Structural and Chemical Modifications of Few-Layer Transition Metal Phosphorous Trisulfides by Electron Irradiation

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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Date
2022-09-15
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Language
en
Pages
15446–15455
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Journal of Physical Chemistry C, Volume 126, issue 36
Abstract
Transition metal phosphorous trisulfides (TMPTs) are inorganic materials with inherent magnetic properties. Due to their layered structure, they can be exfoliated into ultra-thin sheets, which show properties different from their bulk counterparts. Herein, we present a detailed analysis of the interaction of the electron beam (30-80 kV) in a transmission electron microscope with freestanding few-layer TMPTs, with the aim of tailoring their properties. The irradiation-induced structure modifications were systematically investigated by various transmission electron microscopy methods on FePS3, MnPS3, and NiPS3, and the results are rationalized with the help of ab initio calculations, which predict that the knock-on threshold for removing sulfur is significantly lower than that for phosphorus. Therefore, a targeted removal of sulfur is feasible. Eventually, our experiments confirm the dose-dependent, predominant removal of sulfur by the impinging electrons, thus showing the possibility of tuning the sulfur concentration. Using ab initio calculations, we analyze the electronic structure of the TMPTs with single vacancies and oxygen impurities and predict distinct electronic properties depending on the type of defect. Therefore, our study shows the possibility of tuning the properties of ultra-thin freestanding TMPTs by controlling their stoichiometry.
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Funding Information: We want to thank all cooperation associates in the framework of this manuscript. Further, we especially thank the Institute Laue-Langevin, for the syntheses of the TMPT materials used in this work. We thank Gabriele Es-Samlaoui for successfully preparing the samples for TEM investigation. Further, we thank Hannu Pekka-Komsa for the fruitful discussions on Debye temperatures in TMPTs. This work is supported by a project funded by Carl Zeiss foundation. The computational support from the Technical University of Dresden computing cluster (TAURUS) and High-Performance Computing Center (HLRS) in Stuttgart is gratefully appreciated. We further thank the German Research Foundation (DFG) through projects KR 4866/8-1, the collaborative research center “Chemistry of Synthetic 2D Materials” CRC-1415-417590517, and the collaborative research center “Exploiting the Human Peptidome for Novel Antimicrobial and Anticancer Agents” CRC-1279-316249678 for financial support. Publisher Copyright: © 2022 The Authors. Published by American Chemical Society.
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Köster , J , Storm , A , Ghorbani-Asl , M , Kretschmer , S , Gorelik , T E , Krasheninnikov , A V & Kaiser , U 2022 , ' Structural and Chemical Modifications of Few-Layer Transition Metal Phosphorous Trisulfides by Electron Irradiation ' , Journal of Physical Chemistry C , vol. 126 , no. 36 , pp. 15446–15455 . https://doi.org/10.1021/acs.jpcc.2c03800