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Title: Nanoparticle shape evolution and proximity effects during tip-induced electrochemical processes

Abstract

The voltage spectroscopies in scanning probe microscopy (SPM) techniques are widely used to investigate the electrochemical processes in nanoscale volumes, which are important for current key applications, such as batteries, fuel cells, catalysts, and memristors. The spectroscopic measurements are commonly performed on a grid of multiple points to yield spatially resolved maps of reversible and irreversible electrochemical functionalities. Hence, the spacing between measurement points is an important parameter to be considered, especially for irreversible electrochemical processes. Here, we report nonlocal electrochemical dynamics in chains of Ag particles fabricated by the SPM tip on a silver ion solid electrolyte. When the grid spacing is small compared with the size of the formed Ag particles, anomalous chains of unequally sized particles with double periodicity evolve. This behavior is ascribed to a proximity effect during the tip-induced electrochemical process, specifically, size-dependent silver particle growth following the contact between the particles. In addition, fractal shape evolution of the formed Ag structures indicates that the growth-limiting process changes from Ag+/Ag redox reaction to Ag+-ion diffusion with the increase in the applied voltage and pulse duration. Our study shows that characteristic shapes of the electrochemical products are good indicators for determining the underlying growth-limiting process, andmore » emergence of complex phenomena during spectroscopic mapping of electrochemical functionalities.« less

Authors:
 [1];  [2];  [3];  [2];  [2]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Inst. for Basic Science (IBS), Seoul (Korea, Republic of)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Seoul National University, South Korea; Inst. of Basic Science, Seoul (Korea, Republic of)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1237153
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; scanning probe microscopy; electrochemistry; silver; proximity effect; fractal; diffusion-limited aggregation

Citation Formats

Yang, Sangmo, Paranthaman, Mariappan Parans, Noh, Tae Won, Kalinin, Sergei V., and Strelcov, Evgheni. Nanoparticle shape evolution and proximity effects during tip-induced electrochemical processes. United States: N. p., 2016. Web. https://doi.org/10.1021/acsnano.5b05686.
Yang, Sangmo, Paranthaman, Mariappan Parans, Noh, Tae Won, Kalinin, Sergei V., & Strelcov, Evgheni. Nanoparticle shape evolution and proximity effects during tip-induced electrochemical processes. United States. https://doi.org/10.1021/acsnano.5b05686
Yang, Sangmo, Paranthaman, Mariappan Parans, Noh, Tae Won, Kalinin, Sergei V., and Strelcov, Evgheni. Fri . "Nanoparticle shape evolution and proximity effects during tip-induced electrochemical processes". United States. https://doi.org/10.1021/acsnano.5b05686. https://www.osti.gov/servlets/purl/1237153.
@article{osti_1237153,
title = {Nanoparticle shape evolution and proximity effects during tip-induced electrochemical processes},
author = {Yang, Sangmo and Paranthaman, Mariappan Parans and Noh, Tae Won and Kalinin, Sergei V. and Strelcov, Evgheni},
abstractNote = {The voltage spectroscopies in scanning probe microscopy (SPM) techniques are widely used to investigate the electrochemical processes in nanoscale volumes, which are important for current key applications, such as batteries, fuel cells, catalysts, and memristors. The spectroscopic measurements are commonly performed on a grid of multiple points to yield spatially resolved maps of reversible and irreversible electrochemical functionalities. Hence, the spacing between measurement points is an important parameter to be considered, especially for irreversible electrochemical processes. Here, we report nonlocal electrochemical dynamics in chains of Ag particles fabricated by the SPM tip on a silver ion solid electrolyte. When the grid spacing is small compared with the size of the formed Ag particles, anomalous chains of unequally sized particles with double periodicity evolve. This behavior is ascribed to a proximity effect during the tip-induced electrochemical process, specifically, size-dependent silver particle growth following the contact between the particles. In addition, fractal shape evolution of the formed Ag structures indicates that the growth-limiting process changes from Ag+/Ag redox reaction to Ag+-ion diffusion with the increase in the applied voltage and pulse duration. Our study shows that characteristic shapes of the electrochemical products are good indicators for determining the underlying growth-limiting process, and emergence of complex phenomena during spectroscopic mapping of electrochemical functionalities.},
doi = {10.1021/acsnano.5b05686},
journal = {ACS Nano},
number = 1,
volume = 10,
place = {United States},
year = {2016},
month = {1}
}

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Works referenced in this record:

Challenges for Rechargeable Li Batteries
journal, February 2010

  • Goodenough, John B.; Kim, Youngsik
  • Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
  • DOI: 10.1021/cm901452z

Issues and challenges facing rechargeable lithium batteries
journal, November 2001

  • Tarascon, J.-M.; Armand, M.
  • Nature, Vol. 414, Issue 6861, p. 359-367
  • DOI: 10.1038/35104644

Review on Li–air batteries—Opportunities, limitations and perspective
journal, February 2011


Lowering the Temperature of Solid Oxide Fuel Cells
journal, November 2011


Factors Governing Oxygen Reduction in Solid Oxide Fuel Cell Cathodes
journal, October 2004


TiO 2 —a prototypical memristive material
journal, May 2011


Electrochemical metallization memories—fundamentals, applications, prospects
journal, May 2011


Atomically controlled electrochemical nucleation at superionic solid electrolyte surfaces
journal, April 2012

  • Valov, Ilia; Sapezanskaia, Ina; Nayak, Alpana
  • Nature Materials, Vol. 11, Issue 6
  • DOI: 10.1038/nmat3307

Decoupling Electrochemical Reaction and Diffusion Processes in Ionically-Conductive Solids on the Nanometer Scale
journal, November 2010

  • Balke, Nina; Jesse, Stephen; Kim, Yoongu
  • ACS Nano, Vol. 4, Issue 12
  • DOI: 10.1021/nn101502x

Real Space Mapping of Li-Ion Transport in Amorphous Si Anodes with Nanometer Resolution
journal, September 2010

  • Balke, Nina; Jesse, Stephen; Kim, Yoongu
  • Nano Letters, Vol. 10, Issue 9
  • DOI: 10.1021/nl101439x

Nanoscale mapping of ion diffusion in a lithium-ion battery cathode
journal, August 2010


Probing Surface and Bulk Electrochemical Processes on the LaAlO 3 –SrTiO 3 Interface
journal, April 2012

  • Kumar, Amit; Arruda, Thomas M.; Kim, Yunseok
  • ACS Nano, Vol. 6, Issue 5
  • DOI: 10.1021/nn204960c

Mapping Irreversible Electrochemical Processes on the Nanoscale: Ionic Phenomena in Li Ion Conductive Glass Ceramics
journal, October 2011

  • Arruda, Thomas M.; Kumar, Amit; Kalinin, Sergei V.
  • Nano Letters, Vol. 11, Issue 10
  • DOI: 10.1021/nl202039v

The partially reversible formation of Li-metal particles on a solid Li electrolyte: applications toward nanobatteries
journal, July 2012


Measuring oxygen reduction/evolution reactions on the nanoscale
journal, August 2011

  • Kumar, Amit; Ciucci, Francesco; Morozovska, Anna N.
  • Nature Chemistry, Vol. 3, Issue 9
  • DOI: 10.1038/nchem.1112

Humidity Effect on Nanoscale Electrochemistry in Solid Silver Ion Conductors and the Dual Nature of Its Locality
journal, January 2015

  • Yang, Sang Mo; Strelcov, Evgheni; Paranthaman, M. Parans
  • Nano Letters, Vol. 15, Issue 2
  • DOI: 10.1021/nl5040286

Probing Local Ionic Dynamics in Functional Oxides at the Nanoscale
journal, July 2013

  • Strelcov, Evgheni; Kim, Yunseok; Jesse, Stephen
  • Nano Letters, Vol. 13, Issue 8
  • DOI: 10.1021/nl400780d

Correlative Multimodal Probing of Ionically-Mediated Electromechanical Phenomena in Simple Oxides
journal, October 2013

  • Kim, Yunseok; Strelcov, Evgheni; Hwang, In Rok
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep02924

Intermittency, quasiperiodicity and chaos in probe-induced ferroelectric domain switching
journal, November 2013

  • Ievlev, A. V.; Jesse, S.; Morozovska, A. N.
  • Nature Physics, Vol. 10, Issue 1, p. 59-66
  • DOI: 10.1038/nphys2796

Piezoresponse force microscopy and recent advances in nanoscale studies of ferroelectrics
journal, January 2006


Nanoelectromechanics of polarization switching in piezoresponse force microscopy
journal, April 2005

  • Kalinin, S. V.; Gruverman, A.; Rodriguez, B. J.
  • Journal of Applied Physics, Vol. 97, Issue 7
  • DOI: 10.1063/1.1866483

Local polarization dynamics in ferroelectric materials
journal, April 2010

  • Kalinin, Sergei V.; Morozovska, Anna N.; Chen, Long Qing
  • Reports on Progress in Physics, Vol. 73, Issue 5, Article No. 056502
  • DOI: 10.1088/0034-4885/73/5/056502

Nanoscale ferroelectrics: processing, characterization and future trends
journal, July 2006


Bulk and surface nucleation processes in Ag 2 S conductance switches
journal, September 2011


Rate-Limiting Processes Determining the Switching Time in a Ag 2 S Atomic Switch
journal, January 2010

  • Nayak, Alpana; Tamura, Takuro; Tsuruoka, Tohru
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 3
  • DOI: 10.1021/jz900375a

Short-term plasticity and long-term potentiation mimicked in single inorganic synapses
journal, June 2011

  • Ohno, Takeo; Hasegawa, Tsuyoshi; Tsuruoka, Tohru
  • Nature Materials, Vol. 10, Issue 8
  • DOI: 10.1038/nmat3054

Towards a quantitative description of solid electrolyte conductance switches
journal, January 2010

  • Morales-Masis, Monica; Wiemhöfer, Hans-Dieter; van Ruitenbeek, Jan M.
  • Nanoscale, Vol. 2, Issue 10
  • DOI: 10.1039/c0nr00298d

Second harmonic detection in the electrochemical strain microscopy of Ag-ion conducting glass
journal, November 2014

  • Yang, Sang Mo; Baris Okatan, M.; Parans Paranthaman, M.
  • Applied Physics Letters, Vol. 105, Issue 19
  • DOI: 10.1063/1.4901736

Diffusion-Limited Aggregation with Active Edge Diffusion
journal, April 1995


Mechanism of the transition from fractal to dendritic growth of surface aggregates
journal, June 1994

  • Brune, Harald; Romainczyk, Christoph; Röder, Holger
  • Nature, Vol. 369, Issue 6480
  • DOI: 10.1038/369469a0

Diffusion-Limited Aggregation, a Kinetic Critical Phenomenon
journal, November 1981


Diffusion-limited aggregation
journal, May 1983


Diffusion‐Limited Aggregation: A Model for Pattern Formation
journal, November 2000


Radius, perimeter, and density profile for percolation clusters and lattice animals
journal, December 1979

  • Peters, H. P.; Stauffer, D.; H�lters, H. P.
  • Zeitschrift f�r Physik B Condensed Matter and Quanta, Vol. 34, Issue 4
  • DOI: 10.1007/BF01325205

Fractal growth processes
journal, August 1986


Fractal growth of copper electrodeposits
journal, May 1984


Fractal Structures of Zinc Metal Leaves Grown by Electrodeposition
journal, July 1984


Fractal Dimension of Dielectric Breakdown
journal, March 1984


Fractal patterns from chemical dissolution
journal, January 1987

  • Daccord, Gérard; Lenormand, Roland
  • Nature, Vol. 325, Issue 6099
  • DOI: 10.1038/325041a0

Formation of Fractal Clusters and Networks by Irreversible Diffusion-Limited Aggregation
journal, September 1983


Computer Simulation of Dendritic Electrodeposition
journal, January 1985

  • Voss, Richard F.
  • Journal of The Electrochemical Society, Vol. 132, Issue 2
  • DOI: 10.1149/1.2113841

Quantitative Description of Crystal Nucleation and Growth from in Situ Liquid Scanning Transmission Electron Microscopy
journal, October 2015


WSXM : A software for scanning probe microscopy and a tool for nanotechnology
journal, January 2007

  • Horcas, I.; Fernández, R.; Gómez-Rodríguez, J. M.
  • Review of Scientific Instruments, Vol. 78, Issue 1
  • DOI: 10.1063/1.2432410

    Works referencing / citing this record:

    Advanced oxidation scanning probe lithography
    journal, March 2017