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Title: Interaction of Black Phosphorus with Oxygen and Water

Abstract

Black phosphorus (BP) has attracted significant interest as a monolayer or few-layer material with extraordinary electrical and optoelectronic properties. Chemical reactions with different ambient species, notably oxygen and water, are important as they govern key properties such as stability in air, electronic structure and charge transport, wetting by aqueous solutions, etc. Here, we report experiments combined with ab-initio calculations that address the effects of oxygen and water in contact with BP. Our results show that the reaction with oxygen is primarily responsible for changing properties of BP. Oxidation involving the dissociative chemisorption of O2 causes the decomposition of BP and continuously lowers the conductance of BP field-effect transistors (FETs). In contrast, BP is stable in contact with deaerated (i.e., O2 depleted) water and the carrier mobility in BP FETs gated by H2O increases significantly due to efficient dielectric screening of scattering centers by the high-k dielectric. Isotope labeling experiments, contact angle measurements and calculations show that the pristine BP surface is hydrophobic, but is turned progressively hydrophilic by oxidation. Lastly, our results open new avenues for exploring applications that require contact of BP with aqueous solutions including solution gating, electrochemistry, and solution-phase approaches for exfoliation, dispersion, and delivery of BP.

Authors:
 [1];  [2];  [3];  [3];  [4];  [5];  [5];  [3];  [3];  [5];  [2];  [6];  [4]
+ Show Author Affiliations
  1. Institute for Basic Science (IBS), Ulsan (Republic of Korea); Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Renmin Univ. of China, Beijing (China)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Univ. of Nebraska-Lincoln, Lincoln, NE (United States)
  5. Institute for Basic Science (IBS), Ulsan (Republic of Korea)
  6. Institute for Basic Science (IBS), Ulsan (Republic of Korea); Ulsan National Institute of Science and Technology, Ulsan (Republic of Korea)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1433967
Report Number(s):
BNL-203500-2018-JAAM
Journal ID: ISSN 0897-4756; TRN: US1803027
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 22; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
29 ENERGY PLANNING, POLICY AND ECONOMY; black phosphorus; field-effect transistors

Citation Formats

Huang, Yuan, Qiao, Jingsi, He, Kai, Bliznakov, Stoyan, Sutter, Eli, Chen, Xianjue, Luo, Da, Meng, Fanke, Su, Dong, Decker, Jeremy, Ji, Wei, Ruoff, Rodney S., and Sutter, Peter. Interaction of Black Phosphorus with Oxygen and Water. United States: N. p., 2016. Web. doi:10.1021/acs.chemmater.6b03592.
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Huang, Yuan, Qiao, Jingsi, He, Kai, Bliznakov, Stoyan, Sutter, Eli, Chen, Xianjue, Luo, Da, Meng, Fanke, Su, Dong, Decker, Jeremy, Ji, Wei, Ruoff, Rodney S., & Sutter, Peter. Interaction of Black Phosphorus with Oxygen and Water. United States. https://doi.org/10.1021/acs.chemmater.6b03592
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Huang, Yuan, Qiao, Jingsi, He, Kai, Bliznakov, Stoyan, Sutter, Eli, Chen, Xianjue, Luo, Da, Meng, Fanke, Su, Dong, Decker, Jeremy, Ji, Wei, Ruoff, Rodney S., and Sutter, Peter. Mon . "Interaction of Black Phosphorus with Oxygen and Water". United States. https://doi.org/10.1021/acs.chemmater.6b03592. https://www.osti.gov/servlets/purl/1433967.
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@article{osti_1433967,
title = {Interaction of Black Phosphorus with Oxygen and Water},
author = {Huang, Yuan and Qiao, Jingsi and He, Kai and Bliznakov, Stoyan and Sutter, Eli and Chen, Xianjue and Luo, Da and Meng, Fanke and Su, Dong and Decker, Jeremy and Ji, Wei and Ruoff, Rodney S. and Sutter, Peter},
abstractNote = {Black phosphorus (BP) has attracted significant interest as a monolayer or few-layer material with extraordinary electrical and optoelectronic properties. Chemical reactions with different ambient species, notably oxygen and water, are important as they govern key properties such as stability in air, electronic structure and charge transport, wetting by aqueous solutions, etc. Here, we report experiments combined with ab-initio calculations that address the effects of oxygen and water in contact with BP. Our results show that the reaction with oxygen is primarily responsible for changing properties of BP. Oxidation involving the dissociative chemisorption of O2 causes the decomposition of BP and continuously lowers the conductance of BP field-effect transistors (FETs). In contrast, BP is stable in contact with deaerated (i.e., O2 depleted) water and the carrier mobility in BP FETs gated by H2O increases significantly due to efficient dielectric screening of scattering centers by the high-k dielectric. Isotope labeling experiments, contact angle measurements and calculations show that the pristine BP surface is hydrophobic, but is turned progressively hydrophilic by oxidation. Lastly, our results open new avenues for exploring applications that require contact of BP with aqueous solutions including solution gating, electrochemistry, and solution-phase approaches for exfoliation, dispersion, and delivery of BP.},
doi = {10.1021/acs.chemmater.6b03592},
journal = {Chemistry of Materials},
number = 22,
volume = 28,
place = {United States},
year = {2016},
month = {10}
}
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    • DOI: 10.1039/c8cc01789a

    Phosphorene Is the New Graphene in Biomedical Applications
    journal, July 2019

    • Tatullo, Marco; Genovese, Fabio; Aiello, Elisabetta
    • Materials, Vol. 12, Issue 14
    • DOI: 10.3390/ma12142301

    Self-assembly of a parallelogram black phosphorus ribbon into a nanotube
    journal, October 2017

    p-Type BP nanosheet photocatalyst with AQE of 3.9% in the absence of a noble metal cocatalyst: investigation and elucidation of photophysical properties
    journal, January 2018

    • Rahman, Mohammad Z.; Batmunkh, Munkhbayar; Bat-Erdene, Munkhjargal
    • Journal of Materials Chemistry A, Vol. 6, Issue 38
    • DOI: 10.1039/c8ta07034b

    Black phosphorus-based field effect transistor devices for Ag ions detection
    journal, August 2018

    New solvent-stabilized few-layer black phosphorus for antibacterial applications
    journal, January 2018

    pH‐Dependent Degradation of Layered Black Phosphorus: Essential Role of Hydroxide Ions
    journal, January 2019

    • Zhang, Siyu; Zhang, Xuejiao; Lei, Lei
    • Angewandte Chemie International Edition, Vol. 58, Issue 2
    • DOI: 10.1002/anie.201809989

    Rapid exfoliation for few-layer enriched black phosphorus dispersion via a superhydrophobic silicon-nanowire-embedded microfluidic process
    journal, January 2020

    • Choi, Chang-Ho; Ko, Dong-Hyeon; Jun, Ho Young
    • Green Chemistry, Vol. 22, Issue 3
    • DOI: 10.1039/c9gc02337b

    High-quality in situ fabricated Nb Josephson junctions with black phosphorus barriers
    journal, September 2019

    • Chen, Wei; Xu, Zuyu; Tian, Wanghao
    • Superconductor Science and Technology, Vol. 32, Issue 11
    • DOI: 10.1088/1361-6668/ab3dc7

    Water-Catalyzed Oxidation of Few-Layer Black Phosphorous in a Dark Environment
    journal, June 2017

    • Hu, Zehua; Li, Qiang; Lei, Bo
    • Angewandte Chemie International Edition, Vol. 56, Issue 31
    • DOI: 10.1002/anie.201705012

    Stabilizing black phosphorus nanosheets via edge-selective bonding of sacrificial C60 molecules
    journal, October 2018

    2D-Pnictogens: alloy-based anode battery materials with ultrahigh cycling stability
    journal, January 2018

    • Beladi-Mousavi, Seyyed Mohsen; Pumera, Martin
    • Chemical Society Reviews, Vol. 47, Issue 18
    • DOI: 10.1039/c8cs00425k

    Emerging Applications of Elemental 2D Materials
    journal, October 2019

    • Glavin, Nicholas R.; Rao, Rahul; Varshney, Vikas
    • Advanced Materials, Vol. 32, Issue 7
    • DOI: 10.1002/adma.201904302

    Orientation‐Dependent Intercalation Channels for Lithium and Sodium in Black Phosphorus
    journal, September 2019

    • Kim, Sungkyu; Cui, Jiang; Dravid, Vinayak P.
    • Advanced Materials, Vol. 31, Issue 46
    • DOI: 10.1002/adma.201904623

    Monolayer black phosphorus by sequential wet-chemical surface oxidation
    journal, January 2019

    • Wild, Stefan; Lloret, Vicent; Vega-Mayoral, Victor
    • RSC Advances, Vol. 9, Issue 7
    • DOI: 10.1039/c8ra09069f

    Autoperforation of 2D materials for generating two-terminal memristive Janus particles
    journal, October 2018

    Two-Dimensional Materials for Antimicrobial Applications: Graphene Materials and Beyond
    journal, September 2018

    A first-principles study on the adsorption of small molecules on antimonene: oxidation tendency and stability
    journal, January 2018

    • Kistanov, Andrey A.; Cai, Yongqing; Kripalani, Devesh R.
    • Journal of Materials Chemistry C, Vol. 6, Issue 15
    • DOI: 10.1039/c8tc00338f

    2D Elemental Nanomaterials Beyond Graphene
    journal, June 2019

    Effect of TCNQ Layer Cover on Oxidation Dynamics of Black Phosphorus
    journal, May 2018

    • Meingast, Laura; Koleśnik-Gray, Maria; Siebert, Martin
    • physica status solidi (RRL) - Rapid Research Letters, Vol. 12, Issue 8
    • DOI: 10.1002/pssr.201800179

    2D Black Phosphorus–Based Biomedical Applications
    journal, February 2019

    • Luo, Miaomiao; Fan, Taojian; Zhou, Yun
    • Advanced Functional Materials, Vol. 29, Issue 13
    • DOI: 10.1002/adfm.201808306

    A batch-by-batch free route for the continuous production of black phosphorus nanosheets for targeted combination cancer therapy
    journal, August 2018

    Hybrid nanocomposites of 2D black phosphorus nanosheets encapsulated in PMMA polymer material: new platforms for advanced device fabrication
    journal, May 2018

    • Telesio, Francesca; Passaglia, Elisa; Cicogna, Francesca
    • Nanotechnology, Vol. 29, Issue 29
    • DOI: 10.1088/1361-6528/aabd8d

    Mechanistic insights in phosphorene degradation
    journal, July 2019

    Intrinsic Correlation between Electronic Structure and Degradation: From Few‐Layer to Bulk Black Phosphorus
    journal, January 2019

    • Kim, Minju; Kim, Han‐gyu; Park, Soohyung
    • Angewandte Chemie, Vol. 131, Issue 12
    • DOI: 10.1002/ange.201811743

    Azide Passivation of Black Phosphorus Nanosheets: Covalent Functionalization Affords Ambient Stability Enhancement
    journal, December 2018

    Band Structure of the IV-VI Black Phosphorus Analog and Thermoelectric SnSe
    text, January 2018

    • Pletikosić, Ivo; Von Rohr, Fabian; Pervan, Petar
    • American Physical Society
    • DOI: 10.5167/uzh-167495

    Raman and electrical transport properties of few-layered arsenic-doped black phosphorus
    text, January 2019

    • Pradhan, Nihar R.; Garcia, Carlos; Lucking, Michael C.
    • Royal Society of Chemistry
    • DOI: 10.7892/boris.140693

    Water-Catalyzed Oxidation of Few-Layer Black Phosphorous in a Dark Environment
    journal, June 2017

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