An imaging technique able to resolve and identify all individual atoms in non-periodic solids would be a very useful tool for materials analysis. Annular dark-field (ADF) imaging in an aberration-corrected scanning transmission electron microscope optimized for low voltage operation allows such an analysis, as shown by Ondrej Krivanek and co-workers. The technique was used to examine a monolayer of boron nitride, in which it revealed individual atomic substitutions involving carbon and oxygen impurity atoms. Careful analysis of the data enables the construction of a detailed map of the atomic structure, with all the atoms of the four species resolved and identified. An imaging technique that could identify all the individual atoms, including defects, in a material would be a useful tool. Here an electron-microscopy approach to the problem, based on annular dark-field imaging, is described. A monolayer of boron nitride was studied, and three types of atomic substitution were identified. Careful analysis of the data enabled the construction of a detailed map of the atomic structure. Direct imaging and chemical identification of all the atoms in a material with unknown three-dimensional structure would constitute a very powerful general analysis tool. Transmission electron microscopy should in principle be able to fulfil this role, as many scientists including Feynman realized early on1. It images matter with electrons that scatter strongly from individual atoms and whose wavelengths are about 50 times smaller than an atom. Recently the technique has advanced greatly owing to the introduction of aberration-corrected optics2,3,4,5,6,7,8. However, neither electron microscopy nor any other experimental technique has yet been able to resolve and identify all the atoms in a non-periodic material consisting of several atomic species. Here we show that annular dark-field imaging in an aberration-corrected scanning transmission electron microscope optimized for low voltage operation can resolve and identify the chemical type of every atom in monolayer hexagonal boron nitride that contains substitutional defects. Three types of atomic substitutions were found and identified: carbon substituting for boron, carbon substituting for nitrogen, and oxygen substituting for nitrogen. The substitutions caused in-plane distortions in the boron nitride monolayer of about 0.1 A magnitude, which were directly resolved, and verified by density functional theory calculations. The results demonstrate that atom-by-atom structural and chemical analysis of all radiation-damage-resistant atoms present in, and on top of, ultra-thin sheets has now become possible.

Atom-by-atom structural and chemical analysis by annular dark-field electron microscopy

Whereas standard transmission electron microscopy studies are unable to preserve the native state of chemically reactive and beam-sensitive battery materials after operation, such materials remain pristine at cryogenic conditions. It is then possible to atomically resolve individual lithium metal atoms and their interface with the solid electrolyte interphase (SEI). We observe that dendrites in carbonate-based electrolytes grow along the (preferred), , or directions as faceted, single-crystalline nanowires. These growth directions can change at kinks with no observable crystallographic defect. Furthermore, we reveal distinct SEI nanostructures formed in different electrolytes.

Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy

A common misconception is that the irradiation of solids with energetic electrons and ions has exclusively detrimental effects on the properties of target materials. In addition to the well-known cases of doping of bulk semiconductors and ion beam nitriding of steels, recent experiments show that irradiation can also have beneficial effects on nanostructured systems. Electron or ion beams may serve as tools to synthesize nanoclusters and nanowires, change their morphology in a controllable manner, and tailor their mechanical, electronic, and even magnetic properties. Harnessing irradiation as a tool for modifying material properties at the nanoscale requires having the full microscopic picture of defect production and annealing in nanotargets. In this article, we review recent progress in the understanding of effects of irradiation on various zero-dimensional and one-dimensional nanoscale systems, such as semiconductor and metal nanoclusters and nanowires, nanotubes, and fullerenes. We also consider the t...

Ion and electron irradiation-induced effects in nanostructured materials

Following the invention of electron optics during the 1930s, lens aberrations have limited the achievable spatial resolution to about 50 times the wavelength of the imaging electrons. This situation is similar to that faced by Leeuwenhoek in the seventeenth century, whose work to improve the quality of glass lenses led directly to his discovery of the ubiquitous "animalcules" in canal water, the first hints of the cellular basis of life. The electron optical aberration problem was well understood from the start, but more than 60 years elapsed before a practical correction scheme for electron microscopy was demonstrated, and even then the remaining chromatic aberrations still limited the resolution. We report here the implementation of a computer-controlled aberration correction system in a scanning transmission electron microscope, which is less sensitive to chromatic aberration. Using this approach, we achieve an electron probe smaller than 1 A. This performance, about 20 times the electron wavelength at 120 keV energy, allows dynamic imaging of single atoms, clusters of a few atoms, and single atomic layer 'rafts' of atoms coexisting with Au islands on a carbon substrate. This technique should also allow atomic column imaging of semiconductors, for detection of single dopant atoms, using an electron beam with energy below the damage threshold for silicon.

Sub-ångstrom resolution using aberration corrected electron optics

Electron energy-loss spectroscopy (EELS) is an analytical technique that measures the change in kinetic energy of electrons after they have interacted with a specimen. When carried out in a modern transmission electron microscope, EELS is capable of giving structural and chemical information about a solid, with a spatial resolution down to the atomic level in favourable cases. The energy resolution is typically 1 eV but can approach 0.1 eV if an electron-beam monochromator is used. This review provides an overview of EELS instrumentation and of the physics involved in the scattering of kilovolt electrons in solids. Features of the energy-loss spectrum are discussed, including plasmon peaks, inner-shell ionization edges and fine structure related to the electronic densities of states. Examples are given of the use of EELS for the measurement of local properties, including specimen thickness, mechanical and electronic properties (such as bandgap) and chemical composition. Factors that determine the spatial resolution of the analysis are outlined, including radiation damage to the specimen. Comparisons are made with related techniques, particularly x-ray absorption spectroscopy.

http://iopscience.iop.org/article/10.1088/0034-4885/72/1/016502/pdf

Electron energy-loss spectroscopy in the TEM

One of the biggest obstacles in improving the resolution of the electron microscope has always been the blurring of the image caused by lens aberrations. Here we report a solution to this problem for a medium-voltage electron microscope which gives a stunning enhancement of image quality.

Electron microscopy image enhanced

A spherical-aberration-corrected 200 kV transmission electron microscope

Correction of the spherical aberration of a 200 kV TEM by means of a hexapole-corrector

One of the most challenging tasks for high-resolution electron microscopy is the investigation of the atomic structure of defects, interfaces, and grain boundaries. In particular, the application of thin films in electronic devices requires detailed knowledge of the microstructure, which can influence the electronic and optical properties. These tasks require a point resolution down to about 0.1 nm because this enables structure imaging for many semiconductors and metals. The resolution of transmission electron microscopes is limited, besides other parameters, by the spherical aberration coefficient C{sub s} of the objective lens and the wavelength {lambda} of the electrons. Commercial medium-voltage microscopes up to 400 kV offer only a point resolution of 0.16 nm due to the high spherical-aberration constant C{sub s} of the electromagnetic objective lens. Controlling the value of C{sub s} by a corrector lens system can offer the required resolution even at an acceleration voltage of 200 kV. Recently, a lens system for C{sub s}-correction, based on hexapole lenses, has been developed at the European Molecular Biology Laboratory in Heidelberg and incorporated in a commercial 200 kV instrument equipped with a field emission gun. This system allows the C{sub s}-value to be set between +2.0 mm and -0.05 mm.more » For the present investigation, we have adjusted a C{sub s}-value of 50 {mu}m in order to achieve optimum phase contrast, which improved the point resolution to 0.14 nm. Structure imaging can be performed down to atomic distances of 0.14 nm. A further unique advantage of C{sub s} correction is the reduction of contrast delocalization, which is a major obstacle in the interpretation of images of defects and interfaces. The influence of C{sub s} on contrast delocalization is demonstrated for a Si/CoSi{sub 2} interface. The unique combination of a low acceleration voltage and aberration-free imaging down to the information limit offers new prospects for the interpretation of non-periodic structures as defects and interfaces in crystalline materials.« less

Eugen Schwan

Papers

Electron microscopy image enhanced

A spherical-aberration-corrected 200 kV transmission electron microscope

Correction of the spherical aberration of a 200 kV TEM by means of a hexapole-corrector

First application of a spherical-aberration corrected transmission electron microscope in materials science