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Nanoparticle Shape Evolution and Proximity Effects During Tip-Induced Electrochemical Processes.

Sang Mo Yang1,2,3, Mariappan Parans Paranthaman4, Tae Won Noh2,3

  • 1Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.

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Summary

Scanning probe microscopy reveals nonlocal electrochemical dynamics in silver particle chains. Anomalous particle growth and fractal shapes indicate proximity effects and changing growth-limiting processes during nanoscale electrochemical investigations.

Keywords:
diffusion-limited aggregationelectrochemistryfractalproximity effectscanning probe microscopysilver

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Area of Science:

  • Electrochemistry
  • Materials Science
  • Nanotechnology

Background:

  • Scanning probe microscopy (SPM) voltage spectroscopies are crucial for studying nanoscale electrochemical processes relevant to batteries, fuel cells, catalysts, and memristors.
  • Spatially resolved electrochemical mapping relies on grid-based measurements, where point spacing is critical for understanding functionalities, particularly irreversible ones.

Purpose of the Study:

  • To investigate nonlocal electrochemical dynamics and particle formation in silver (Ag) particle chains fabricated using SPM on a silver ion solid electrolyte.
  • To understand the influence of measurement grid spacing on the resulting Ag particle structures and electrochemical behavior.

Main Methods:

  • Fabrication of silver particle chains using the SPM tip on a silver ion solid electrolyte.
  • Electrochemical spectroscopy performed on a grid of measurement points with varying spacing.
  • Analysis of the size, periodicity, and shape evolution of the formed Ag structures.

Main Results:

  • Anomalous chains of unequally sized Ag particles with double periodicity were observed when grid spacing was small relative to particle size, attributed to a proximity effect.
  • Fractal shape evolution of Ag structures indicated a transition in the growth-limiting process from Ag(+)/Ag redox to Ag(+)-ion diffusion with increased voltage and pulse duration.

Conclusions:

  • Characteristic shapes of electrochemical products serve as indicators for the underlying growth-limiting processes.
  • Complex phenomena, such as anomalous growth and fractal evolution, emerge during spectroscopic mapping of nanoscale electrochemical functionalities, highlighting the importance of parameter control.