Title: Self-consistent modeling of electrochemical strain microscopy of solid electrolytes

Abstract

Electrochemical strain microscopy (ESM) employs a strong electromechanical coupling in solid ionic conductors to map ionic transport and electrochemical processes with nanometer-scale spatial resolution. To elucidate the mechanisms of the ESM image formation, we performed self-consistent numerical modeling of the electromechanical response in solid electrolytes under the probe tip in a linear, small-signal regime using the Boltzmann–Planck–Nernst–Einstein theory and Vegard's law while taking account of the electromigration and diffusion. We identified the characteristic time scales involved in the formation of the ESM response and found that the dynamics of the charge carriers in the tip-electrolyte system with blocking interfaces can be described as charging of the diffuse layer at the tip-electrolyte interface through the tip contact spreading resistance. At the high frequencies used in the detection regime, the distribution of the charge carriers under the tip is governed by evanescent concentration waves generated at the tip-electrolyte interface. The ion drift length in the electric field produced by the tip determines the ESM response at high frequencies, which follows a 1/f asymptotic law. The electronic conductivity, as well as the electron transport through the electrode-electrolyte interface, do not have a significant effect on the ESM signal in the detection regime. Themore » results indicate, however, that for typical solid electrolytes at room temperature, the ESM response originates at and contains information about the very surface layer of a sample, and the properties of the one-unit-cell-thick surface layer may significantly contribute to the ESM response, implying a high surface sensitivity and a high lateral resolution of the technique. On the other hand, it follows that a rigorous analysis of the ESM signals requires techniques that account for the discrete nature of a solid.« less

Authors:

Tselev, Alexander ^[1]; Morozovska, Anna N. ^[2]; Udod, Alexei ^[3]; Eliseev, Eugene A. ^[4]; Kalinin, Sergei V. ^[1]

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+ Show Author Affiliations

1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
2. National Academy of Sciences of Ukraine (NASU), Kiev (Ukraine). Inst. of Physics (ISP)
3. Taras Shevchenko Kiev National Univ., Kiev, Ukraine (United States)
4. National Academy of Sciences of Ukraine (NASU), Kiev (Ukraine). Inst. for Problems of Materials Science

Publication Date:

Fri Oct 10 00:00:00 EDT 2014

Research Org.:

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

1185359

Grant/Contract Number:  

AC05-00OR22725

Resource Type:

Accepted Manuscript

Journal Name:

Nanotechnology

Additional Journal Information:

Journal Volume: 25; Journal Issue: 44; Journal ID: ISSN 0957-4484

Publisher:

IOP Publishing

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; scanning probe microscopy; ionic processes; chemical strain; electrochemical strain microscopy; numerical simulations; frequency response