High-Resolution Transmission Electron Microscopy Re-examined as a Tool in Solid State Chemistry

Transmission electron microscopy (TEM) can be used with crystalline solids to obtain direct images of small structural groups comprising a few coordination polyhedra with resolution nearly down to atomic scale (“lattice imaging”). More exact knowledge of the conditions required for direct imaging, as well as improvements in the instruments themselves, have now made it possible to examine very small defect regions (microdomains), faults in the stacking sequence of structural groups or atom layers (planar or Wadsley defects), and isolated defects in narrowly delimited areas that may actually be below the dimensions of the unit cell. The structural principle of the very smallest ordered regions can even be determined when X-ray structure analysis proves unable to do this. “Block structures” are particularly suitable as models for the testing and further development of the high-resolution method; the detection of three-dimensional, two-dimensional, and one-dimensional defects has been studied on such structures.     

Electron Diffraction with the Transmission Electron Microscope as a Phase-Determining Diffractometer—From Spatial Frequency Filtering to the Three-Dimensional Structure Analysis of Ribosomes

Chemists recognize X-ray crystal structure analysis and electron microscopy as powerful methods of analysis. In the last 20 years the basic ideas of X-ray diffraction analysis have been extended to the field of electron microscopy, whereby an image-forming apparatus is converted into an electron diffractometer, and through which an old dream of crystallographers can be realized—the measurement of the phase shift of scattered waves, a prerequisite for the direct calculation of structures. Its most important area of application, like that of the X-ray diffractometer, is in three-dimensional structure analysis—in all fields of science. However, beyond crystallography, aperiodic structures (comparable to crystals with a single unit cell) can also be analyzed three-dimensionally. In this progress report, the development of the first idea (spatial frequency filtering) to the analysis of ribosomal particles is outlined. Attention will be focused primarily on quantitative methods for the measurement of scattered rays, which are also usable beyond the conventional limit of resolution, down to atomic resolution. In the course of this work in 1968, the principle of the three-dimensional analysis of native biological crystal structures using the electron microscope, as worked with today in many laboratories, was developed. In Munich, however, further research focused on the three-dimensional analysis of aperiodic and individual (especially biological) objects. The analysis of 50S-subunits of the procaryotic ribosome of E. coli showed surprisingly good reproducibility of the results (although only within the same orientation), allowing the deduction of almost ideal average model structures from a limited number of particles.     

Characterization of nanomaterials in food by electron microscopy

Engineered nanomaterials (ENMs) are increasingly being used in the food industry. In order to assess the efficacy and the risks of these materials, it is essential to have access to methods that not only detect the nanomaterials, but also provide information on the characteristics of the materials (e.g., size and shape).This review presents an overview of electron microscopy (EM)-based methods that have been, or have the potential to be, applied to imaging ENMs in foodstuffs. We provide an overview of approaches to sample preparation, including drying, chemical treatment, fixation and cryogenic methods. We then describe standard and non-standard EM-based approaches that are available for imaging prepared samples. Finally, we present a strategy for selecting the most appropriate method for a particular foodstuff.     

Imaging fibrinogen adsorbed on noble metal surfaces with scanning tunneling microscopy: correlation of images with electron spectroscopy for chemical analysis, secondary ion mass spectrometry, and radiolabeling studies

Fibrinogen adsorption on gold and platinum surfaces has been studied with electron spectroscopy for chemical analysis (ESCA), secondary ion mass spectrometry (SIMS), ¹²⁵I labeling, and scanning tunneling microscopy (STM). Stable images of single molecules have been obtained, but are rare. ESCA, SIMS, and labeling studies confirm that absorbed fibrinogen is present on samples at monolayer and submonolayer coverages even when STM images show only a bare substrate. Imaging is more reproducible at high coverages at which single molecules cannot be resolved. Possible explanations for the failure of STM to observe adsorbed fibrinogen molecules are discussed.     

Quantification of the pore size distribution (porosity profiles) in microfiltration membranes by SEM,TEM and computer image analysis

Transport properties of membranes are closely related to morphological properties like surface porosity and variation of their inner pore structure. Scanning electron microscopy (SEM) as well as transmission electron microscopy (TEM) are powerful tools to characterise the microscopical pore structure of membranes in a qualitative manner. In order to provide more quantitative data of surface and cross-sectional pores computer image analysis can be used. Parameters like ‘porous area fraction’ and ‘mean free path length’ have been selected to describe the pore distribution within porosity profiles in order to consider the effect that the pores within the cross-section are connected to each other.     

Recent progress in probing atomic and molecular quantum coherence with scanning tunneling microscopy

Quantum coherent physics and chemistry concern the creation and manipulation of an excited-state manifold that contains the superposition and entanglement of multiple quantum levels. Electromagnetic waves such as light and microwave can be used to generate and probe different quantum coherent phenomena. The recent advances in scanning tunneling microscopy (STM) techniques including ultrafast laser coupled STM and electron spin resonance STM combine electromagnetic excitation with tunneling electron detection, bringing the investigation of quantum coherence down to the atomic and molecular level. Here, we survey the latest STM studies of different quantum coherent phenomena covering molecular vibration, electron transfer, surface plasmon resonance, phonon, spin oscillation, and electronic transition, and discuss the state and promise of characterizing and manipulating quantum coherence at the atomic or molecular scale.     

The Cross‐Sectional Structure of Vanadium Oxide Nanotubes Studied by Transmission Electron Microscopy and Electron Spectroscopic Imaging

Vanadium oxide nanotubes (VO_x‐NTs) are easily accessible in pure form from vanadium(V) alkoxides and amines by a sol‐gel reaction and a subsequent hydrothermal treatment. The wall structure of VO_x‐NTs containing hexadecylamine or dodecylamine as the structure‐directing template has been characterised by transmission electron microscopy (TEM). A standard method for preparing TEM specimens was modified in order to investigate the cross‐sectional structure of the tubes. The elemental distribution in the layered structure inside the tube walls has been visualised by electron spectroscopic imaging: vanadium oxide builds up the layers that appear with dark contrast in the TEM images while carbon, i. e., the organic template, is present in between. The bent VO_x layers inside the tube walls are preferentially scrolls rather than concentric cylinders. Moreover, some tubes are formed by a combination of both types. The layer structure inside the tube walls is frequently disordered, and several types of defects appear.     

球形纳米银与人血清白蛋白相互作用的研究

通过化学还原法合成了球形银纳米颗粒,并利用电子显微镜方法对其形貌进行了表征;利用紫外可见吸收光谱法(UV)、荧光光谱法(FL) 以及扫描电子显微镜(SEM) 研究了球形纳米银与人血清白蛋白(HSA) 的结合反应。随着纳米银溶液浓度的增加,混合溶液的紫外吸收峰强度增加,但荧光强度则发生了明显的猝灭。光谱学实验结果表明,球形纳米银与人血清白蛋白在溶液中发生了相互作用,此结果也通过扫描电子显微镜实验得到了验证。由荧光实验还可获得纳米银与HSA 相互作用的结合常数、结合位点数以及吉布斯自由能变,由这些热力学数据可知纳米银与人血清白蛋白可以自发结合发生反应,并形成缔合物。     

Granitic groundwater colloids sampling and characterisation: the strategy for artefact elimination

Colloids were separated by submicro-filtration of granitic groundwater samples collected at-line under in-situ thermodynamic conditions after down-hole groundwater sampling and transfer at the well head. The methodology avoids the generation of artefacts produced by pH changes due to CO(2) exchange, yielding potential carbonate precipitation, or by O(2) contamination yielding oxidized insoluble phases. The enhanced pressure and the anoxic conditions are also maintained through the filtering procedure. This procedure was carried out after a period of regular sampling of groundwater pumped to the ground surface and continuous on-line long-term measurements (weeks, months) of chemical and physical parameters in the unbroken sample water both at the ground surface and at depth down-hole. Colloid samples were characterized on the submicro-filtration membrane by scanning electron microscopy. Under deep granite groundwater conditions, natural colloids occur sparsely. The colloid concentration was determined C(col) approximately 1 and approximately 50 microg L(-1) for sizes ranging from 50 to 200 nm or n(col) approximately 3.9 x 10(9) and 47 x 10(9) L(-1) for sizes larger than 50 nm for KFM11A, Forsmark, and KLX17A, Laxemar, Oskarshamn, respectively, Sweden. These colloids are expected to be clay particles with an average size smaller than 200 nm for the Na-Ca-Cl and Na-Cl groundwaters (pH 7.6 and 8.00, ionic strength approximately 10(-1) and approximately 10(-2) mol L(-1), respectively, for KFM11A and KLX17A), the colloid concentrations were comparable with values previously reported in the literature.     

Imaging Nanocarbon Materials: Soot Particles in Flames are Not Structurally Homogeneous

For the first time, nascent soot particles are probed by using helium‐ion microscopy (HIM). HIM is a technique that is similar to scanning electron microscopy (SEM) but it can achieve higher contrast and improved surface sensitivity, especially for carbonaceous materials. The HIM microscope yields images with a high contrast, which allows for the unambiguous recognition of smaller nascent soot particles than those observed in previous transmission electron microscopy studies. The results indicate that HIM is ideal for rapid and reliable probing of the morphology of nascent soot, with surface details visible down to approximately 5 nm, and particles as small as 2 nm are detectable. The results also show that nascent soot is structurally and chemically inhomogeneous, and even the smallest particles can have shapes that deviate from a perfect sphere.     

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。     

Direct Atomic-Level Imaging of Zeolites: Oxygen,Sodium in Na-LTA and Iron in Fe-MFI

Zeolites are becoming more versatile in their chemical functions through rational design of their frameworks. Therefore, direct imaging of all atoms at the atomic scale, basic units (Si, Al, and O), heteroatoms in the framework, and extra-framework cations, is needed. TEM provides local information at the atomic level, but the serious problem of electron-beam damage needs to be overcome. Herein, all framework atoms, including oxygen and most of the extra-framework Na cations, are successfully observed in one of the most electron-beam-sensitive and lowest framework density zeolites, Na- LTA . Zeolite performance, for instance in catalysis, is highly dependent on the location of incorporated heteroatoms. Fe single atomic sites in the MFI framework have been imaged for the first time. The approach presented here, combining image analysis, electron diffraction, and DFT calculations, can provide essential structural keys for tuning catalytically active sites at the atomic level.     

Crystal structure of the parent misfit-layered cobalt oxide [Sr2O2]qCoO2

The crystal structure of our newly discovered Sr-Co-O phase is investigated in detail through high-resolution electron microscopy (HREM) techniques. Electron diffraction (ED) measurement together with energy dispersive X-ray spectroscopy (EDS) analysis show that an ampoule-synthesized sample contains an unknown Sr-Co-O ternary phase with monoclinic symmetry and the cation ratio of Sr/Co=1. From HREM images a layered structure with a regular stacking of a CdI₂-type CoO₂ sheet and a rock-salt-type Sr₂O₂ double-layered block is observed, which confirms that the phase is the parent of the more complex “misfit-layered (ML)” cobalt oxides of [M_mA₂O_m+2]_qCoO₂ with the formula of [Sr₂O₂]_qCoO₂, i.e. m=0. It is revealed that the misfit parameter q is 0.5, i.e. the two sublattices of the CoO₂ sheet and the Sr₂O₂ block coexist to form a commensurate composite structure. We propose a structural model with monoclinic P2₁/m symmetry, which is supported by simulations of ED patterns and HREM images based on dynamical diffraction theory.     

Advanced TEM Characterization for Single-atom Catalysts: from Ex-situ Towards In-situ

Clean energy innovation has triggered the development of single-atom catalysts(SACs) due to their excellent catalytic activity, high tunability and low cost. The success of SACs for many catalytic reactions has opened a new field, where the fundamentals of catalytic property-structure relationship at atomic level await exploration, and thus raises challenges for structural characterization. Among the characterization techniques for SACs, aberration-corrected transmission electron microscopy(TEM) has become an essential tool for direct visualization of single atoms. In this review, we briefly summarize recent studies on SACs using advanced TEM. We first introduce TEM methods, which are particularly important for SACs characterization, and then discuss the applications of advanced TEM for SAC characterization, where not only atomic dispersion of single atoms can be studied, but also the distribution of elements and the valence state with local coordination can be resolved. We further extend our review towards in-situ TEM, which has increasing importance for the fundamental understanding of catalytic mechanism. Perspectives of TEM for SACs are finally discussed.     

Structure of sputtered Co-Se thin films prepared for an application in catalysis

Co-Se thin films prepared by magnetron sputtering have shown significant activity for the oxygen reduction reaction. One sample, after sectioning by ultramicrotomy, was studied by high-resolution scanning transmission electron microscopy (HRSTEM) and scanning Auger microscopy (SAM), and X-ray diffraction (XRD) was used for characterizing further samples. These thin films were shown to have Co-Se nanocrystals embedded into Se-rich matrices. The TEM and XRD results were consistent with the nanocrystallites being non-stoichiometric with structures related to those of monoclinic Co_1−xSe (x=0.125-0.25).     

衬底对N@C60分子电子自旋共振谱的影响

N@C₆₀内嵌富勒烯是一种在量子科技领域有较高应用前景的分子。科学家们设计了一系列以内嵌富勒烯分子为基本量子单元的量子计算机模型,而构筑这样的模型具有极高的挑战。其中,由于内嵌富勒烯分子阵列的制备通常需要合适的衬底,而衬底与分子之间的相互作用会影响甚至破坏内嵌N原子的自旋信号。因此研究和理解衬底与内嵌富勒烯分子的相互作用具有重要的意义。本文制备了高质量的N@C₆₀分子,并采用扫描隧道显微镜对其在Au(111)表面的结构及电子态进行表征。通过对比N@C₆₀分子在Au(111)、Si(111)、SiO₂表面的电子自旋共振(ESR)信号随时间及其抽真空处理的变化,表明Au原子的核自旋与内嵌N原子的电子自旋的耦合作用是Au(111)表面N@C₆₀单分子层的ESR谱中内嵌N原子的信号衰减的主要原因。     

FIB, TEM and LA-ICPMS investigations on melt inclusions in Martian meteorites-Analytical capabilities and geochemical insights

In order to obtain full information coverage on melt inclusions in Martian meteorites (subgroup nakhlites) complementary micro-analytical techniques were used, i.e. focused ion beam, transmission electron microscopy and laser ablation. Using focused ion beam several lamellae for transmission electron microscopy were prepared and secondary electron images of cross-sections could be acquired. Laser ablation–inductively coupled plasma mass spectrometry analyses were performed on selected inclusions to obtain mass-oriented bulk composition of inclusions at depth. The differences in composition between melt inclusions in olivine and augite crystals would suggest a xenocrystic origin for olivine. Furthermore, electron diffraction patterns clearly indicated that the SiO₂-rich phase in inclusions from augite in meteorites from Northwest Africa site is re-crystallized, whereas it is still vitreous in the inclusions from Nakhla sampling site. Therefore, different post-entrapment evolutions were active for the two nakhlite meteorite sets, the Nakhla and the NWA817 set. Melt inclusions in Nakhla olivine presented alteration veins, which were presumably produced before their landing on Earth. If this is the case, this would indicate a alteration stage already on Mars with all the consequence in terms of climate history. Melt inclusions in Nakhla augite resulted unaffected by any alteration or modification following the entrapment, and therefore represent the best candidate to indicate the pristine magma composition.     

The Use of Electron Backscatter Diffraction for the Investigation of Nano Crystalline Materials and the Move Towards Orientation Imaging in the TEM

Electron backscatter diffraction is shown to have a spatial resolution between 5nm and 10nm and is well suited for the investigation of nano crystalline materials. A study of texture and mesotexture in copper Damascene interconnect lines is used as an illustration. Samples were prepared by electro deposition from baths of different compositions and under various power cycles. The resulting grain structures were visually smaller than the 0.3 micron interconnect line width. However, if twin boundaries were considered as substructure rather than true grain boundaries, the effective grain size become larger than the line width. The bath composition affected the 111 texture component from times 5 random to 26 times random whereas different power cycles affected the texture much less. For structures with a grain size smaller than 20nm a new transmission electron microscope technique has been developed. Automated examination of a sequence of dark field images collected from a selected area lead to the reconstruction of a diffraction pattern for each pixel within the area. These patterns are indexed automatically, permitting crystal orientation as a function of spatial positioning to be mapped. The resulting orientation information is equivalent to that obtained using electron backscatter patterns. The practical resolution limit of this technique approaches 1 to 2 nanometers.