Quantitative High Resolution Electron Microscopy

 With the resolution becoming sufficient to reveal individual atoms, HREM is now entering the stage where it can compete with X-ray methods to quantitatively determine atomic structures of materials without much prior knowledge, but with the advantage of being applicable to aperiodic objects such as crystal defects. In our view the future electron microscope will be characterised by a large versatility in experimental settings under computer control such as the illumination conditions (TEM-STEM), CBED, detecting conditions (diffraction, image, ptychography) and many other tunable parameters such as focus (g), voltage, spherical aberration (C _s ), beam tilt, etc. Since modern detectors can detect single electrons, also the counting statistics is known. The only limiting factor in the experiment will be the total number of electrons that interact with the object during the experiment due to the limitations in the exposure time or in the object damage. However, instrumental potentialities will never be exploited fully if not guided by an experimental strategy. Here intuitive guidelines can be very deceptive. For instance an image made with the best electron microscope (C _s  = 0) at the best focus (g = 0) from the best object (phase object) would show no contrast at all. Hence, questions such as what is the best C _s , focus, object thickness, etc. can only be answered properly if done using a method of experiment design.     

Orientation Imaging in Scanning Electron and Transmission Electron Microscopy for Characterization of the Shear Banding Phenomenon

The texture evolution during deformation of high purity fcc single crystals with initial (112) [11 ] orientation has been characterised in detail by transmission (TEM) and scanning (SEM–FEG) electron microscopes. The channel-die deformed samples up to reduction of about 1–1.5, first developing strongly anisotropic layers of elongated cells or twin-matrix plates and then compact clusters of SB. Substantial progress in understanding the mechanism of the SB formation was possible thanks to systematic local orientation measurements (orientation mapping) using SEM and TEM. These two techniques of local orientation measurements have been compared with respect to their applicability for the study of shear banding phenomenon and for characterization of the specific nanostructure of SB in metals with fcc lattice. It was shown that well-developed SB exhibit large orientation spreads up to 35–40° with respect to the adjacent areas outside the band. Most of these misorientations occur by rotations about the TD‖〈110〉 axis with significant further rotations about 〈112〉 poles. This ultimately leads to the formation of the texture components whose occurrence cannot be explained by models homogeneous deformation.     

低电压扫描电子显微术

低电压扫描电子显微术是研究半导体、绝缘体和生物材料的有效方法。本文综述了这种方法的优点、限制和关于扫描电镜的改进,并且提供了实际操作的某些要领。     

Imaging and Microanalysis in Environmental Scanning Electron Microscopy

A variety of gas cascade amplification and signal detection strategies have evolved for use in low vacuum and environmental scanning electron microscopy on poorly conducting specimens. These detectors have been optimized to perform well under various limitations on the range of gas pressure and working distance which may be imposed by experimental requirements. All of the detectors must produce high gains, low backgrounds, and generate a sufficient positive ion flux to the specimen to enable charge neutralization. The underlying principles of operation of each detector type are discussed, along with the range of experimental conditions appropriate to each.     

Studying Ice with Environmental Scanning Electron Microscopy

Scanning electron microscopy (SEM) is a powerful imaging technique able to obtain astonishing images of the micro- and the nano-world. Unfortunately, the technique has been limited to vacuum conditions for many years. In the last decades, the ability to introduce water vapor into the SEM chamber and still collect the electrons by the detector, combined with the temperature control of the sample, has enabled the study of ice at nanoscale. Astounding images of hexagonal ice crystals suddenly became real. Since these first images were produced, several studies have been focusing their interest on using SEM to study ice nucleation, morphology, thaw, etc. In this paper, we want to review the different investigations devoted to this goal that have been conducted in recent years in the literature and the kind of information, beyond images, that was obtained. We focus our attention on studies trying to clarify the mechanisms of ice nucleation and those devoted to the study of ice dynamics. We also discuss these findings to elucidate the present and future of SEM applied to this field.     

扫描电镜中背散射电子成像功能的应用

简单介绍了扫描电镜背散射电子成像的工作原理及其应用.利用扫描电镜背散射电子成像结合X-射线能谱来研究样品的微区成分变化,从而快速的了解样品的组成和结构特征,为物相的鉴别提供了有效的分析手段.     

四维扫描透射电子显微镜技术：从材料微观结构到物性分析

扫描透射电子显微镜(Scanning transmission electron microscopy,STEM)目前已经达到了原子级分辨率,并且由于其具有灵活的多通道成像能力以及强大的与谱学分析相结合的特点,因此在材料科学、生命科学等领域展现出强大的微尺度表征能力。但传统STEM的探测器受单像素积分式探测机制的限制,使其只能收集特定角度的散射电子,这导致不仅丢失了散射电子的角分辨信息,还降低了入射电子的剂量效率,因此迫切需要发展全新成像技术来实现高通量、高电子剂量效率成像。近年来,电子探测技术和分区或像素化探测器的研发联合计算机运算、存储能力的大幅提高,推动了四维扫描透射电子显微镜技术(Four-dimensional scanning transmission electron microscopy,4D-STEM)的蓬勃发展,并为最大化、最高效挖掘散射电子信息带来希望。在采集4D-STEM数据时,会聚电子束在样品平面上进行二维扫描,与此同时使用一块具有高帧速、高动态范围以及高信噪比的像素化阵列式探测器在远场收集二维的衍射数据。因为这些衍射数据是角度解析的,所以既可以用来进行常规的...     

Evaluation of Morphology and Deformation Micromechanisms in Multilayered PP/PS Films: An Electron Microscopy Study

Nanostructured polymers and ultra-thin polymer layers are used more and more in technical applications like nanotechnology and microelectronics. Therefore, it is really important to understand the size-scale dependent properties as bulk polymers become thinner and more two-dimensional. Here the morphology as well as the macroscopic and the microscopic deformation behaviour of multilayered films of polypropylene (PP) and polystyrene (PS) have been investigated. For investigation different microscopic techniques and tensile testing were used. The films were prepared by multilayer coextrusion, whereas the composition of PP and PS and the film thickness – and therefore the thickness of each layer – varied. The thinnest calculated thickness of a single layer was about 5 nm. It is shown that the PP/PS films consist usually of homogeneous layers with only few defects. As the composition of PP/PS deviates strongly from 50/50 or the films get thinner the number of defects increases and the layered system turns to irregular lamellar system. In macroscopic tensile tests the small PS layers affect the elongation at break enormously: Most of the samples are brittle. For the films with a composition of PP/PS 90/10 and the film PP/PS 70/30 with a film thickness of 25 µm an elongation at break of 66% and higher could be reached. Transmission electron microscopy on these samples shows that the layers are characterized by plastic yielding in local deformation zones.     

Development of In Situ Electrochemical Scanning Electron Microscopy with Ionic Liquids as Electrolytes

We report that ionic liquids (ILs) can be observed by electron microscopy without any charging of the liquid. Based on this, we present an in situ electrochemical scanning electron microscopy (in situ ECSEM) system. The key technology that enables in situ ECSEM is that charges can be removed from an IL by grounding it with a Pt wire, even if the IL is in an insulating glass cell. As a first demonstration, we describe the redox reaction of a polypyrrole (PPy) film accompanied by changes in its thickness when it is polarized by the film‐deposited Pt electrode in the IL. Furthermore, energy‐dispersive X‐ray fluorescence (EDX) analysis can be employed for the electrode polarized in the IL. The component analysis by EDX of PPy in an IL containing K⁺ as a marker, reveals doping of electrolyte cations into the PPy film upon the latter′s reduction and dedoping of cations from the film upon oxidation.     

失活加氢精制催化剂中硫铁相的高分辨透射电镜研究

利用高分辨透射电镜(HRTEM)结合X射线能谱仪(EDS)和选区电子衍射(SAED)分析,对运转后的加氢精制催化剂中含有的微量未知相的化学组成、晶体结构进行了研究.通过X射线能谱仪确定该未知相主要成分为硫和铁.根据选区电子衍射结果,该硫铁相为单晶结构.采用样品倾转的方法,获得3幅不同取向的选区电子衍射图,根据衍射谱中衍射斑点对应的晶体学信息及3幅电子衍射图取向间的夹角关系,确定该硫铁化合物属于正交晶系的硫化亚铁,分子式为Fe0.91S.该催化剂应用于高温高压下的加氢环境中,其中原料油中的酸性物质,尤其是环烷酸对加氢设备材质的腐蚀是导致硫铁化合物相形成的主要原因,并由此探讨了硫铁化合物相的形成机制.     

珍珠形胆结石的红外光谱和扫描电镜分析

磁疗获得的珍珠形胆结石是罕见的病例,作者利用红外光谱、扫描电子显微镜及Ｘ射线能谱对该胆结石进行了观察和研究。结果表明该胆结石的主要成分为胆固醇,并混有少量的蛋白质和无机钙盐,说明珍珠形胆结石虽然和珍珠具有相似的形貌,但组成是完全不同的。根据扫描电子显微镜的照片,作者推测结石的珍珠外形可能是因为片状的胆固醇分子形成胆甾型晶体而形成的。     

Electron Microscopy Studies of Local Structural Modulations in Zeolite Crystals

Zeolites are widely used in catalysis, gas separation, ion exchange, etc. due to their superior physicochemical properties, which are closely related to specific features of their framework structures. Although more than two hundred different framework types have been recognized, it is of great interest to explore from a crystallographic perspective, the atomic positions, surface terminations, pore connectivity and structural defects that deviate from the ideal framework structures, namely local structural modulation. In this article, we review different types of local modulations in zeolite frameworks using various techniques, especially electron microscopy (EM). The most recent advances in resolving structural information at the atomic level with aberration corrected EM are also presented, commencing a new era of gaining atomic structural information, not only for all tetrahedral atoms including point vacancies in framework but also for extra-framework cations and surface terminations.     

Orientation Imaging Microscopy for the Transmission Electron Microscope

The resolution limit of Orientation Imaging Microscopy in the Scanning Electron Microscope is between 20 nA and 80 nA depending on the basic resolution/beam current performance of the SEM, the sample atomic number and the level of residual strain within it. The newer technique of orientation imaging in the transmission electron microscope, TEM, improves on this resolution limit by a factor of five to ten. The new technique is based on a novel procedure for determining the crystallography of separate small volumes in the sample by examination of a large series of dark field images. Each image is recorded for a different diffraction condition. This is achieved by using a computer to direct the electron beam onto the same area of the sample so that it covers all directions within a cone of semi-apex angle 3 degrees. Analysis of the intensity of the same point in each of the dark field images permits reconstruction of a diffraction pattern for that point providing the data to calculate its crystal orientation. The process is repeated for each point in the image. The Orientation Image Micrograph is constructed from the orientations so determined. The technique is shown to be capable of producing orientation micrographs of high spatial resolution for unstrained samples. For highly strained samples difficulties are encountered in accurately indexing the complicated diffraction patterns that are observed. Methods to improve the indexing procedures involve determining the sub-cell structure first from a comparison of patterns from adjacent pixels and then summing all patterns belonging to a single sub-cell. The resultant improvement in pattern quality permits more reliable determination of orientation. Examples of this procedure are taken from studies of deformed aluminum.     

High Resolution Scanning Tunneling Microscopy of a 1D Coordination Polymer with Imidazole‐Based N,N,O Ligands on HOPG

Novel κ³‐N,N,O ligands tend to form 1D coordination polymer strands. Deposition of 1D structures on highly oriented pyrolytic graphite (HOPG) was achieved from diluted solutions and polymer strands have been studied on HOPG by AFM/STM. Single strands were mapped by STM and their electronic properties were subsequently characterized by current imaging tunneling spectroscopy (CITS). Periodic density functional calculations simulating a polymer strand deposited on a HOPG surface are in agreement with the zig‐zag structure indicated by experimental findings. Both the observed periodicity and the Zn–Zn distances can be reproduced in the simulations. Van der Waals interactions were found to play a major role for the geometry of the isolated polymer strand, for the adsorption geometry on HOPG, as well as for the adsorption energy.     

Fabrication of Active Horseradish Peroxidase Micropatterns with a High Resolution by Scanning Electrochemical Microscopy

We used a new reactive species OH^? to fabricate active horseradish peroxidase (HRP) micropatterns with a high resolution by scanning electrochemical microscopy (SECM) coupled with a carbon fiber disk electrode as the SECM tip. In this method, except for active HRP micropatterns predesigned other regions on a HRP‐immobilized substrate were deactivated by OH^? generated at the tip held at ?1.7 V in 1.0 mol/L KCl containing 2.0×10^?3 mol/L benzoquinone (BQ) (pH 8.0). The feedback mode of SECM with a tip potential of ?0.2 V was used to characterize the active HRP micropatterns in 1.0 mol/L KCl containing 2.0×10^?3 mol/L BQ and 2.0×10^?3 mol/L H₂O₂.     

扫描电化学显微镜用于研究生物膜微环境的电子传递

生物电化学系统(BESs)的核心是生物膜在电极/溶液界面的电子传递反应,研究生物膜微区环境中的电子传递有助于阐明微生物的胞外电子传递(EET)机制,从而有针对性地提高BESs中的电子转移效率。微生物的EET机制包括直接电子传递和间接电子传递,由于生物膜组成复杂,含有多种分泌物、胞外聚合物等,常规电化学方法只能从生物膜宏观层面研究EET机制,无法有效区分这两种电子传递途径的贡献。本文采用电化学循环伏安方法研究了电子穿梭体二茂铁甲醇(FcMeOH)与希瓦氏菌(Shewanella)相互作用的界面过程;基于扫描电化学显微技术构建了穿透模式,通过微电极介导FcMeOH与Shewanella反应,收集仅来自间接电子传递途径产生的电流,同时测定了Shewanella在电极/溶液界面的氧化还原性质和空间分布。本论文将电化学扫描探针显微技术应用于EET的研究,从物理化学角度揭示微生物在代谢过程中与外界的电子传输机制。     

熔体结晶聚乙烯晶体的高分辨电子显微学研究

聚乙烯在一定的不良溶剂中或在熔融结晶的条件下可以得到具有弧形生长边缘的单晶,对于具有弧形边的（200）晶面的形成机理,已有一些研究报道,但由于高分子链具有成千上万个结构单元,使其结晶过程很复杂,可能会导致弧形边的成因有所不同,因此对于弧形边的形成机理有不同的解释。