Chemical Changes in Layered Ferroelectric Semiconductors Induced by Helium Ion Beam

Alex Belianinov; Matthew J. Burch; Holland E. Hysmith; Anton V. Ievlev; Vighter Iberi; Michael A. Susner; Michael A. McGuire; Peter Maksymovych; Marius Chyasnavichyus; Stephen Jesse; Olga S. Ovchinnikova

doi:10.1038/s41598-017-16949-3

Chemical Changes in Layered Ferroelectric Semiconductors Induced by Helium Ion Beam

Alex Belianinov, Matthew J. Burch, Holland E. Hysmith, Anton V. Ievlev, Vighter Iberi, Michael A. Susner, Michael A. McGuire, Peter Maksymovych, Marius Chyasnavichyus, Stephen Jesse, Olga S. Ovchinnikova

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4 Scopus citations

Abstract

Multi-material systems interfaced with 2D materials, or entirely new 3D heterostructures can lead to the next generation multi-functional device architectures. Physical and chemical control at the nanoscale is also necessary tailor these materials as functional structures approach physical limit. 2D transition metal thiophosphates (TPS), with a general formulae Cu_1-xIn_1+x/3P₂S_6, have shown ferroelectric polarization behavior with a T _c above the room temperature, making them attractive candidates for designing both: chemical and physical properties. 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 discuss the chemical changes induced by helium ion irradiation. We explore the TPS compound library with varying Cu/In ratio, using Helium Ion Microscopy, Atomic Force Microscopy (AFM), and Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS). We correlate physical nano-and micro-structures to the helium ion dose, as well as chemical signatures of copper, oxygen and sulfur. Our ToF-SIMS results show that He ion irradiation leads to oxygen penetration into the irradiated areas, and diffuses along the Cu-rich domains to the extent of the stopping distance of the helium ions.

Original language	English
Article number	16619
Journal	Scientific Reports
Volume	7
Issue number	1
DOIs	https://doi.org/10.1038/s41598-017-16949-3
State	Published - Dec 1 2017

Funding

Research was supported (M.B., H.H., V.I., A.V.I., M.C., P.M., O.S.O.) and partially conducted (AFM, HIM, ToF-SIMS) at the Center for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division, Office of Basic Energy Sciences, US Department of Energy. Research for HIM – A. B., crystal growth – M.A.S. and M.A.M. was partially sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the U. S. Department of Energy.

Funders	Funder number
Center for Nanophase Materials Sciences
H.H.
HIM
Scientific User Facilities Division
US Department of Energy
UT-Battelle
U.S. Department of Energy
Basic Energy Sciences
Oak Ridge National Laboratory
Laboratory Directed Research and Development
Advanced Foods and Materials Canada

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title = "Chemical Changes in Layered Ferroelectric Semiconductors Induced by Helium Ion Beam",

abstract = "Multi-material systems interfaced with 2D materials, or entirely new 3D heterostructures can lead to the next generation multi-functional device architectures. Physical and chemical control at the nanoscale is also necessary tailor these materials as functional structures approach physical limit. 2D transition metal thiophosphates (TPS), with a general formulae Cu1-xIn1+x/3P2S6, have shown ferroelectric polarization behavior with a T c above the room temperature, making them attractive candidates for designing both: chemical and physical properties. 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 discuss the chemical changes induced by helium ion irradiation. We explore the TPS compound library with varying Cu/In ratio, using Helium Ion Microscopy, Atomic Force Microscopy (AFM), and Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS). We correlate physical nano-and micro-structures to the helium ion dose, as well as chemical signatures of copper, oxygen and sulfur. Our ToF-SIMS results show that He ion irradiation leads to oxygen penetration into the irradiated areas, and diffuses along the Cu-rich domains to the extent of the stopping distance of the helium ions.",

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AU - McGuire, Michael A.

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AB - Multi-material systems interfaced with 2D materials, or entirely new 3D heterostructures can lead to the next generation multi-functional device architectures. Physical and chemical control at the nanoscale is also necessary tailor these materials as functional structures approach physical limit. 2D transition metal thiophosphates (TPS), with a general formulae Cu1-xIn1+x/3P2S6, have shown ferroelectric polarization behavior with a T c above the room temperature, making them attractive candidates for designing both: chemical and physical properties. 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 discuss the chemical changes induced by helium ion irradiation. We explore the TPS compound library with varying Cu/In ratio, using Helium Ion Microscopy, Atomic Force Microscopy (AFM), and Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS). We correlate physical nano-and micro-structures to the helium ion dose, as well as chemical signatures of copper, oxygen and sulfur. Our ToF-SIMS results show that He ion irradiation leads to oxygen penetration into the irradiated areas, and diffuses along the Cu-rich domains to the extent of the stopping distance of the helium ions.

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Chemical Changes in Layered Ferroelectric Semiconductors Induced by Helium Ion Beam

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