Z衬度扫描透射电子显微术的前沿进展

文章介绍了Z衬度扫描透射电子显微术(Z-scanning transmission electron microscopy，Z-STEM，Z为原子序数)的最新进展：Z-STEM可以直接“观察”到晶体中原子的真实位置，Z衬度图像的分辨率在经过球差校正后可达0．6A；在利用Z衬度成像技术对材料的阴极荧光(cathodoluminescence，CL)性质的研究中，首次观察到了“死层”(dead layer)的存在．然后，文章以半导体与结晶氧化物界面结构、Al72Ni20Co8十角形准晶结构以及SrTiO3晶界结构为例，具体介绍了Z衬度成像在测定物质结构与化学组成方面独特的优势。     

Aberration-corrected scanning transmission electron microscopy for complex transition metal oxides

Lattice,charge,orbital,and spin are the four fundamental degrees of freedom in condensed matter,of which the interactive coupling derives tremendous novel physical phenomena,such as high-temperature superconductivity(high-T_c SC) and colossal magnetoresistance(CMR) in strongly correlated electronic system.Direct experimental observation of these freedoms is essential to understanding the structure-property relationship and the physics behind it,and also indispensable for designing new materials and devices.Scanning transmission electron microscopy(STEM) integrating multiple techniques of structure imaging and spectrum analysis,is a comprehensive platform for providing structural,chemical and electronic information of materials with a high spatial resolution.Benefiting from the development of aberration correctors,STEM has taken a big breakthrough towards sub-angstrom resolution in last decade and always steps forward to improve the capability of material characterization;many improvements have been achieved in recent years,thereby giving an indepth insight into material research.Here,we present a brief review of the recent advances of STEM by some representative examples of perovskite transition metal oxides;atomic-scale mapping of ferroelectric polarization,octahedral distortions and rotations,valence state,coordination and spin ordering are presented.We expect that this brief introduction about the current capability of STEM could facilitate the understanding of the relationship between functional properties and these fundamental degrees of freedom in complex oxides.     

The image potential in scanning transmission electron microscopy and scanning tunneling microscopy

Abstract

We sketch developments in the theory of the self-energy of charged particles moving near condensed matter surfaces. Some applications to experimental results from spectroscopy with electrons localized in microprobe beams and to electrons tunneling across a gap between two metals are considered.     

Quantitative atomic resolution scanning transmission electron microscopy

Complete understanding of atomic resolution high-angle annular dark-field (Z-contrast) images requires quantitative agreement between simulations and experiments. We show that intensity variations can be placed on an absolute scale by normalizing the measured image intensities to the incident beam. We construct fractional intensity images of a SrTiO3 single crystal for regions of different thickness up to 120 nm. Experimental images are compared directly with image simulations. Provided that spatial incoherence is taken into account in the simulations, almost perfect agreement is found between simulation and experiment.     

Structure and mass analysis by scanning transmission electron microscopy.

In the scanning transmission electron microscope (STEM) an electron beam of a few angstroms diameter is raster scanned over a thin sample and the scattered electrons are sequentially measured for each sample element irradiated. The mass, the elemental composition and the structure of a protein can be simultaneously assessed if all detector systems of the STEM are used. Aspects affecting the accuracy of the mass measurement technique and the demands placed on the instrument's dark-field detector system are outlined. In addition, the influences of some sample preparation techniques are noted and the mass-loss induced at ambient temperatures by the incidence of 80kV electrons on various biological samples is reported. Finally, the importance of the STEM for the structural analysis of proteins is documented by examples.     

Characterization of superconducting YBaCuO-films by low temperature scanning electron microscopy

Low-temperature scanning electron microscopy has been performed for imaging the spatial distribution of the critical current densityj _c(x,y) and of the critical temperatureT _c(x,y) in polycrystalline superconducting YBaCuO films. Strongly inhomogeneous behavior has been observed, and the spatial resolution limit has been found to be 1–2 m. The local temperature increment in the specimen film caused by the electron beam scanning has been demonstrated experimentally as the underlying mechanism of the imaging principle, and the beam-induced thermal perturbation of the high-T _c film/substrate configuration is discussed in detail. The radiation hardness of the sample films against the electron beam irradiation in our imaging experiments has been evaluated. No radiation damage could be detected up to the maximum applied dose of well above 10²⁰ electrons/cm² for a typical beam energy of 26 keV.     

Instrumental requirements for the detection of electron beam-induced object excitations at the single atom level in high-resolution transmission electron microscopy

This contribution touches on essential requirements for instrument stability and resolution that allows operating advanced electron microscopes at the edge to technological capabilities. They enable the detection of single atoms and their dynamic behavior on a length scale of picometers in real time. It is understood that the observed atom dynamic is intimately linked to the relaxation and thermalization of electron beam-induced sample excitation. Resulting contrast fluctuations are beam current dependent and largely contribute to a contrast mismatch between experiments and theory if not considered. If explored, they open the possibility to study functional behavior of nanocrystals and single molecules at the atomic level in real time.     

Electron tomography algorithms in scanning transmission electron microscopy

Different weighting filters used in tomographic algorithms are investigated. Algorithms for the recovery of tomographic structures are produced for general application in graphic processors. Software for a Carl Zeiss Libra 200FE microscope that enables us to record a series of projections in the STEM mode is developed. Calculation experiments show the improvement in tomogram quality when using cosine and 1/z ² filters instead of a linear filter at high noise levels for objects larger than 25 points.     

Contamination mitigation strategies for scanning transmission electron microscopy

Modern scanning transmission electron microscopy (STEM) enables imaging and microanalysis at very high magnification. In the case of aberration-corrected STEM, atomic resolution is readily achieved. However, the electron fluxes used may be up to three orders of magnitude greater than those typically employed in conventional STEM. Since specimen contamination often increases with electron flux, specimen cleanliness is a critical factor in obtaining meaningful data when carrying out high magnification STEM. A range of different specimen cleaning methods have been applied to a variety of specimen types. The contamination rate has been measured quantitatively to assess the effectiveness of cleaning. The methods studied include: baking, cooling, plasma cleaning, beam showering and UV/ozone exposure. Of the methods tested, beam showering is rapid, experimentally convenient and very effective on a wide range of specimens. Oxidative plasma cleaning is also very effective and can be applied to specimens on carbon support films, albeit with some care. For electron beam-sensitive materials, cooling may be the method of choice. In most cases, preliminary removal of the bulk of the contamination by methods such as baking or plasma cleaning, followed by beam showering, where necessary, can result in a contamination-free specimen suitable for extended atomic scale imaging and analysis.     

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.     

Characterization of SIPOS films by spectroscopic ellipsometry and transmission electron microscopy

The structural and compositional properties of undoped SIPOS thin films have been studied by spectroscopic ellipsometry and transmission electron microscopy. It is shown that in most cases the former method provides fast and reliable results. The growth rate and crystallinity of SIPOS layers are studied as a function of N₂O concentration in the gas phase and annealing temperature.     

High-resolution transmission and scanning electron microscopy of boride-nitride nanostructured films

The results of electron-microscopic studies of grain boundaries and the structure of fractures of titanium boride-and nitride-based films obtained by nonreactive magnetron sputtering are considered. The chemical and phase composition of the films is analyzed with the help of Auger electron spectroscopy and microscopic electron diffraction analysis. The structure of boundaries and the presence of amorphous inclusions, dislocations, and other structural distortions are discussed and the nature of the deformation under indentation is considered.     

Atomic-resolution electron energy loss spectroscopy imaging in aberration corrected scanning transmission electron microscopy

The "delocalization" of inelastic scattering is an important issue for the ultimate spatial resolution of innershell spectroscopy in the electron microscope. It is demonstrated in a nonlocal model for electron energy loss spectroscopy (EELS) that delocalization of scanning transmission electron microscopy (STEM) images for single, isolated atoms is primarily determined by the width of the probe, even for light atoms. We present experimental data and theoretical simulations for Ti L-shell EELS in a [100] SrTiO3 crystal showing that, in this case, delocalization is not significantly increased by dynamical propagation. Issues relating to the use of aberration correctors in the STEM geometry are discussed.     

Video-frequency scanning transmission electron microscopy of moving gold nanoparticles in liquid

Immobilized gold nanoparticles were imaged in a liquid containing water and 50% glycerol with scanning transmission electron microscopy (STEM). The specimen was enclosed in a liquid compartment formed by two silicon microchips with electron transparent windows. A series of images was recorded at video frequency with a spatial resolution of 1.5nm. The nanoparticles detached from their support after imaging them for several seconds at a magnification of 250,000. Their movement was found to be much different than the movement of nanoparticles moving freely in liquid as described by Brownian Motion. The direction of motion was not random-the nanoparticles moved either in a preferred direction, or radially outwards from the center of the image. The displacement of the gold nanoparticles over time was three orders of magnitude smaller than expected on the basis of Brownian Motion. This finding implies that nanoscale objects of flexible structure or freely floating, including nanoparticles and biological objects, can be imaged with nanoscale resolution, as long as they are in close proximity to a solid support structure.     

Visualizing macromolecular complexes with in situ liquid scanning transmission electron microscopy

A central focus of biological research is understanding the structure/function relationship of macromolecular protein complexes. Yet conventional transmission electron microscopy techniques are limited to static observations. Here we present the first direct images of purified macromolecular protein complexes using in situ liquid scanning transmission electron microscopy. Our results establish the capability of this technique for visualizing the interface between biology and nanotechnology with high fidelity while also probing the interactions of biomolecules within solution. This method represents an important advancement towards allowing future high-resolution observations of biological processes and conformational dynamics in real-time.     

扫描透射离子显微成像系统的建立和实验研究

 基于上海应用物理研究所的扫描质子微探针系统,对扫描透射离子显微成像（STIM）技术进行了仿真分析和实验研究,建立了基于中值滤波方法的数据处理程序,获得了大鼠股骨切片的面密度分布和薄壁小球的离轴STIM图像。理论分析和实验结果显示：由在轴探测数据的中值滤波结果可以计算出定量的面密度分布信息,由能量窗滤波的离轴探测数据则可以给出高分辨的定性图像,这在薄样品、强束流、以及质子激发X荧光（PIXE）分析同时进行的STIM分析中尤为有用;增加获取的事件数、选择合适的滤波方法可以使测量误差远小于阻止本领计算带来的误差。该方法可以用于测量几十μm尺度样品的绝对质量以及辅助PIXE技术进行元素定量分布分析。     

Practical spatial resolution of electron energy loss spectroscopy in aberration corrected scanning transmission electron microscopy

The resolution of electron energy loss spectroscopy (EELS) is limited by delocalization of inelastic electron scattering rather than probe size in an aberration corrected scanning transmission electron microscope (STEM). In this study, we present an experimental quantification of EELS spatial resolution using chemically modulated 2×(LaMnO(3))/2×(SrTiO(3)) and 2×(SrVO(3))/2×(SrTiO(3)) superlattices by measuring the full width at half maxima (FWHM) of integrated Ti M(2,3), Ti L(2,3), V L(2,3), Mn L(2,3), La N(4,5), La N(2,3) La M(4,5) and Sr L(3) edges over the superlattices. The EELS signals recorded using large collection angles are peaked at atomic columns. The FWHM of the EELS profile, obtained by curve-fitting, reveals a systematic trend with the energy loss for the Ti, V, and Mn edges. However, the experimental FWHM of the Sr and La edges deviates significantly from the observed experimental tendency.     

扫描透射离子显微成像系统的建立和实验研究

基于上海应用物理研究所的扫描质子微探针系统,对扫描透射离子显微成像（STIM）技术进行了仿真分析和实验研究,建立了基于中值滤波方法的数据处理程序,获得了大鼠股骨切片的面密度分布和薄壁小球的离轴STIM图像。理论分析和实验结果显示：由在轴探测数据的中值滤波结果可以计算出定量的面密度分布信息,由能量窗滤波的离轴探测数据则可以给出高分辨的定性图像,这在薄样品、强束流、以及质子激发X荧光（PIXE）分析同时进行的STIM分析中尤为有用;增加获取的事件数、选择合适的滤波方法可以使测量误差远小于阻止本领计算带来的误差。该方法可以用于测量几十μm尺度样品的绝对质量以及辅助PIXE技术进行元素定量分布分析。     

Characterization of a growth-front interface in a HPHT-grown diamond crystal by transmission electron microscopy

The growth-front interface of a diamond single crystal, which was grown from the Fe-Ni-C system under high pressure and high temperature (HPHT), has been directly observed by transmission electron microscopy (TEM) for the first time. The presence of a cellular interface suggests that the diamond is grown from solution and there exists a narrow supercooling zone in front of the solid–liquid interface. Diamond-growth parallel layers were also found, which indicates that the diamond grows from solution layer by layer. It provides direct evidence that the diamond is synthesized through graphite dissolution and transformation to subcritical diamond particles in a molten catalyst, diamond subcritical particle connection to form diamond clusters, diffusion of the diamond clusters to the growing diamond, and unification of the diamond clusters on the growing diamond crystal. Received: 17 July 2000 / Accepted: 27 October 2000 / Published online: 10 January 2001