Imaging Vibrational Excitations in the Electron Microscope

Abstract

Vibrational spectroscopy is a powerful tool for probing atomic motions in molecules and extended solids. Recent advances in aberration-corrected, monochromated-scanning transmission electron microscopy (STEM) now allow imaging of individual phonon modes at the nanoscale, overcoming the spatial limit imposed by diffraction-limited optical spectroscopy techniques. In this Perspective, we summarize the recent progress in high-resolution electron energy-loss spectroscopy (EELS), which now enables vibrational spectroscopy to be performed in the electron microscope. The high spatial and energy resolution of low-loss EELS can be used to directly image phonons inside or near inorganic and organic materials without considerable sample damage. Monochromated EELS can furthermore resolve isotope specific vibrational signatures and phonon modes arising from single-atom dopants. In parallel with these advances, we highlight the ability of spatial- and momentum-resolved EELS to measure the phonon dispersions at material interfaces, obtaining valuable knowledge about interfacial thermal and electrical transport phenomena. Before concluding, we illustrate how imaging infrared (IR) plasmons at high spatial resolution deepens our understanding of how plasmons interact with molecular vibrations. Taken together, these diverse studies illustrate the capability of monochromated STEM-EELS to image low-energy phonon and plasmon excitations at the nanoscale and the new insights from these studies can be leveraged to engineer the specific material properties needed for next-generation devices.