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:
-
- Institute for Basic Science (IBS), Ulsan (Republic of Korea); Brookhaven National Lab. (BNL), Upton, NY (United States)
- Renmin Univ. of China, Beijing (China)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Univ. of Nebraska-Lincoln, Lincoln, NE (United States)
- Institute for Basic Science (IBS), Ulsan (Republic of Korea)
- 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 Laboratory (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.
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
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.
@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 = {Mon Oct 24 00:00:00 EDT 2016},
month = {Mon Oct 24 00:00:00 EDT 2016}
}
Web of Science
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- Liu, Pingwei; Liu, Albert Tianxiang; Kozawa, Daichi
- Nature Materials, Vol. 17, Issue 11
Two-Dimensional Materials for Antimicrobial Applications: Graphene Materials and Beyond
journal, September 2018
- Sun, Wei; Wu, Fu-Gen
- Chemistry - An Asian Journal, Vol. 13, Issue 22
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
2D Elemental Nanomaterials Beyond Graphene
journal, June 2019
- Vishnoi, Pratap; Pramoda, K.; Rao, C. N. R.
- ChemNanoMat, Vol. 5, Issue 9
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
2D Black Phosphorus–Based Biomedical Applications
journal, February 2019
- Luo, Miaomiao; Fan, Taojian; Zhou, Yun
- Advanced Functional Materials, Vol. 29, Issue 13
A batch-by-batch free route for the continuous production of black phosphorus nanosheets for targeted combination cancer therapy
journal, August 2018
- Poudel, Bijay Kumar; Hwang, Jungho; Ku, Sae Kwang
- NPG Asia Materials, Vol. 10, Issue 8
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
Mechanistic insights in phosphorene degradation
journal, July 2019
- Babar, Rohit; Kabir, Mukul
- Physical Review Materials, Vol. 3, Issue 7
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
Azide Passivation of Black Phosphorus Nanosheets: Covalent Functionalization Affords Ambient Stability Enhancement
journal, December 2018
- Yang, Shangfeng; Liu, Yajuan; Gao, Pengfei
- Angewandte Chemie
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
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
Water-Catalyzed Oxidation of Few-Layer Black Phosphorous in a Dark Environment
journal, June 2017
- Hu, Zehua; Li, Qiang; Lei, Bo
- Angewandte Chemie, Vol. 129, Issue 31
Few Layer 2D Pnictogens (P & Sb) Catalyze the Alkylation of Soft Nucleophiles with Esters
preprint, September 2018
- Lioret, Vincet; Rivero-Crespo, Miguel Angel; Vidal-Moya, Jose Alejandro
- Nanoscience
Emerging Applications of Elemental 2D Materials.
text, January 2020
- Glavin, Nicholas R.; Rao, Rahul; Varshney, Vikas
- Apollo - University of Cambridge Repository
Few Layer 2D Pnictogens (P & Sb) Catalyze the Alkylation of Soft Nucleophiles with Esters
preprint, September 2018
- Lloret, Vicent; Rivero-Crespo, Miguel Angel; Vidal-Moya, Jose Alejandro
- Nanoscience
A First-Principles Study on the Adsorption of Small Molecules on Antimonene: Oxidation Tendency and Stability
text, January 2018
- Kistanov, Andrey A.; Cai, Yongqing; Kripalani, Devesh R.
- arXiv
Atomically thin p-n junctions based on two-dimensional materials
text, January 2018
- Frisenda, Riccardo; Molina-Mendoza, Aday J.; Mueller, Thomas
- arXiv
Effect of TCNQ layer cover on oxidation dynamics of black phosphorus
text, January 2018
- Meingast, Laura; Koleśnik-Gray, Maria; Siebert, Martin
- arXiv
Mechanistic insights on the phosphorene degradation
text, January 2019
- Babar, Rohit; Kabir, Mukul
- arXiv
Environmental Stability of Bismuthene: Oxidation Mechanism and Structural Stability of 2D Pnictogens
text, January 2019
- Kistanov, Andrey A.; Khadiullin, Salavat Kh.; Zhou, Kun
- arXiv