原位液相透射电子显微镜及其在 纳米粒子表征方面的应用

近年来,基于透射电子显微技术、微纳加工技术和薄膜制造技术的发展,原位液相透射电子显微技术产生,为构建多种纳米级分辨率尺度下的微实验平台,发展新型纳米表征技术和众多领域的相关研究提供了途径.本文首先介绍了应用于原位液相透射电子显微技术的液体腔设计要求,然后介绍了液体腔的发展和典型的制备工艺,最后综述了近年来液体腔透射电子显微镜在纳米粒子成核和生长方面的应用研究,并探讨了该技术前沿发展面临的机遇和挑战.本文将为提高我国先进纳米表征技术和原子精准构筑技术提供相关讨论和支持.     

钼酸根离子钝化层对氧化铁薄膜光电催化氧化水的性能影响研究（英文）

本文研究了氧化铁(α-Fe_2O_3)薄膜光阳极的合成及其光电催化分解水产氧的性能.在合成氧化铁过程中,采用原位和非原位方式引入钼酸根离子,调控氧化铁薄膜的生长模式和表面特性.实验发现原位引入钼酸根离子会显著影响氧化铁薄膜的形貌以及厚度.而非原位表面修饰钼酸根离子则会保持氧化铁的纳米棒形貌,并有效提高其光电催化分解水的性能.文章通过紫外-可见吸收光谱,透射电子显微镜(TEM),扫描电子显微镜(SEM),莫特-肖特基测试(M-S),电化学阻抗(EIS)以及光电催化性能测试等手段对材料的结构和性能进行了研究.     

锂离子电池电极材料原子尺度结构表征

材料显微结构与性能之间的关联是材料科学领域的基本问题。球差校正透射电子显微镜的成功问世为表征材料原子尺度精细结构、揭示材料结构和性能的关系提供了重要机遇。文章主要从作者自身的研究工作出发,综述了原子分辨球差校正扫描透射成像技术在研究锂离子电池电极材料不同电化学状态下的表/界面结构及其反应机理方面的应用,探讨了电极材料原子尺度结构与性能之间的内在联系。     

原位表征技术在全固态锂电池中的应用

近年来,可移动消费电子与电动汽车等产业发展迅速,迫切需要发展高能量密度与高安全稳定性的锂电池,以提高这些设备的长续航与长期稳定运行的能力.这使得全固态锂电池极具潜力,并获得迅速发展.然而,高性能全固态锂电池的发展需要对其充放电机制与性能衰减机理等有深入的认识,对电池内部及界面的微观结构、物相组成、化学成分及局域化学环境等动态演变规律有系统深入的理解.基于此,本文总结归纳了典型原位表征技术,包括原位显微技术(原位扫描电子显微镜(SEM),原位透射电子显微镜(TEM))、原位X射线技术(原位X射线衍射(XRD)、原位X射线光电子能谱(XPS)、原位近边结构X射线吸收光谱(XANES)、原位X射线层析成像等)、原位中子技术(原位中子衍射(ND)、原位中子深度剖析(NDP))以及原位波谱技术(原位拉曼光谱、原位核磁共振(NMR)与原位核磁共振成像(MRI))等的基本原理、功能、及其应用于研究固态锂电池中电极材料与界面在服役状态下、真实电化学过程中的动态过程与失效机制的代表性研究进展,并对未来先进原位表征技术在全固态锂电池研究中的应用进行了探讨和展望.     

钼酸根离子钝化层对氧化铁薄膜光电催化氧化水的性能影响研究

本文研究了氧化铁(α-Fe₂O₃)薄膜光阳极的合成及其光电催化分解水产氧的性能. 在合成氧化铁过程中,采用原位和非原位方式引入钼酸根离子,调控氧化铁薄膜的生长模式和表面特性. 实验发现原位引入钼酸根离子会显著影响氧化铁薄膜的形貌以及厚度. 而非原位表面修饰钼酸根离子则会保持氧化铁的纳米棒形貌,并有效提高其光电催化分解水的性能. 文章通过紫外-可见吸收光谱,透射电子显微镜(TEM),扫描电子显微镜(SEM),莫特-肖特基测试(M-S),电化学阻抗(EIS)以及光电催化性能测试等手段对材料的结构和性能进行了研究.     

二维原子晶体的低电压扫描透射电子显微学研究

二维原子晶体材料,如石墨烯和过渡金属硫族化合物等,具有不同于其块体的独特性能,有望在二维半导体器件中得到广泛应用.晶体中的结构缺陷对材料的物理化学性能有直接的影响,因此研究结构缺陷和局域物性之间的关联是当前二维原子晶体研究中的重要内容,需要高空间分辨率的结构研究手段.由于绝大部分二维原子晶体在高能量高剂量的电子束辐照下容易发生结构损伤,利用电子显微方法对二维原子晶体缺陷的研究面临诸多挑战.低电压球差校正扫描透射电子显微(STEM)技术的发展,一个主要目标就是希望在不损伤结构的前提下对二维原子晶体的本征结构缺陷进行研究.在STEM下,多种不同的信号能够被同步采集,包括原子序数衬度高分辨像和电子能量损失谱等,是表征二维原子晶体缺陷的有力工具,不但能对材料的本征结构进行单原子尺度的成像和能谱分析,还能记录材料结构的动态变化.通过调节电子束加速电压和电子辐照剂量,扫描透射电子显微镜也可以作为电子刻蚀二维原子晶体材料的平台,用于加工新型纳米结构以及探索新型二维原子晶体的原位制备.本综述主要以本课题组在石墨烯和二维过渡金属硫族化合物体系的研究为例,介绍低电压扫描透射电子显微学在二维原子晶体材料研究中的实际应用.     

醇体系中合成CuGaS2纳米晶及其形貌演变

以CuCl2·2H2O,自制的GaCl3和(NH2)2CS为原料,在乙二醇体系中合成了花状结构的CuGaS2纳米晶．产物分别用X射线粉末衍射仪、透射电子显微镜、场发射扫描电子显微镜、高分辩透射电子显微镜和X射线光电子能谱仪进行了表征．实验结果表明,220℃反应24 h得到均匀的花状纳米结构CuGaS2,它是由厚度80-100 nm的片晶组成．同时,通过反应时间的控制,可以清楚的看到由纳米颗粒到纳米球以及花状纳米结构的演变过程．另外,研究了反应温度、反应时间、溶剂等对产物和形貌的影响．此外,对花状结构纳米晶的生长机理进行了初步的探讨．室温荧光光谱表明,随粒径的降低,发光位发生了部分蓝移．     

催化剂对类石墨烯纳米片结构和发光性能的影响

利用热丝化学气相沉积在沉积有碳点和金催化剂层的Si衬底上制备了类石墨烯纳米片。分别用扫描电子显微镜、透射电子显微镜、显微Raman光谱仪、傅立叶变换红外光谱仪、X光电子谱仪和Ramalog系统对它的结构、组成和发光性能进行了研究。结果表明碳点和金引起了类石墨烯纳米片厚度和缺陷的变化,进而导致了发光带的漂移和发光强度的改变。根据表征结果,分析了类石墨烯纳米片结构的变化引起发光性能改变的原因。     

电子辐照诱发固态相变导致的氮化硼纳米结构生长

报道了N+离子轰击产生的氮化硼(BN)纳米结构,及在电子辐照时结构演化的高分辨透射电子显微镜的原位测定结果.应当强调的是,这种类富勒烯和发夹结构的演化,实际上是电子辐照诱发固态相变的发展,观察中发现的一些BN颗粒、卷曲物,可以被认为是类富勒烯等纳米结构形成的前体或早期阶段.提出了一种类富勒烯等结构的电子辐照动力学模型,并进行了讨论. 关键词： 氮化硼 电子辐照 透射电子显微镜 氮化硼纳米形成物     

Yb/TiO_2/杭锦2~#土的制备及其光催化降解苯的原位红外研究

实验以杭锦2~#土为原料,制备了TiO_2/杭锦2~#土,并在其上添加稀土金属镱作为Yb/TiO_2/杭锦2~#土催化剂,通过X射线粉末衍射(XRD)、透射电子显微镜分析(TEM)、比表面(BET)等对催化剂结构进行了表征,并以苯为目标降解物使用原位红外光谱在不同温度,光源下催化剂催化降解苯的性能进行了研究。     

Experimental set up for in situ transmission electron microscopy observations of chemical processes

Recently, the applications of transmission electron microscopy (TEM) related techniques have extended from ex situ nanoscale characterization of structure and chemistry of products to dynamic measurements of nanostructures during reaction processes. Commercially available modified TEM specimen holders and TEM columns are being routinely employed to follow the structural and chemical changes at elevated temperatures and even under controlled atmosphere. Experiments performed under these rigorous conditions require careful considerations to avoid undesirable effects from the gas impurities or contaminations from TEM grids and/or holders. The reactivity of sample, grid, holder, TEM components, and gaseous environments must be evaluated for each reaction process. This tutorial is aimed to outline some of the important factors that should be considered for experimental set up used for in situ observations to ensure the results are comparable to the ones obtained during ex situ experiments under identical conditions.     

Formation of amorphous sapphire by a femtosecond laser pulse induced micro-explosion

We report on structural characterization of void-structures created by a micro-explosion at the locus of a tightly focused femtosecond laser pulse inside the crystalline phase of Al₂O₃ (R3c space group). The transmission electron microscopy (TEM), micro-X-ray diffraction (XRD) analysis, and Raman scattering revealed a presence of strongly structurally modified amorphous regions around the void-structures. We discuss issues of achieving the required resolution for structural characterization and assignment of newly formed phases of nano-crystallites by TEM, XRD, and Raman scattering from micro-volumes of modified materials enclosed inside the bulk of the host phase.     

Linking chiral indices and transport properties of double-walled carbon nanotubes

We performed in situ transport measurements in a transmission-electron microscope (TEM) on individual double-walled carbon nanotubes (DWNT). Using selected-area electron diffraction, the chiral indices of the two tubes constituting the DWNTs were determined through careful comparison with theory. We discuss the case of a DWNT whose two tubes have a gap at half filling and show a finite density of delocalized state at the Fermi level. The exact determination of chiral indices should be reachable in any transport-measurement experiment with samples that allow TEM characterization.     

In situ growth of CdSe/CdS quantum dots inside and outside of MWCNTs

The CdSe/CdS quantum dots were grown in situ inside and outside of the multiwalled carbon nanotubes in an innocuous solvent and at a lower temperature. The CdSe/CdS-CNTs nanoheterostructures were characterized by TEM, HRTEM, EDS, XPS and PL. The CdSe/CdS nanocrystals with diameters about 5 nm exhibit an improved PL emission.     

Field emission scanning electron microscopy (FE-SEM) as an approach for nanoparticle detection inside cells

When developing new nanoparticles for bio-applications, it is important to fully characterize the nanoparticle's behavior in biological systems. The most common techniques employed for mapping nanoparticles inside cells include transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). These techniques entail passing an electron beam through a thin specimen. STEM or TEM imaging is often used for the detection of nanoparticles inside cellular organelles. However, lengthy sample preparation is required (i.e., fixation, dehydration, drying, resin embedding, and cutting). In the present work, a new matrix (FTO glass) for biological samples was used and characterized by field emission scanning electron microscopy (FE-SEM) to generate images comparable to those obtained by TEM. Using FE-SEM, nanoparticle images were acquired inside endo/lysosomes without disruption of the cellular shape. Furthermore, the initial steps of nanoparticle incorporation into the cells were captured. In addition, the conductive FTO glass endowed the sample with high stability under the required accelerating voltage. Owing to these features of the sample, further analyses could be performed (material contrast and energy-dispersive X-ray spectroscopy (EDS)), which confirmed the presence of nanoparticles inside the cells. The results showed that FE-SEM can enable detailed characterization of nanoparticles in endosomes without the need for contrast staining or metal coating of the sample. Images showing the intracellular distribution of nanoparticles together with cellular morphology can give important information on the biocompatibility and demonstrate the potential of nanoparticle utilization in medicine.     

Experimental and theoretical investigations of absorbance spectra for edge-plasma monitoring in fusion reactors

This present paper deals with the spectral characterization of dusty plasmas such as those produced during ITER fusion experiments. Such plasma formed in a small radio frequency plasma reactor with acetylene was characterized using in situ Fourier transform infrared (FTIR) absorption spectroscopy and laser scattering, and ex situ transmission electron microscopy (TEM). The plasma absorbance spectra thus obtained in the visible and infrared wavelengths exhibit special features associated with the dust particle growth which absorbs and scatters IR light. This experimental absorbance behavior is reproduced using a dedicated radiation modeling based on the Mie theory and the Monte Carlo simulation. The bimodal distribution assumed for particle sizes brings the model-determined optical properties closer to the experimental dust absorbance than the normal and uniform distributions. Dust formation mechanism is further discussed comparing the experimental and simulated absorbance.     

Synthesis and structural characterization of nanostructured copper

In this paper, we report on the preparation and characterization of nanocrystalline powder of copper by dc-magnetron sputtering. Liquid nitrogen cooled cold finger arrangement has been used to prepare nanocrystalline powder. The particle size, crystal structure, and morphology of the samples were characterized by in situ high temperature X-ray diffraction (XRD) and transmission electron microscope (TEM). Results of high temperature XRD showed that highly oriented (111) phase becomes randomly oriented at higher temperature with a systematic shift in peak positions toward lower 2θ values due to changes in lattice parameters. Temperature dependence of lattice constants under vacuum shows linear increase in their values. Diffraction patterns obtained from TEM are also in accordance with the XRD data.     

Temperature effect on the Cu2O oxide morphology created by oxidation of Cu(0 0 1) as investigated by in situ UHV TEM

The temperature effect on the Cu₂O oxide morphology was investigated by oxidizing Cu(1 0 0) thin films at the temperature ranging from 150 to 1000 °C and constant oxygen partial pressure of 5×10⁻⁴ Torr. The evolution of the oxide island size and shape was followed inside an in situ ultrahigh vacuum transmission electron microscope (UHV TEM). Of particular interest, we find that the oxide morphology can be triangular, hut, rod or pyramid shaped depending only on the oxidation temperature.     

Unveiling metal-cage hybrid states in a single endohedral metallofullerene

The local structural and electronic properties of individual metallofullerenes are studied using scanning tunneling microscopy, scanning tunneling spectroscopy, and theoretical simulations. The energy-resolved metal-cage hybrid states of a single endohedral metallofullerene Dy@C82 isomer I have been spatially mapped, supporting a complex picture consisting of the orbital hybridization and charge transfer for the interaction between the cage and the metal atom. The relative position of the encapsulated Dy atom inside the cage and the molecular orientation on the surface have been inferred by comparing the experimental results with theoretical simulations. The combined technique provides promising applications in the fields of in situ characterization and diagnostics of metallofullerene-based nanodevices.     

Dynamic all-optical tuning of transverse resonant cavity modes in photonic bandgap fibers

Photonic bandgap fibers for transverse illumination containing half-wavelength microcavities have recently been designed and fabricated. We report on the fabrication and characterization of an all-optical tunable microcavity fiber. The fiber is made by incorporating a photorefractive material inside a Fabry-Perot cavity structure with a quality factor Q >200 operating at 1.5 microm. Under short-wavelength transverse external illumination, a 2 nm reversible shift of the cavity resonant mode is achieved. Dynamic all-optical tuning is reported at frequencies up to 400 Hz. Experimental results are compared with simulations based on the amplitude and kinetics of the transient photodarkening effect measured in situ in thin films.