Locally Controlled Cu-Ion Transport in Layered Ferroelectric CuInP2S6

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

doi:10.1021/acsami.8b08079

Title: Locally Controlled Cu-Ion Transport in Layered Ferroelectric CuInP₂S₆

Journal Article · Mon Jul 23 00:00:00 EDT 2018 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.8b08079· OSTI ID:1543692

^[1];

^[2];

^[3]; Susner, Michael A. ^[4];

^[5]; Jesse, Stephen ^[1];

^[1]; Pantelides, Sokrates T. ^[3];

^[1]; Maksymovych, Petro ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. College Dublin (Ireland)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Vanderbilt Univ., Nashville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Air Force Research Lab. (AFRL), Wright-Patterson AFB, OH (United States)
Univ. College Dublin (Ireland)

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.

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Research Organization:: Lawrence Berkeley National Lab. (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); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; FG02-09ER46554; AC05-00OR22725

OSTI ID:: 1543692

Alternate ID(s):: OSTI ID: 1597901; OSTI ID: 1784196

Journal Information:: ACS Applied Materials and Interfaces, Vol. 10, Issue 32; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 47 works

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Title: Locally Controlled Cu-Ion Transport in Layered Ferroelectric CuInP2S6

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Title: Locally Controlled Cu-Ion Transport in Layered Ferroelectric CuInP₂S₆