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Title: Locally Controlled Cu-Ion Transport in Layered Ferroelectric CuInP 2S 6

Abstract

Metal thiophosphates are gaining attention in the context of quasi-two-dimensional van der Waals functional materials. Alkali thiophosphates are investigated as ion conductors for solid electrolytes, and transition-metal thiophosphates are explored as a new class of ferroelectric materials. For the latter, a representative copper indium thiophosphate is ferrielectric at room temperature and, despite low polarization, exhibits giant negative electrostrictive coefficients. In this work, we reveal that ionic conductivity in this material enables localized extraction of Cu ions from the lattice with a biased scanning probe microscopy tip, which is surprisingly reversible. The ionic conduction is tracked through local volume changes with a scanning probe microscopy tip providing a current-free probing technique, which can be explored for other thiophosphates of interest. Nearly 90 nm-tall crystallites can be formed and erased reversibly on the surface of this material as a result of ionic motion, the size of which can be sensitively controlled by both magnitude and frequency of the electric field, as well as the ambient temperature. These experimental results and density functional theory calculations point to a remarkable resilience of CuInP 2S 6 to large-scale ionic displacement and Cu vacancies, in part enabled by the metastability of Cu-deficient phases. Moreover, we havemore » found that the piezoelectric response of CuInP 2S 6 is enhanced by about 45% when a slight ionic modification is carried out with applied field. This new mode of modifying the lattice of CuInP 2S 6, and more generally ionically conducting thiophosphates, posits new prospects for their applications in van der Waals heterostructures, possibly in the context of catalytic or electronic functionalities.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [4]; ORCiD logo [5];  [1]; ORCiD logo [1];  [3]; ORCiD logo [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. College Dublin (Ireland)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Vanderbilt Univ., Nashville, TN (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Air Force Research Lab. (AFRL), Wright-Patterson AFB, OH (United States)
  5. Univ. College Dublin (Ireland)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Vanderbilt Univ., Nashville, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC)
OSTI Identifier:
1543692
Alternate Identifier(s):
OSTI ID: 1597901
Grant/Contract Number:  
AC02-05CH11231; FG02-09ER46554
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 32; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; transition-metal chalcogenophosphate; copper indium thiophosphate; layered ferroelectric; ionic transport; scanning probe microscopy

Citation Formats

Balke, Nina, Neumayer, Sabine M., Brehm, John A., Susner, Michael A., Rodriguez, Brian J., Jesse, Stephen, Kalinin, Sergei V., Pantelides, Sokrates T., McGuire, Michael A., and Maksymovych, Petro. Locally Controlled Cu-Ion Transport in Layered Ferroelectric CuInP2S6. United States: N. p., 2018. Web. doi:10.1021/acsami.8b08079.
Balke, Nina, Neumayer, Sabine M., Brehm, John A., Susner, Michael A., Rodriguez, Brian J., Jesse, Stephen, Kalinin, Sergei V., Pantelides, Sokrates T., McGuire, Michael A., & Maksymovych, Petro. Locally Controlled Cu-Ion Transport in Layered Ferroelectric CuInP2S6. United States. doi:10.1021/acsami.8b08079.
Balke, Nina, Neumayer, Sabine M., Brehm, John A., Susner, Michael A., Rodriguez, Brian J., Jesse, Stephen, Kalinin, Sergei V., Pantelides, Sokrates T., McGuire, Michael A., and Maksymovych, Petro. Mon . "Locally Controlled Cu-Ion Transport in Layered Ferroelectric CuInP2S6". United States. doi:10.1021/acsami.8b08079. https://www.osti.gov/servlets/purl/1543692.
@article{osti_1543692,
title = {Locally Controlled Cu-Ion Transport in Layered Ferroelectric CuInP2S6},
author = {Balke, Nina and Neumayer, Sabine M. and Brehm, John A. and Susner, Michael A. and Rodriguez, Brian J. and Jesse, Stephen and Kalinin, Sergei V. and Pantelides, Sokrates T. and McGuire, Michael A. and Maksymovych, Petro},
abstractNote = {Metal thiophosphates are gaining attention in the context of quasi-two-dimensional van der Waals functional materials. Alkali thiophosphates are investigated as ion conductors for solid electrolytes, and transition-metal thiophosphates are explored as a new class of ferroelectric materials. For the latter, a representative copper indium thiophosphate is ferrielectric at room temperature and, despite low polarization, exhibits giant negative electrostrictive coefficients. In this work, we reveal that ionic conductivity in this material enables localized extraction of Cu ions from the lattice with a biased scanning probe microscopy tip, which is surprisingly reversible. The ionic conduction is tracked through local volume changes with a scanning probe microscopy tip providing a current-free probing technique, which can be explored for other thiophosphates of interest. Nearly 90 nm-tall crystallites can be formed and erased reversibly on the surface of this material as a result of ionic motion, the size of which can be sensitively controlled by both magnitude and frequency of the electric field, as well as the ambient temperature. These experimental results and density functional theory calculations point to a remarkable resilience of CuInP2S6 to large-scale ionic displacement and Cu vacancies, in part enabled by the metastability of Cu-deficient phases. Moreover, we have found that the piezoelectric response of CuInP2S6 is enhanced by about 45% when a slight ionic modification is carried out with applied field. This new mode of modifying the lattice of CuInP2S6, and more generally ionically conducting thiophosphates, posits new prospects for their applications in van der Waals heterostructures, possibly in the context of catalytic or electronic functionalities.},
doi = {10.1021/acsami.8b08079},
journal = {ACS Applied Materials and Interfaces},
issn = {1944-8244},
number = 32,
volume = 10,
place = {United States},
year = {2018},
month = {7}
}

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