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A clean dry transfer of hexagonal boron nitride with improved oxidation resistance

一种提升六方氮化硼抗氧化性的洁净干转移方法

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Abstract

Hexagonal boron nitride (h-BN) is an outstanding two-dimensional material in terms of thermal stability and chemical inertness, enabling its versatile applications under harsh conditions. However, the oxidation resistance of h-BN is significantly reduced in the presence of metallic catalysts, which could be readily introduced during commonly adapted transfer methods of chemical vapor-deposited samples through the wet etching of metallic substrates. Here we propose a clean dry transfer method for monolayer h- BN film grown on the copper (Cu) surface. Thus, the mechanical delamination of the h-BN film from the substrates becomes feasible as their interfacial adhesion energy is significantly reduced because of the oxygen intercalation and surface oxidation of Cu during exposure to air. The drytransferred h-BN film is proven to be free of metallic (iron) contaminants, in sharp contrast to the wet-transferred h-BN film, which contains significant amounts of metallic residues. The clean transfer of h-BN considerably enhances its oxidation resistance by 50–100°C, yielding nearly the ideal performance of h-BN. As a result, graphene layers coated with drytransferred monolayer h-BN film exhibit enhanced robustness to temperatures in the air up to 700°C, indicating the advantage of the proposed dry transfer method.

摘要

六方氮化硼(h-BN)是一种具有出色热稳定性和化学惰性的二维 材料, 在苛刻条件下应用广泛. 然而, 表面金属催化剂会使其抗氧化性 显著降低. 对于通过化学气相沉积制备的样品, 常规通过湿法蚀刻金属 基底的转移方法不可避免地会引入金属残留. 我们这里提出了一种针 对铜表面生长的单层h-BN薄膜的洁净干转移方法. 空气环境下界面氧 插层和表面铜氧化导致界面粘附能量显著降低, 因而h-BN薄膜可以从 基底上被直接机械剥离开. 与湿法转移制备的薄膜形成鲜明对比, 干法 转移得到的h-BN薄膜几乎没有金属(铁)污染, 使其抗氧化性提高了 50–100°C, 甚至接**其本征性能. 在干法转移的单层h-BN薄膜保护下, 单层石墨烯在空气中的耐受温度提高到700°C, 展示了这一干转移方法 的优势.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2019YFA0705400), the National Natural Science Foundation of China (12172176, 52002175, and 11802121), the Joint Fund of Advanced Aerospace Manufacturing Technology Research (U1937601), the Natural Science Foundation of Jiangsu Province (BK20211191 and BK20212008), the Research Fund of State Key Laboratory of Mechanics and Control of Mechanical Structures (MCMS-I-0421G01 and MCMS-I-0421K01), China Postdoctoral Science Foundation (2018T110494, 2020TQ0146, 2021M701703, and 2021M701705), the Fundamental Research Funds for the Central Universities (NE2020001, NJ2020003, NZ2020001, and NS2021042), and the Priority Academic Program Development of Jiangsu Higher Education Institutions.

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Authors and Affiliations

  1. State Key Laboratory of Mechanics and Control of Mechanical Structures, Key Laboratory for Intelligent Nano Materials and Devices of the Ministry of Education, Nan**g University of Aeronautics and Astronautics, Nan**g, 210016, China

    Xuemei Li  (**雪梅), Luqiao Qi  (祁陆乔), Yuyang Long  (龙雨洋), Baowen Li  (**保文), Jianxin Zhou  (周建新), Yan Shi  (师岩), Jun Yin  (殷俊) & Wanlin Guo  (郭万林)

  2. College of Material Science and Engineering, Nan**g University of Aeronautics and Astronautics, Nan**g, 210016, China

    Xuemei Li  (**雪梅) & Zhengyang Li  (**郑扬)

  3. College of Aerospace engineering, Nan**g University of Aeronautics and Astronautics, Nan**g, 210016, China

    Luqiao Qi  (祁陆乔), Yan Shi  (师岩) & Jun Yin  (殷俊)

  4. Institute for Frontier Science, Nan**g University of Aeronautics and Astronautics, Nan**g, 210016, China

    Jidong Li  (**基东) & Wanlin Guo  (郭万林)

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  1. Xuemei Li  (**雪梅)
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  2. Zhengyang Li  (**郑扬)
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  3. Luqiao Qi  (祁陆乔)
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  4. Yuyang Long  (龙雨洋)
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  5. Baowen Li  (**保文)
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  6. Jidong Li  (**基东)
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  7. Jianxin Zhou  (周建新)
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  8. Yan Shi  (师岩)
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  9. Jun Yin  (殷俊)
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  10. Wanlin Guo  (郭万林)
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Contributions

Yin J and Li X provided the ideas, designed the experiments, conceived the framework of this paper and revised the original manuscript; Li Z designed and performed the experiments, analyzed the data, and drafted the original manuscript; Qi L, Long Y, and Shi Y provided pivotal advice; Li B, Li J, and Zhou J contributed to manuscript revision; Guo W was responsible for the overall project administration. All authors contributed to the general discussion.

Corresponding author

Correspondence to Jun Yin  (殷俊).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Supporting data are available in the online version of the paper.

Xuemei Li received her PhD degree in 2016 for the thesis on the synthesis and properties of two-dimensional materials. Now she is an associate professor at Nan**g University of Aeronautics and Astronautics (NUAA) and focuses on the physical mechanics of nano-materials.

Jun Yin obtained his PhD degree from NUAA in 2016, following which he worked at the University of Manchester as a research associate for three years. Then, he joined NUAA in 2019 as a professor. His research focuses on the surface/interface interaction of nanomaterials and their applications.

Wanlin Guo received his PhD degree in aerospace engineering and solid mechanics from the Northwestern Polytechnical University in 1991. He is an academician of Chinese Academy of Sciences, chair professor in mechanics and nanoscience, founder and director of the Institute of Nanoscience, NUAA. His current research focuses on 3D fatigue fracture and damage tolerance and durability design of structures; intelligent nanomaterials and devices, multiscale physical mechanics, novel conception and technology for efficient energy conversion; molecular physical mechanics for neuronal signaling and molecular biomimics.

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Li, X., Li, Z., Qi, L. et al. A clean dry transfer of hexagonal boron nitride with improved oxidation resistance. Sci. China Mater. 66, 327–334 (2023). https://doi.org/10.1007/s40843-022-2112-y

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