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Title: Kelvin Probe Force Microscopy in liquid using Electrochemical Force Microscopy

Abstract

Conventional closed loop-Kelvin probe force microscopy (KPFM) has emerged as a powerful technique for probing electric and transport phenomena at the solid-gas interface. The extension of KPFM capabilities to probe electrostatic and electrochemical phenomena at the solid–liquid interface is of interest for a broad range of applications from energy storage to biological systems. However, the operation of KPFM implicitly relies on the presence of a linear lossless dielectric in the probe-sample gap, a condition which is violated for ionically-active liquids (e.g., when diffuse charge dynamics are present). Here, electrostatic and electrochemical measurements are demonstrated in ionically-active (polar isopropanol, milli-Q water and aqueous NaCl) and ionically-inactive (non-polar decane) liquids by electrochemical force microscopy (EcFM), a multidimensional (i.e., bias- and time-resolved) spectroscopy method. In the absence of mobile charges (ambient and non-polar liquids), KPFM and EcFM are both feasible, yielding comparable contact potential difference (CPD) values. In ionically-active liquids, KPFM is not possible and EcFM can be used to measure the dynamic CPD and a rich spectrum of information pertaining to charge screening, ion diffusion, and electrochemical processes (e.g., Faradaic reactions). EcFM measurements conducted in isopropanol and milli-Q water over Au and highly ordered pyrolytic graphite electrodes demonstrate both sample- and solvent-dependentmore » features. Finally, the feasibility of using EcFM as a local force-based mapping technique of material-dependent electrostatic and electrochemical response is investigated. The resultant high dimensional dataset is visualized using a purely statistical approach that does not require a priori physical models, allowing for qualitative mapping of electrostatic and electrochemical material properties at the solid–liquid interface.« less

Authors:
 [1];  [2];  [3];  [2];  [2];  [4];  [1]
  1. Univ. College, Dublin (Ireland). School of Physics and Conway Inst. of Biomolecular and Biomedical Research
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences
  3. Univ. College, Dublin (Ireland). Conway Inst. of Biomolecular and Biomedical Research
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences and Inst. for Functioning Imaging of Materials
Publication Date:
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)
OSTI Identifier:
1185854
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Beilstein Journal of Nanotechnology
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2190-4286
Publisher:
Beilstein Institute
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Collins, Liam, Jesse, Stephen, Kilpatrick, J., Tselev, Alexander, Okatan, Mahmut Baris, Kalinin, Sergei V., and Rodriguez, Brian. Kelvin Probe Force Microscopy in liquid using Electrochemical Force Microscopy. United States: N. p., 2015. Web. doi:10.3762/bjnano.6.19.
Collins, Liam, Jesse, Stephen, Kilpatrick, J., Tselev, Alexander, Okatan, Mahmut Baris, Kalinin, Sergei V., & Rodriguez, Brian. Kelvin Probe Force Microscopy in liquid using Electrochemical Force Microscopy. United States. doi:10.3762/bjnano.6.19.
Collins, Liam, Jesse, Stephen, Kilpatrick, J., Tselev, Alexander, Okatan, Mahmut Baris, Kalinin, Sergei V., and Rodriguez, Brian. Mon . "Kelvin Probe Force Microscopy in liquid using Electrochemical Force Microscopy". United States. doi:10.3762/bjnano.6.19. https://www.osti.gov/servlets/purl/1185854.
@article{osti_1185854,
title = {Kelvin Probe Force Microscopy in liquid using Electrochemical Force Microscopy},
author = {Collins, Liam and Jesse, Stephen and Kilpatrick, J. and Tselev, Alexander and Okatan, Mahmut Baris and Kalinin, Sergei V. and Rodriguez, Brian},
abstractNote = {Conventional closed loop-Kelvin probe force microscopy (KPFM) has emerged as a powerful technique for probing electric and transport phenomena at the solid-gas interface. The extension of KPFM capabilities to probe electrostatic and electrochemical phenomena at the solid–liquid interface is of interest for a broad range of applications from energy storage to biological systems. However, the operation of KPFM implicitly relies on the presence of a linear lossless dielectric in the probe-sample gap, a condition which is violated for ionically-active liquids (e.g., when diffuse charge dynamics are present). Here, electrostatic and electrochemical measurements are demonstrated in ionically-active (polar isopropanol, milli-Q water and aqueous NaCl) and ionically-inactive (non-polar decane) liquids by electrochemical force microscopy (EcFM), a multidimensional (i.e., bias- and time-resolved) spectroscopy method. In the absence of mobile charges (ambient and non-polar liquids), KPFM and EcFM are both feasible, yielding comparable contact potential difference (CPD) values. In ionically-active liquids, KPFM is not possible and EcFM can be used to measure the dynamic CPD and a rich spectrum of information pertaining to charge screening, ion diffusion, and electrochemical processes (e.g., Faradaic reactions). EcFM measurements conducted in isopropanol and milli-Q water over Au and highly ordered pyrolytic graphite electrodes demonstrate both sample- and solvent-dependent features. Finally, the feasibility of using EcFM as a local force-based mapping technique of material-dependent electrostatic and electrochemical response is investigated. The resultant high dimensional dataset is visualized using a purely statistical approach that does not require a priori physical models, allowing for qualitative mapping of electrostatic and electrochemical material properties at the solid–liquid interface.},
doi = {10.3762/bjnano.6.19},
journal = {Beilstein Journal of Nanotechnology},
number = ,
volume = 6,
place = {United States},
year = {2015},
month = {1}
}

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