Transmission Electron Microscopy Measurements of Ge Nanowire Synthesis with Liquid Metal Nanodroplets in Water.

Quintin Cheek, Eli Fahrenkrug, Sofiya Hlynchuk, Daan Hein Alsem, Norman J Salmon, Stephen Maldonado
Author Information
  1. Quintin Cheek: Department of Chemistry, University of Michigan, 930 N. University, Ann Arbor, Michigan 48109-1055, United States.
  2. Eli Fahrenkrug: Department of Chemistry, Colorado College, 14 East Cache la Poudre St., Colorado Springs, Colorado 80903, United States. ORCID
  3. Sofiya Hlynchuk: Department of Chemistry, University of Michigan, 930 N. University, Ann Arbor, Michigan 48109-1055, United States.
  4. Daan Hein Alsem: Hummingbird Scientific, 2610 Willamette Drive NE, Suite A, Lacey, Washington 98516, United States.
  5. Norman J Salmon: Hummingbird Scientific, 2610 Willamette Drive NE, Suite A, Lacey, Washington 98516, United States.
  6. Stephen Maldonado: Department of Chemistry, University of Michigan, 930 N. University, Ann Arbor, Michigan 48109-1055, United States. ORCID

Abstract

The growth of Ge nanowires in water inside a liquid transmission electron microscope (TEM) holder has been demonstrated at room temperature. Each nanowire growth event was stimulated by the incident electron beam on otherwise unsupported liquid Ga or liquid In nanodroplets. A variety of conditions were explored, including liquid metal nanodroplet surface condition, liquid metal nanodroplet size and density, formal concentration of dissolved GeO, and electron beam intensity. The cumulative observations from a series of videos recorded during growth events suggested the following points. First, the conditions necessary for initiating nanowire growth at uncontacted liquid metal nanodroplets in a liquid TEM cell indicate the process was governed by solvated electrons generated from secondary electrons scattered by the liquid metal nanodroplets. The attained current densities were comparable to those achieved in conventional electrochemical liquid-liquid-solid (ec-LLS) growths outside of a TEM. Second, the surface condition of the liquid metal nanodroplets was quite influential on whether nanowire growth occurred and surface diffusion of Ge adatoms contributed to the rate of crystallization. Third, the Ge nanowire growth rates were limited by the feed rate of Ge to the crystal growth front rather than the rate of crystallization at the liquid metal/solid Ge interface. Estimates of an electrochemical current for the reduction of dissolved GeO were nominally in line with currents used for Ge nanowire growth by ec-LLS outside of the TEM. Fourth, the Ge nanowire growths in the liquid TEM cell occurred far from thermodynamic equilibrium, with supersaturation values of 10 prior to nucleation. These collective points provide insight on how to further control and improve Ge nanowire morphology and crystallographic quality by the ec-LLS method.

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