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Theoretical prediction of the mechanisms for defect healing or oxygen doping in a hexagonal boron nitride (h-BN) sheet with nitrogen vacancies by NO2 molecules

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Abstract

Healing defects in hexagonal boron nitride (h-BN sheet) or doping it with oxygen can modify or restore its physical properties, which would increase its range of potential applications. Thus, it is very important to find an efficient method of healing or a BN sheet or doping it with oxygen. In this work, using density functional theory (DFT) calculations, we identified a mechanism for healing h-BN sheets with nitrogen vacancies (VN) or doping BN sheets with oxygen using NO2 molecules. The results indicate that such reactions involve three steps: (1) the chemisorption of NO2, (2) the incorporation of the N or O atom of NO2 into the defective h-BN sheet, and (3) the removal of the adsorbed O atom or NO molecule. We found that the proposed mechanism is theoretically possible and has the following advantages. First, the barrier is about 0.60 eV for the formation of the O-doped h-BN sheet. For the healing process, because the energy released during NO2 chemisorption (−4.94 eV) completely offsets the subsequent barrier (1.17 eV), a perfect h-BN sheet can easily be achieved by using NO2 and an h-BN sheet with VB defects as reactants. Second, no catalyst is needed, and thus there is no need for a purification step to remove the catalyst. Third, NO2, a toxic gas, can be used as a reactant and will then be reduced to O2 or NO. Fourth, NO2 shows high selectivity for vacancy defect sites. Our findings show that this is an effective theoretical method of synthesizing O-doped h-BN sheets or of healing defective h-BN sheets, which should prove useful in the design of h-BN sheet-based devices.

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Acknowledgments

This work is supported by the National Nature Science Foundation of China (no. 21203048), and the Scientific Research Fund of the Heilongjiang Provincial Education Department (no. 12531195).

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Authors and Affiliations

  1. Key Laboratory of Photonic and Electronic Bandgap Materials, Ministry of Education, College of Chemistry and Chemical Engineering, Harbin Normal University, Harbin, 150025, People’s Republic of China

    Jing-wen Feng, Yue-Jie Liu & Jing-xiang Zhao

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Correspondence to Jing-xiang Zhao.

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Feng, Jw., Liu, YJ. & Zhao, Jx. Theoretical prediction of the mechanisms for defect healing or oxygen doping in a hexagonal boron nitride (h-BN) sheet with nitrogen vacancies by NO2 molecules. J Mol Model 20, 2307 (2014). https://doi.org/10.1007/s00894-014-2307-4

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