中具有广阔的前景,但目前以离子液体为溶剂超声制备纳米材料的报道还不多见,相关的反应机理研究也亟待开展.本文首次在室温离子液体1-丁基-3-甲基咪唑四氟硼酸盐中超声制备了氧化锌纳米棒,该方法具有简便、快速和环境友好等特点.采用X射线衍射(XRD)、透射电子显微镜(TEM)对纳米氧化锌的结构和形貌进行表征.作为比较研究,采用传统的低蒸汽压有机溶剂二缩三乙二醇在同样的超声反应条件制备了纳米氧化锌材料.离子液体中超声合成样品为直径约20 nm,长度30-50 nm的纳米棒,而在二缩三乙二醇中超声制备的样品为直径6～8 nm的纳米颗粒.利用光声光谱(PAS)研究了纳米氧化锌样品的光学性能和量子尺寸效应.对离子液体中超声制备氧化锌纳米棒可能的反应机理进行了讨论并建立了的反应模型.结果表明在在超声辐照和离子液体溶剂的共同作用下氧化锌纳米棒得以生成.     

水溶液中PbS纳米晶生长过程的原位光谱检测

为了研究纳米晶在溶液中的生长规律,设计并实现了一个能够实时监测纳米晶生长的原位透射光谱系统。利用该系统对PbS纳米线和纳米点在水相中生长过程进行了原位光谱检测,发现十二烷基硫酸钠对PbS纳米晶的定向生长起了非常重要的作用。     

Imaging the Hydrated Microbe‐Metal Interface Using Nanoscale Spectrum Imaging

PdAu nanocrystals are synthesised by Geobacter sulfurreducens, a dissimilatory metal‐reducing bacterium, and the resulting bimetallic nanocrystal‐decorated microbes are imaged using a range of advanced electron microscopy techniques. Specifically, the first example of elemental mapping of fully hydrated biological nanostructures using scanning transmission electron microscope (STEM) energy dispersive X‐ray (EDX) spectrum imaging within an environmental liquid‐cell is reported. These results are combined with cryo‐TEM and ex situ STEM imaging and EDX analysis with the aim of better understanding microbial synthesis of bimetallic nanoparticles. It is demonstrated that although Au and Pd are colocalized across the cells, the population of nanoparticles produced is bimodal, containing ultrasmall alloyed nanocrystals with diameters <3 nm and significantly larger core‐shell structures (>200 nm in diameter) which show higher Pd contents and exhibit a Pd enriched shell only a few nanometers thick. The application of high‐resolution imaging techniques described here offers the potential to visualize the microbe‐metal interface during the bioproduction of a range of functional materials by microbial “green” synthesis routes, and also key interfaces underpinning globally relevant environmental processes (e.g., metal cycling).     

Effect of Pt and Fe catalysts in the transformation of carbon black into carbon nanotubes

In this research carbon nanotubes and carbon nano onion-like structures were synthesized from carbon black using metal catalysts at 400 °C and 700 °C. Platinum and iron-group metals were used as catalysts for the transformation of CB into graphitized nanocarbon and the effect of both metals was compared. The synthesized products were characterized using X-ray diffraction (XRD), transmission electron microscope (TEM), high resolution transmission electron microscope (HRTEM) and Raman spectroscopy. The characterization shows that this process is very efficient in the synthesis of high quality graphitized products from amorphous carbon black, even though the process temperature was relatively low in comparison with previous studies. Distinguished graphitic walls of the newly formed carbon nanostructures were clearly visible in the HRTEM images. Possible growth difference related to the type of catalyst used is briefly explained with the basis of electron vacancies in d-orbitals of metals.     

Multiscale characterization of dislocation processes in Al 5754

Multiscale characterization was performed on an Al–Mg alloy, Al 5754 O-temper, including in situ mechanical deformation in both the scanning electron microscope and the transmission electron microscope. Scanning electron microscopy characterization showed corresponding inhomogeneity in the dislocation and Mg distribution, with higher levels of Mg correlating with elevated levels of dislocation density. At the nanoscale, in situ transmission electron microscopy straining experiments showed that dislocation propagation through the Al matrix is characterized by frequent interactions with obstacles smaller than the imaging resolution that resulted in the formation of dislocation debris in the form of dislocation loops. Post-mortem chemical characterization and comparison to dislocation loop behaviour in an Al–Cr alloy suggests that these obstacles are small Mg clusters. Previous theoretical work and indirect experimental evidence have suggested that these Mg nanoclusters are important factors contributing to strain instabilities in Al–Mg alloys. This study provides direct experimental characterization of the interaction of glissile dislocations with these nanoclusters and the stress needed for dislocations to overcome them.     

In situ synthesis of Cu2O nano/microstructures on a copper substrate assisted with mixed cationic/anionic surfactants

Different morphologies of Cu₂O nano/microstructures have been successfully prepared on copper foil via a mild hydrothermal process in the presence of mixed cationic/anionic surfactants, by using copper foil to serve as both copper source and substrate. The reaction system of mixed cationic/anionic surfactants and the reaction temperature play key roles in the formation of different morphologies of Cu₂O nano/microstructures. X-ray diffraction (XRD), field emission scanning electron microscope (SEM), transmission electron microscope (TEM), selected area electron diffraction (SAED) and room temperature photoluminescence (PL) spectra are used to characterize the as-obtained products. The PL results confirmed that the Cu₂O structures exhibited good optical properties. A reasonable formation mechanism was proposed based on the experimental results.     

Nanocomposite ZnO/Au formation by pulsed laser irradiation

The ZnO/Au nanocomposite formation involves synthesis of Au and ZnO colloidal solutions by 532 nm pulse laser ablation of metal targets in deionized water followed by laser irradiation of the mixed colloidal solution. The transmission electron microscope (TEM) and high-resolution transmission electron microscope (HRTEM) images show evolution of spherical particles into ZnO/Au nanonetworks with irradiation time. The formation mechanism of the nanonetwork can be explained on the basis of near resonance absorption of 532 nm irradiation by gold nanoparticles which can cause selective melting and fusion of gold nanoparticles to form network. The ZnO/Au nanocomposites show blue shift in the ZnO exciton absorption and red shift in the Au plasmon resonance absorption due to interfacial charge transfer.     

High‐temperature stability of suspended single‐layer graphene

We report in situ Joule heating on suspended single‐layer graphene in a transmission electron microscope (TEM). Thermally‐driven degradation of pre‐deposited nanoparticles on the membrane is monitored and used for local temperature estimation. By extrapolating the Joule heating power and temperature relation, we find that the suspended single‐layer graphene has exceptional thermal stability up to at least 2600 K. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nanoscale Imaging and Stabilization of Silica Nanospheres in Liquid Phase Transmission Electron Microscopy

Liquid phase transmission electron microscopy (LP‐TEM) is a novel and highly promising technique for the in situ study of important nanoscale processes, in particular the synthesis and modification of various nanostructures in a liquid. Destabilization of the samples, including reduction, oxidation, or dissolution by interactions between electron beam, liquid, and sample, is still one of the main challenges of this technique. This work focuses on amorphous silica nanospheres and the phenomena behind their reshaping and dissolution in LP‐TEM. It is proposed that silica degradation is primarily the result of reducing radical formation in the liquid phase and the subsequent accelerated hydroxylation of the silica, while alterations in silica solid structure, pH, and oxidizing species formation had limited influence. Furthermore, the presence of water vapor instead of liquid water also results in degradation of silica. Most importantly however, it is shown that the addition of scavengers for reducing radicals significantly improved amorphous silica stability during LP‐TEM imaging. Devising such methods to overcome adverse effects in LP‐TEM is of the utmost importance for further development and implementation of this technique in studies of nanoscale processes in liquid.     

高质量大面积石墨烯的化学气相沉积制备方法研究

石墨烯因其奇特的能带结构和优异的物理性能而成为近年来大家研究的热点, 但是目前单层石墨烯的质量与尺寸制约了其实际应用的发展. 本文采用常压化学气相沉积(CVD)方法, 基于铜箔衬底, 利用甲烷作为碳源制备了高质量大面积的单层与多层石墨烯. 研究发现: 高温度、稀薄的甲烷浓度、较短的生长时间以及合适的气体流速是制备高质量、大面积石墨烯的关键. Raman光谱, 扫描电子显微镜、透射电子显微镜等表征结果表明: 制备的石墨烯主要为单层, 仅铜箔晶界处有少量多层石墨烯. 电学测试表明CVD制备的石墨烯在低温时呈现出较明显的类半导体特性; 薄膜电阻随外界磁场的增大而减小.     

In Situ Transmission Electron Microscopy Observation of Melted Germanium Encapsulated in Multilayer Graphene

Germanene is a two-dimensional germanium (Ge) analogous of graphene, and its unique topological properties are expected to make it a material for next-generation electronics. However, no germanene electronic devices have yet been reported. One of the reasons for this is that germanene is easily oxidized in air due to its lack of chemical stability. Therefore, growing germanene at solid interfaces where it is not oxidized is one of the key steps for realizing electronic devices based on germanene. In this study, the behavior of Ge at the solid interface at high temperatures is observed by transmission electron microscopy (TEM). To achieve such in situ heating TEM observation, this work fabricates a graphene/Ge/graphene encapsulated structure. In situ heating TEM experiments reveal that Ge like droplets move and coalesce with other Ge droplets, indicating that Ge remains as a liquid phase between graphene layers at temperatures higher than the Ge melting point. It is also observed that Ge droplets incorporate the surrounding amorphous Ge as Ge nuclei, thereby increasing its size (domain growth). These results indicate that Ge crystals can be grown at the interface of van der Waals materials, which will be important for future germanene growth at solid interfaces.