Nanoscale Control of Polar Surface Phases in Layered van der Waals CuInP2S6

Neumayer, Sabine M.; Zhao, Zhenghang; O’Hara, Andrew; McGuire, Michael A.; Susner, Michael A.; Pantelides, Sokrates T.; Maksymovych, Petro; Balke, Nina

doi:10.1021/acsnano.1c08970

Title: Nanoscale Control of Polar Surface Phases in Layered van der Waals CuInP₂S₆

Journal Article · Mon Feb 07 00:00:00 EST 2022 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.1c08970· OSTI ID:1846525

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
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)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); North Carolina State Univ., Raleigh, NC (United States)

Antiferroelectric (AFE) materials, in which alternating dipole moments cancel out to a zero net macroscopic polarization, can be used for high-density energy storage and memory applications. The AFE phase can exist in bulk CuInP₂Se₆, CuBiP₂S₆, and a few other transition-metal thiophosphates below 200 K. The required low temperature poses challenges for practical applications. In this work, we report the coexistence of ferrielectric (FE) states and a stable surface phase that does not show piezoelectric response (“zero-response phase”) in bulk CuInP₂S₆ at room temperature. Using piezoresponse force microscopy (PFM) tomographic imaging together with density functional theory, we find that direct and alternating voltages can locally and stably convert FE to zero-response phases and vice versa. While PFM loops show pinched hystereses reminiscent of antiferroelectricity, PFM tomography reveals that the zero-response areas form only on top of the FE phase in which the polarization vector is pointing up. Theoretical calculations suggest that the zero-response phase may correspond to AFE ordering where stacked CuInP₂S₆ layers have alternating polarization orientations thereby leading to a net-zero polarization. Consistent with experimental findings, theory predicts that the FE polarization pointing down is robust up to the top surface, whereas FE polarization pointing up energetically favors the formation of an AFE surface layer, whose thickness is likely to be sensitive to local strains. AFE order is likely to be more robust against detrimental size effects than polar order, therefore providing additional opportunities to create multifunctional heterostructures with 2D electronic materials.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; US Air Force Office of Scientific Research (AFOSR)

Grant/Contract Number:: AC05-00OR22725; FG02-09ER46554; AC02-05CH11231; F4GGA21207H002

OSTI ID:: 1846525

Journal Information:: ACS Nano, Vol. 16, Issue 2; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Nanoscale Control of Polar Surface Phases in Layered van der Waals CuInP2S6

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Title: Nanoscale Control of Polar Surface Phases in Layered van der Waals CuInP₂S₆