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Photo-oxidative Crack Propagation in Transition Metal Dichalcogenides

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    Photo-oxidative Crack Propagation in Transition Metal Dichalcogenides
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    • Andrew Ben-Smith
      Andrew Ben-Smith
      Center for Integrated Nanostructure Physics (CINAP), Institute for Basic Science (IBS), Suwon 16419, Republic of Korea
      Department of Energy Science, Sungkyunkwan University (SKKU), Suwon 16419, Republic of Korea
      More by Andrew Ben-Smith
    • Soo Ho Choi
      Soo Ho Choi
      Center for Integrated Nanostructure Physics (CINAP), Institute for Basic Science (IBS), Suwon 16419, Republic of Korea
      Department of Energy Science, Sungkyunkwan University (SKKU), Suwon 16419, Republic of Korea
      More by Soo Ho Choi
    • Stephen Boandoh
      Stephen Boandoh
      Center for Integrated Nanostructure Physics (CINAP), Institute for Basic Science (IBS), Suwon 16419, Republic of Korea
      Department of Energy Science, Sungkyunkwan University (SKKU), Suwon 16419, Republic of Korea
      More by Stephen Boandoh
    • Byung Hoon Lee
      Byung Hoon Lee
      Department of Energy Science, Sungkyunkwan University (SKKU), Suwon 16419, Republic of Korea
      More by Byung Hoon Lee
    • Duc Anh Vu
      Duc Anh Vu
      Department of Energy Science, Sungkyunkwan University (SKKU), Suwon 16419, Republic of Korea
      More by Duc Anh Vu
    • Huong Thi Thanh Nguyen
      Huong Thi Thanh Nguyen
      Department of Energy Science, Sungkyunkwan University (SKKU), Suwon 16419, Republic of Korea
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    • Laud Anim Adofo
      Laud Anim Adofo
      Department of Energy Science, Sungkyunkwan University (SKKU), Suwon 16419, Republic of Korea
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    • Jeong Won Jin
      Jeong Won Jin
      Department of Energy Science, Sungkyunkwan University (SKKU), Suwon 16419, Republic of Korea
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    • Soo Min Kim*
      Soo Min Kim
      Department of Chemistry, Sookmyung Women’s University, Seoul 14072, Republic of Korea
      *Email: [email protected]
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    • Young Hee Lee*
      Young Hee Lee
      Center for Integrated Nanostructure Physics (CINAP), Institute for Basic Science (IBS), Suwon 16419, Republic of Korea
      Department of Energy Science, Sungkyunkwan University (SKKU), Suwon 16419, Republic of Korea
      *Email: [email protected]
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      Orcidhttps://orcid.org/0000-0001-7403-8157
    • Ki Kang Kim*
      Ki Kang Kim
      Center for Integrated Nanostructure Physics (CINAP), Institute for Basic Science (IBS), Suwon 16419, Republic of Korea
      Department of Energy Science, Sungkyunkwan University (SKKU), Suwon 16419, Republic of Korea
      *Email: [email protected]
      More by Ki Kang Kim
      Orcidhttps://orcid.org/0000-0003-1008-6744
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    ACS Nano

    Cite this: ACS Nano 2024, 18, 4, 3125–3133
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    https://doi.org/10.1021/acsnano.3c08755
    Published January 16, 2024
    Copyright © 2024 American Chemical Society
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    Abstract

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    Monolayered transition-metal dichalcogenides (TMDs) are easily exposed to air, and their crystal quality can often be degraded via oxidation, leading to poor electronic and optical device performance. The degradation becomes more severe in the presence of defects, grain boundaries, and residues. Here, we report crack propagation in pristine TMD monolayers grown by chemical vapor deposition under ambient conditions and light illumination. Under a high relative humidity (RH) of ∼60% and white light illumination, the cracks appear randomly. Photo-oxidative cracks gradually propagated along the grain boundaries of the TMD monolayers. In contrast, under low RH conditions of ∼2%, cracks were scarcely observed. Crack propagation is predominantly attributed to the accumulation of water underneath the TMD monolayers, which is preferentially absorbed by hygroscopic alkali metal-based precursor residues. Crack propagation is further accelerated by the cyclic process of photo-oxidation in a basic medium, leading to localized tensile strain. We also found that such crack propagation is prevented after the removal of alkali metals via the transfer of the sample to other substrates.

    Copyright © 2024 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsnano.3c08755.

    • Optical images of WSe2 monolayers upon exposure to moderate RH and white light; optical images of diverse transition metal dichalcogenides (TMDs) such as MoS2, WS2, and WSe2 monolayers using either sodium or potassium alkali metal precursors; I–V transfer curves of monolayer WSe2 FET devices before and after exposure to high RH conditions under white light (0.76 mW) for 24 h; SEM images of monolayer WSe2 before and after exposure to high RH under different light power intensities; optical images of WSe2 grains and film as a function of exposure time; images captured from Video S2 for small WSe2 grain and Video S3 for large WSe2 grain; AFM topography and phase images of small sized WSe2 grains after exposure to high RH under white light for 30 min; EDX spectra of alkali metal precursor removal from WSe2 sample before and after transfer; SEM images of transferred WSe2 grains before and after exposure to high RH conditions in darkness and under white light; Optical and SEM images of WSe2 grains grown by ammonium tungstate precursor before and after exposure to high RH under white light for 24 h; optical image of the FET device and I–V transfer characteristics of the device fabricated on monolayer WSe2 grain grown by ammonium tungstate precursor before and after exposure to high RH under white light for 24 h; and optical images of mechanically exfoliated WSe2 monolayer before and after exposure to high humidity under white light (PDF)

    • Video S1: Depiction of time-dependent photo-oxidation cracking of the WSe2 monolayer under RH (60%) and OM light (MP4)

    • Video S2: In situ evolution of random cracking in small WSe2 grain under the direct exposure to a humidifier (RH 80%) and OM light (MP4)

    • Video S3: In situ evolution of no cracking in large WSe2 grain under the direct exposure to a humidifier (RH 80%) and OM light (MP4)

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    1. Zheng Liu, Mengjie Li, Jie Wu, Jinjuan Zhao, Shuwen Li, Honglei Yang. Boosting photocatalytic reduction over perylene-C3N5 driven by constructing donor-acceptor structure. Journal of Alloys and Compounds 2025, 1014 , 178730. https://doi.org/10.1016/j.jallcom.2025.178730
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    ACS Nano

    Cite this: ACS Nano 2024, 18, 4, 3125–3133
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsnano.3c08755
    Published January 16, 2024
    Copyright © 2024 American Chemical Society
    Request reuse permissions

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