In Situ Electron Energy-Loss Spectroscopy in Liquids

Holtz, Megan E., Yingchao Yu, Hector D. Abruna and David Muller, 2013
Poseidon Select TEM holder tip
Image courtesy of Microsc Microanal

Abstract

In situ scanning transmission electron microscopy (STEM) through liquids is a promising approach for exploring biological and materials processes. However, options for in situ chemical identification are limited: X-ray analysis is precluded because the liquid cell holder shadows the detector and electron energy-loss spectroscopy (EELS) is degraded by multiple scattering events in thick layers. Here, we explore the limits of EELS in the study of chemical reactions in their native environments in real time and on the nanometer scale. The determination of the local electron density, optical gap, and thickness of the liquid layer by valence EELS is demonstrated. By comparing theoretical and experimental plasmon energies, we find that liquids appear to follow the free-electron model that has been previously established for solids. Signals at energies below the optical gap and plasmon energy of the liquid provide a high signal-to-background ratio regime as demonstrated for LiFePO4 in an aqueous solution. The potential for the use of valence EELS to understand in situ STEM reactions is demonstrated for beam-induced deposition of metallic copper: as copper clusters grow, EELS develops low-loss peaks corresponding to metallic copper. From these techniques, in situ imaging and valence EELS offer insights into the local electronic structure of nanoparticles and chemical reactions.

Impact Statement

Paper demonstrates how in situ EELS can benefit materials analysis in both spectroscopy and imaging (EFTEM) modes for liquid electron microscopy. The capabilities of EELS in liquid are examined, and core and low-loss areas of the EELS spectrum are evaluated as a function of liquid thickness. EFTEM imaging in the low and zero-loss region is also discussed.
Keywords: Nanoparticles; EELS