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Red Phosphorus: An Elementary Semiconductor for Room-Temperature NO2 Gas Sensing

  • Qiang Zhu
    Qiang Zhu
    Department of Electronic Engineering, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, China
    More by Qiang Zhu
  • Hao Wang
    Hao Wang
    State Key Laboratory of Material Processing and Die & Mould Technology, Department of Materials Science and Engineering, Huazhong University of Science and Technology, Luoyu Road, Wuhan, 430074, China
    More by Hao Wang
  • Jun Yang
    Jun Yang
    Department of Chemistry, University of Hong Kong, Pokfulam Road, Pokfulam, Hong Kong SAR, China
    More by Jun Yang
  • Changsheng Xie
    Changsheng Xie
    State Key Laboratory of Material Processing and Die & Mould Technology, Department of Materials Science and Engineering, Huazhong University of Science and Technology, Luoyu Road, Wuhan, 430074, China
  • Dawen Zeng
    Dawen Zeng
    State Key Laboratory of Material Processing and Die & Mould Technology, Department of Materials Science and Engineering, Huazhong University of Science and Technology, Luoyu Road, Wuhan, 430074, China
    More by Dawen Zeng
  • Ni Zhao*
    Ni Zhao
    Department of Electronic Engineering, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, China
    *E-mail: [email protected].
    More by Ni Zhao
Cite this: ACS Sens. 2018, 3, 12, 2629-2636
Publication Date (Web):November 20, 2018
https://doi.org/10.1021/acssensors.8b01041
Copyright © 2018 American Chemical Society
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Abstract

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Black and blue phosphorus (both allotropes of elementary phosphorus) have recently been widely explored as an active material for electronic devices, and their potential in gas sensing applications has been demonstrated. On the other hand, amorphous red phosphorus (a-RP), a much cheaper and readily available phosphorus allotrope, has seldom been investigated as an electronic material, and its gas sensing properties have never been studied. In this work we have investigated these properties of a-RP by combining experimental characterizations with theoretical calculations. We found that a-RP exhibited an amphoteric character for detecting both commonly regarded reducing and oxidizing gas molecules, featuring a negative correlation between the electrical resistance of a-RP and the gas concentration. Interestingly, the a-RP based sensors appear to be particularly suitable for room-temperature NO2 detection, exhibiting excellent sensitivity and selectivity, as well as fast temporal response and recovery. A unique sensing feature of a-RP toward NO2 was identified, which is associated with the expansion of P–P bonds upon NO2 chemisorption. Based on density functional theory calculations we proposed a physiochemical model to elaborate the synergistic effects of the P–P bond expansion and Langmuir isotherm adsorption on the electronic properties and gas sensing processes of a-RP.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssensors.8b01041.

  • Structure of amorphous red phosphorus (a-RP); electronic properties of a-RP and gas sensing properties of a-RP sensor; effect of NO2 chemisorption on carrier hopping mobility of a-RP; density functional theory calculations on electronic structures and gas adsorption/desorption processes on a-RP (PDF)

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