TY - JOUR
T1 - Interaction of black phosphorus with oxygen and water
AU - Huang, Yuan
AU - Qiao, Jingsi
AU - He, Kai
AU - Bliznakov, Stoyan
AU - Sutter, Eli
AU - Chen, Xianjue
AU - Luo, Da
AU - Meng, Fanke
AU - Su, Dong
AU - Decker, Jeremy
AU - Ji, Wei
AU - Ruoff, Rodney S.
AU - Sutter, Peter
N1 - Funding Information:
This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DESC0012704. Work done at the Center for Multidimensional Carbon Materials was supported by IBS-R019-D1. Work done in Beijing was financially supported by the Ministry of Science and Technology (MOST) of China under Grant No. 2012CB932704, the National Natural Science Foundation of China (NSFC) under Grant Nos. 11274380, 91433103, 11622437, 61674171, and the Fundamental Research Funds for the Central Universities, and the Research Funds of Renmin University of China under Grant No. 16XNH062. The authors would like to thank Dr. Mingzhao Liu for use of his electrochemical characterization facility, and Dr. Bin Wang for technical assistance with the contact angle measurements. Work at the University of Nebraska-Lincoln was supported by the U.S. Department of Energy, Office of Basic Energy Sciences under Grant No. DE-SC0016343, and by UNL program development funds. Calculations were performed at the Physics Laboratory for High-Performance Computing of Renmin University of China and at the Shanghai Supercomputer Center.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/11/22
Y1 - 2016/11/22
N2 - 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, and so on. 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. 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.
AB - 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, and so on. 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. 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.
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U2 - 10.1021/acs.chemmater.6b03592
DO - 10.1021/acs.chemmater.6b03592
M3 - Article
AN - SCOPUS:84997764830
SN - 0897-4756
VL - 28
SP - 8330
EP - 8339
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 22
ER -