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In Situ Electron Energy-Loss Spectroscopy in Liquids

Published online by Cambridge University Press:  31 May 2013

Megan E. Holtz ,
Yingchao Yu ,
Jie Gao ,
Héctor D. Abruña  and
David A. Muller
Megan E. Holtz*
Affiliation:
School of Applied and Engineering Physics, Cornell University, Ithaca, NY 14850, USA
Yingchao Yu
Affiliation:
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14850, USA
Jie Gao
Affiliation:
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14850, USA
Héctor D. Abruña
Affiliation:
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14850, USA
David A. Muller
Affiliation:
School of Applied and Engineering Physics, Cornell University, Ithaca, NY 14850, USA Kavli Institute at Cornell for Nanoscale Science, Cornell University, Ithaca, NY 14850, USA
*
*Corresponding author. E-mail: meh282@cornell.edu
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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.

Keywords

STEMEELSEFTEMliquidin situenvironmentalCuSO4LiFePO4
Type
Materials Applications
Information
Microscopy and Microanalysis , Volume 19 , Issue 4 , August 2013 , pp. 1027 - 1035
Copyright
Copyright © Microscopy Society of America 2013 

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