Surprising microscopy subtleties: measuring picoscale thicknesses, visualizing core orbitals, and detecting charge transfer using the TEM

Abstract

50 years ago, Richard Feynman delivered a now-famous address outlining why there was ''plenty of room left at the bottom'': there remained much progress to be made in seeing and manipulating matter all the way down to the atomic scale. One of many means to that end, argued Feynman, was to make electron microscopes better. Why could not electrons with wavelengths of a few picometers not be used to clearly image atoms hundreds of picometers in size? Why could not electron beams be used to pattern miniscule wires a handful of metal atoms across? Over the course of decades, Feynman’s vision has been pursued zealously with rich reward, not least in the electron microscopy field. Enabled by the development of bright field-emission electron sources, high-resolution polepieces, and now aberration correctors, transmission electron microscopy (TEM) at atomic resolution has become routine. Seemingly, there is little room left at the bottom; after all, once you can clearly see atoms, what more is there left to do? Thankfully, there is plenty. Much of the hard work has been in the development of equipment that expands TEM to allow unprecedented spatially resolved analysis of elemental composition, inelastic scattering, and temporal processes. But there are also many opportunities to uncover new information using now widely available techniques and equipment. In the studies presented here, there has been some success in following the latter path. In tandem with careful computational analysis, selected-area electron diffraction allows not only determination of crystal symmetry, lattice parameter, and microstructure, but also measurements of material thickness on the scale of atomic layers. Supported by careful data processing and rigorous simulations, spatially resolved X-ray spectroscopy data is converted into real-space measurements of core-level electronic orbitals, in addition to providing routine atomic resolution chemical mapping. And aided by the development of novel bonding-inclusive TEM simulations, the detection of chemical bonding using nominally bonding-independent high-angle elastic scattering is both theoretically predicted and experimentally observed. Even once you have gone all the way down to the bottom, there is still a wide world of wonders left to explore.