Ondrej L. Krivanek

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

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 on. 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 optics. 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 Å 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.

Sub-ångstrom resolution using aberration corrected electron optics

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 Å. 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.

Vibrational spectroscopy in the electron microscope

Vibrational spectroscopies using infrared radiation, Raman scattering, neutrons, low-energy electrons and inelastic electron tunnelling are powerful techniques that can analyse bonding arrangements, identify chemical compounds and probe many other important properties of materials. The spatial resolution of these spectroscopies is typically one micrometre or more, although it can reach a few tens of nanometres or even a few ångströms when enhanced by the presence of a sharp metallic tip. If vibrational spectroscopy could be combined with the spatial resolution and flexibility of the transmission electron microscope, it would open up the study of vibrational modes in many different types of nanostructures. Unfortunately, the energy resolution of electron energy loss spectroscopy performed in the electron microscope has until now been too poor to allow such a combination. Recent developments that have improved the attainable energy resolution of electron energy loss spectroscopy in a scanning transmission electron microscope to around ten millielectronvolts now allow vibrational spectroscopy to be carried out in the electron microscope. Here we describe the innovations responsible for the progress, and present examples of applications in inorganic and organic materials, including the detection of hydrogen. We also demonstrate that the vibrational signal has both high- and low-spatial-resolution components, that the first component can be used to map vibrational features at nanometre-level resolution, and that the second component can be used for analysis carried out with the beam positioned just outside the sample—that is, for ‘aloof’ spectroscopy that largely avoids radiation damage.

Elnes of 3d transition-metal oxides: II. Variations with oxidation state and crystal structure

Abstract The energy-loss near-edge structure (ELNES) in spectra from transition-metal oxides varies with the oxidation state of the metal, and with the crystal structure. This makes electron energy-loss spectroscopy (EELS) a powerful technique for probing these properties. The information provided is particularly rich when the energy resolution is better than 0.5 eV.

Towards sub-0.5 Å electron beams

In the 4 years since the previous meeting in the SALSA series, aberration correction has progressed from a promising concept to a powerful research tool. We summarize the factors that have enabled 100-120kV scanning transmission electron microscopes to achieve sub-A resolution, and to increase the current available in an atom-sized probe by a factor of 10 and more. Once C(s) is corrected, fifth-order spherical aberration (C(5)) and chromatic aberration (C(c)) pose new limits on resolution. We describe a quadrupole/octupole corrector of a new design, which will correct all fifth-order aberrations while introducing less than 0.2mm of additional C(c). Coupled to an optimized STEM column, the new corrector promises to lead to routine sub-A electron probes at 100kV, and to sub-0.5A probes at higher operating voltages.

High-energy-resolution monochromator for aberration-corrected scanning transmission electron microscopy/electron energy-loss spectroscopy

An all-magnetic monochromator/spectrometer system for sub-30 meV energy-resolution electron energy-loss spectroscopy in the scanning transmission electron microscope is described. It will link the energy being selected by the monochromator to the energy being analysed by the spectrometer, without resorting to decelerating the electron beam. This will allow it to attain spectral energy stability comparable to systems using monochromators and spectrometers that are raised to near the high voltage of the instrument. It will also be able to correct the chromatic aberration of the probe-forming column. It should be able to provide variable energy resolution down to approximately 10 meV and spatial resolution less than 1 Å.

Elnes of 3d transition-metal oxides: I. Variations across the periodic table

Abstract Nearly all transition-metal oxides show interesting multiplet splittings in energy-loss near-edge structure (ELNES) of the metal L2,3 edge. The multiplet structure only becomes apparent at an energy resolution of 0.5 eV or better. It is due to atomic as well as solid-state effects. Together with the ELNES of the oxygen K edge, it can be used to provide rich information about these technologically important materials.

Applications of a post-column imaging filter in biology and materials science

We have developed an energy-selecting imaging filter which can be attached to most transmission electron microscopes, and is capable of operating at primary energies of up to 400 keV. We review the filters design and operation, and illustrate them with several applications including imaging of thick biological materials, energy-filtered diffraction, energy-filtered high-resolution imaging, and elemental mapping. We conclude the paper with a discussion of the areas of transmission electron microscopy in which the filter is likely to make especially significant contributions.

Monochromated STEM with a 30 meV-wide, atom-sized electron probe

The origins and the recent accomplishments of aberration correction in scanning transmission electron microscopy (STEM) are reviewed. It is remembered that the successful correction of imaging aberrations of round lenses owes much to the successful correction of spectrum aberrations achieved in electron energy loss spectrometers 2-3 decades earlier. Two noteworthy examples of the types of STEM investigation that aberration correction has made possible are shown: imaging of single-atom impurities in graphene and analyzing atomic bonding of single atoms by electron energy loss spectroscopy (EELS). Looking towards the future, a new all-magnetic monochromator is described. The monochromator uses several of the principles pioneered in round lens aberration correction, and it employs stabilization schemes that make it immune to variations in the high voltage of the microscope and in the monochromator main prism current. Tests of the monochromator carried out at 60 keV have demonstrated energy resolution as good as 12 meV and monochromated probe size of ∼1.2 Å. These results were obtained in separate experiments, but they indicate that the instrument can perform imaging and EELS with an atom-sized probe <30 meV wide in energy, and that an improvement in energy resolution to 10 meV and beyond should be possible in the future.

An imaging filter for biological applications

A recently developed post-column imaging filter optimized for biological electron microscopy is described. The filter uses a single magnetic prism, four strong quadrupole lenses and five sextupole lenses to form images and spectra free of all important aberrations and distortions of first and second order. The performance of the filter is illustrated with practical applications. It is shown that the filter offers several important advantages over currently existing in-column filters, particularly in the areas of imaging at low magnifications, attainable collection efficiency, energy resolution, and general spectroscopic operation.