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Title: Chemical Changes in Layered Ferroelectric Semiconductors Induced by Helium Ion Beam

Abstract

Transitioning to multi-material systems as either interfaced 2D materials or 3D heterostructures can lead to the next generation multi-functional device architectures. Combined direct physical and chemical nanoscale control of these systems offers a new way to tailor material and device functionality as functional structures reach their physical limit. Transition metal thiophosphate (TPS), Cu1-xIn1+x/3P2S6, that have ferroelectric polarization behavior as layered crystals at room temperature and above make them attractive candidates for direct material sculpting of both chemical and functional properties. The bulk material exhibits stable ferroelectric polarization corroborated by domain structures, rewritable polarization, and hysteresis loops. Our previous studies have demonstrated that ferroic order persists on the surface and that spinoidal decomposition of ferroelectric and paraelectric phases occurs in non-stoichiometric Cu/In ratio formulations. Here, we elucidate the chemical changes induced through helium ion irradiation in the TPS family library with varying Cu/In ratio formulations using correlated AFM and ToF-SIMS imaging. We correlate nano- and micro- structures that scale, in area and volume, to the total dose of the helium ion beam, as well as the overall copper concentration in the sample. Furthermore, our ToF-SIMS results show that ion irradiation leads to oxygen penetration as a function of Cu concentration, andmore » proceeds along the Cu domains to the stopping distance of the helium ions in the TPS material. These results opens up new opportunities to understand and implement ferroicly coupled van der Waal devices into an existing framework of 2D heterostructures by locally tuning material chemistry and functionality.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1412062
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Belianinov, Alex, Burch, Matthew J., Hysmith, Holland E., Ievlev, Anton V., Iberi, Vighter, Susner, Michael A., McGuire, Michael A., Maksymovych, Peter, Chyasnavichyus, Marius, Jesse, Stephen, and Ovchinnikova, Olga S. Chemical Changes in Layered Ferroelectric Semiconductors Induced by Helium Ion Beam. United States: N. p., 2017. Web. doi:10.1038/s41598-017-16949-3.
Belianinov, Alex, Burch, Matthew J., Hysmith, Holland E., Ievlev, Anton V., Iberi, Vighter, Susner, Michael A., McGuire, Michael A., Maksymovych, Peter, Chyasnavichyus, Marius, Jesse, Stephen, & Ovchinnikova, Olga S. Chemical Changes in Layered Ferroelectric Semiconductors Induced by Helium Ion Beam. United States. doi:10.1038/s41598-017-16949-3.
Belianinov, Alex, Burch, Matthew J., Hysmith, Holland E., Ievlev, Anton V., Iberi, Vighter, Susner, Michael A., McGuire, Michael A., Maksymovych, Peter, Chyasnavichyus, Marius, Jesse, Stephen, and Ovchinnikova, Olga S. Thu . "Chemical Changes in Layered Ferroelectric Semiconductors Induced by Helium Ion Beam". United States. doi:10.1038/s41598-017-16949-3. https://www.osti.gov/servlets/purl/1412062.
@article{osti_1412062,
title = {Chemical Changes in Layered Ferroelectric Semiconductors Induced by Helium Ion Beam},
author = {Belianinov, Alex and Burch, Matthew J. and Hysmith, Holland E. and Ievlev, Anton V. and Iberi, Vighter and Susner, Michael A. and McGuire, Michael A. and Maksymovych, Peter and Chyasnavichyus, Marius and Jesse, Stephen and Ovchinnikova, Olga S.},
abstractNote = {Transitioning to multi-material systems as either interfaced 2D materials or 3D heterostructures can lead to the next generation multi-functional device architectures. Combined direct physical and chemical nanoscale control of these systems offers a new way to tailor material and device functionality as functional structures reach their physical limit. Transition metal thiophosphate (TPS), Cu1-xIn1+x/3P2S6, that have ferroelectric polarization behavior as layered crystals at room temperature and above make them attractive candidates for direct material sculpting of both chemical and functional properties. The bulk material exhibits stable ferroelectric polarization corroborated by domain structures, rewritable polarization, and hysteresis loops. Our previous studies have demonstrated that ferroic order persists on the surface and that spinoidal decomposition of ferroelectric and paraelectric phases occurs in non-stoichiometric Cu/In ratio formulations. Here, we elucidate the chemical changes induced through helium ion irradiation in the TPS family library with varying Cu/In ratio formulations using correlated AFM and ToF-SIMS imaging. We correlate nano- and micro- structures that scale, in area and volume, to the total dose of the helium ion beam, as well as the overall copper concentration in the sample. Furthermore, our ToF-SIMS results show that ion irradiation leads to oxygen penetration as a function of Cu concentration, and proceeds along the Cu domains to the stopping distance of the helium ions in the TPS material. These results opens up new opportunities to understand and implement ferroicly coupled van der Waal devices into an existing framework of 2D heterostructures by locally tuning material chemistry and functionality.},
doi = {10.1038/s41598-017-16949-3},
journal = {Scientific Reports},
number = 1,
volume = 7,
place = {United States},
year = {2017},
month = {11}
}

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