Atomic Structure and Dynamics of Self-Limiting Sub-Nanometer Pores in Monolayer WS 2

© 2018 American Chemical Society. We reveal a self-limiting mechanism during the formation of a specific type of circular nanopore in monolayer WS2 that limits its diameter to sub-nm. A single W atom vacancy (triangular nanopore) is transformed into the self-limiting nanopore (SLNP) through the atom...

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Main Authors: Ryu, Gyeong Hee, France-Lanord, Arthur, Wen, Yi, Zhou, Si, Grossman, Jeffrey C, Warner, Jamie H
Format: Article
Language:English
Published: American Chemical Society (ACS) 2021
Online Access:https://hdl.handle.net/1721.1/136334
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author Ryu, Gyeong Hee
France-Lanord, Arthur
Wen, Yi
Zhou, Si
Grossman, Jeffrey C
Warner, Jamie H
author_facet Ryu, Gyeong Hee
France-Lanord, Arthur
Wen, Yi
Zhou, Si
Grossman, Jeffrey C
Warner, Jamie H
author_sort Ryu, Gyeong Hee
collection MIT
description © 2018 American Chemical Society. We reveal a self-limiting mechanism during the formation of a specific type of circular nanopore in monolayer WS2 that limits its diameter to sub-nm. A single W atom vacancy (triangular nanopore) is transformed into the self-limiting nanopore (SLNP) through the atomic restructuring of S atoms around the area, reducing the number of dangling bonds at the nanopore edge by shifting them further in-plane with W-W bonding instead. Bond rotations in WS2 help accommodate the electron beam induced atomic loss and ensure the stability of the SLNP. The SLNP shows significant improvement in diameter stability during electron beam irradiation compared to other triangular nanopores in WS2 that typically continue to expand in diameter during atom loss. The atomic structure of these SLNPs is studied using aberration-corrected scanning transmission electron microscopy with an in situ heating holder, revealing that the SLNPs are mostly formed at a temperature of -500 °C, which is a balance between thermally activated S vacancy diffusion and sufficient S vacancy density to initiate local atomic reconstruction. At higher temperatures (i.e., 1000 °C), S vacancies quickly migrate away into long line vacancies, resulting in low S vacancy density and rapidly expanding holes generated at the edges of the line vacancies. At room temperature, S vacancy migration is low and vacancy density is very high, which limits atomic reconstruction, and instead many small holes open up. These results provide insights into the factors that lead to uniform sized nanopores in the sub-nm range in transition-metal dichalcogenides.
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spelling mit-1721.1/1363342022-04-01T16:23:45Z Atomic Structure and Dynamics of Self-Limiting Sub-Nanometer Pores in Monolayer WS 2 Ryu, Gyeong Hee France-Lanord, Arthur Wen, Yi Zhou, Si Grossman, Jeffrey C Warner, Jamie H © 2018 American Chemical Society. We reveal a self-limiting mechanism during the formation of a specific type of circular nanopore in monolayer WS2 that limits its diameter to sub-nm. A single W atom vacancy (triangular nanopore) is transformed into the self-limiting nanopore (SLNP) through the atomic restructuring of S atoms around the area, reducing the number of dangling bonds at the nanopore edge by shifting them further in-plane with W-W bonding instead. Bond rotations in WS2 help accommodate the electron beam induced atomic loss and ensure the stability of the SLNP. The SLNP shows significant improvement in diameter stability during electron beam irradiation compared to other triangular nanopores in WS2 that typically continue to expand in diameter during atom loss. The atomic structure of these SLNPs is studied using aberration-corrected scanning transmission electron microscopy with an in situ heating holder, revealing that the SLNPs are mostly formed at a temperature of -500 °C, which is a balance between thermally activated S vacancy diffusion and sufficient S vacancy density to initiate local atomic reconstruction. At higher temperatures (i.e., 1000 °C), S vacancies quickly migrate away into long line vacancies, resulting in low S vacancy density and rapidly expanding holes generated at the edges of the line vacancies. At room temperature, S vacancy migration is low and vacancy density is very high, which limits atomic reconstruction, and instead many small holes open up. These results provide insights into the factors that lead to uniform sized nanopores in the sub-nm range in transition-metal dichalcogenides. 2021-10-27T20:34:54Z 2021-10-27T20:34:54Z 2018 2019-09-19T13:27:40Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/136334 en 10.1021/ACSNANO.8B07051 ACS Nano Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) MIT web domain
spellingShingle Ryu, Gyeong Hee
France-Lanord, Arthur
Wen, Yi
Zhou, Si
Grossman, Jeffrey C
Warner, Jamie H
Atomic Structure and Dynamics of Self-Limiting Sub-Nanometer Pores in Monolayer WS 2
title Atomic Structure and Dynamics of Self-Limiting Sub-Nanometer Pores in Monolayer WS 2
title_full Atomic Structure and Dynamics of Self-Limiting Sub-Nanometer Pores in Monolayer WS 2
title_fullStr Atomic Structure and Dynamics of Self-Limiting Sub-Nanometer Pores in Monolayer WS 2
title_full_unstemmed Atomic Structure and Dynamics of Self-Limiting Sub-Nanometer Pores in Monolayer WS 2
title_short Atomic Structure and Dynamics of Self-Limiting Sub-Nanometer Pores in Monolayer WS 2
title_sort atomic structure and dynamics of self limiting sub nanometer pores in monolayer ws 2
url https://hdl.handle.net/1721.1/136334
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