The identification of isotopic labels by conventional macroscopic techniques lacks spatial resolution and requires relatively large quantities of material for measurements. We recorded the ...vibrational spectra of an α amino acid, l-alanine, with damage-free "aloof" electron energy-loss spectroscopy in a scanning transmission electron microscope to directly resolve carbon-site-specific isotopic labels in real space with nanoscale spatial resolution. An isotopic red shift of 4.8 ± 0.4 milli-electron volts in C-O asymmetric stretching modes was observed for
C-labeled l-alanine at the carboxylate carbon site, which was confirmed by macroscopic infrared spectroscopy and theoretical calculations. The accurate measurement of this shift opens the door to nondestructive, site-specific, spatially resolved identification of isotopically labeled molecules with the electron microscope.
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.
Vibrational spectroscopy in the electron microscope would be transformative in the study of biological samples, provided that radiation damage could be prevented. However, electron beams typically ...create high-energy excitations that severely accelerate sample degradation. Here this major difficulty is overcome using an 'aloof' electron beam, positioned tens of nanometres away from the sample: high-energy excitations are suppressed, while vibrational modes of energies <1 eV can be 'safely' investigated. To demonstrate the potential of aloof spectroscopy, we record electron energy loss spectra from biogenic guanine crystals in their native state, resolving their characteristic C-H, N-H and C=O vibrational signatures with no observable radiation damage. The technique opens up the possibility of non-damaging compositional analyses of organic functional groups, including non-crystalline biological materials, at a spatial resolution of ∼10 nm, simultaneously combined with imaging in the electron microscope.
Vibrational modes affect fundamental physical properties such as the conduction of sound and heat and can be sensitive to nano- and atomic-scale structure. Probing the momentum transfer dependence of ...vibrational modes provides a wealth of information about a materials system; however, experimental work has been limited to essentially bulk and averaged surface approaches or to small wave vectors. We demonstrate a combined experimental and theoretical methodology for nanoscale mapping of optical and acoustic phonons across the first Brillouin zone, in the electron microscope, probing a volume ~10
to 10
times smaller than that of comparable bulk and surface techniques. In combination with more conventional electron microscopy techniques, the presented methodology should allow for direct correlation of nanoscale vibrational mode dispersions with atomic-scale structure and chemistry.
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.
Some four decades were needed to catch up with the vision that Albert Crewe and his group had for the scanning transmission electron microscope (STEM) in the nineteen sixties and seventies: attaining ...0.5Å resolution, and identifying single atoms spectroscopically. With these goals now attained, STEM developments are turning toward new directions, such as rapid atomic resolution imaging and exploring atomic bonding and electronic properties of samples at atomic resolution. The accomplishments and the future challenges are reviewed and illustrated with practical examples.
► TV-rate STEM imaging of heavy atoms is demonstrated. ► DNA sequencing by STEM dark field imaging should be possible at a rate of 106bases/s. ► Individual silicon atom impurities in graphene are imaged atom-by-atom. ► Single atoms of nitrogen and boron incorporated in graphene are imaged spectroscopically. ► Bonding of individual atoms can be probed by analyzing the fine structures of their EEL spectra.
Nature Communications 7, Article number: 10945 (2016); Published: 10 March 2016; Updated: 4 May 2016 The author Hagai Cohen is incorrectly omitted from the list of corresponding authors. The ...corresponding authors are Peter Rez and Hagai Cohen. The correct information for correspondence is: ‘Correspondence and requests for materials should be addressed to P.
We propose a practical method of producing a single mode electron vortex beam suitable for use in a scanning transmission electron microscope (STEM). The method involves using a holographic “fork” ...aperture to produce a row of beams of different orbital angular momenta, as is now well established, magnifying the row so that neighboring beams are separated by about 1 µm, selecting the desired beam with a narrow slit, and demagnifying the selected beam down to 1–2 Å in size. We show that the method can be implemented by adding two condenser lenses plus a selection slit to a straight-column cold-field emission STEM. It can also be carried out in an existing instrument, the monochromated Nion high-energy-resolution monochromated electron energy-loss spectroscopy-STEM, by using its monochromator in a novel way. We estimate that atom-sized vortex beams with ≥20 pA of current should be attainable at 100–200 keV in either instrument.
Crystal defects affect the thermal and heat-transport properties of materials by scattering phonons and modifying phonon spectra
. To appreciate how imperfections in solids influence thermal ...conductivity and diffusivity, it is thus essential to understand phonon-defect interactions. Sophisticated theories are available to explore such interactions, but experimental validation is limited because most phonon-detecting spectroscopic methods do not reach the high spatial resolution needed to resolve local vibrational spectra near individual defects. Here we demonstrate that space- and angle-resolved vibrational spectroscopy in a transmission electron microscope makes it possible to map the vibrational spectra of individual crystal defects. We detect a red shift of several millielectronvolts in the energy of acoustic vibration modes near a single stacking fault in cubic silicon carbide, together with substantial changes in their intensity, and find that these changes are confined to within a few nanometres of the stacking fault. These observations illustrate that the capabilities of a state-of-the-art transmission electron microscope open the door to the direct mapping of phonon propagation around defects, which is expected to provide useful guidance for engineering the thermal properties of materials.
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