Mingyuan Wang*, Hui Shi, Shahid Hussain, Guiwu Liu, Shuang-Ying Lei* and Neng Wan*,
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The results indicate that a twin boundary with 558-N/B structures would be formed when two different orientation domains meet, and the h-BN domains can seamlessly stitch together for the same orientations or h-BN domains located in the different adjacent single atomic layer. Next, the failure mechanism of the antioxidant is considered and the synthesized h-BN at the Cu foil was treated by thermal oxidation, and we found the generation of Cu<sub>2</sub>O/CuO induced the decoupling phenomenon between h-BN and Cu. Further DFT calculations indicate that the presence of twin boundaries and point defects can also facilitate the diffusion of the O atom, and h-BN edges terminated with H can promote the diffusion of the O atom and the diffusion and decomposition of H<sub>2</sub>O molecules more than Cu(111) passivated h-BN, which accelerates the oxidation of Cu foil, leading to the formation of Cu<sub>2</sub>O/CuO. This process increases the distance between h-BN and Cu and decreases the amount of Bader transfer and orbital hybridization of B, N, and Cu atoms between h-BN and Cu foil, thereby reducing the coupling between h-BN and Cu foil. This study can provide experimental and theoretical explanations for the failure mechanism of h-BN films in protecting metals from oxidation.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2000,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Study on the Failure Mechanism of Antioxidant on Copper Foils with Growing Hexagonal Boron Nitride Films\",\"authors\":\"Mingyuan Wang*, Hui Shi, Shahid Hussain, Guiwu Liu, Shuang-Ying Lei* and Neng Wan*, \",\"doi\":\"10.1021/acs.chemmater.4c00986\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Recently, hexagonal boron nitride (h-BN) films have been considered as an effective alternative material for preventing metal oxidation due to its electrical insulating properties and ultrathin thickness. 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Further DFT calculations indicate that the presence of twin boundaries and point defects can also facilitate the diffusion of the O atom, and h-BN edges terminated with H can promote the diffusion of the O atom and the diffusion and decomposition of H<sub>2</sub>O molecules more than Cu(111) passivated h-BN, which accelerates the oxidation of Cu foil, leading to the formation of Cu<sub>2</sub>O/CuO. This process increases the distance between h-BN and Cu and decreases the amount of Bader transfer and orbital hybridization of B, N, and Cu atoms between h-BN and Cu foil, thereby reducing the coupling between h-BN and Cu foil. 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引用次数: 0
摘要
最近,六方氮化硼(h-BN)薄膜因其电绝缘特性和超薄厚度而被认为是防止金属氧化的有效替代材料。然而,在使用合成的 h-BN 保护金属时也存在一些问题,特别是在使用一段时间后,其抗氧化性能会下降。针对这一问题,我们采用化学气相沉积(CVD)方法在商用铜箔上合成了 h-BN 薄膜,并通过实验和密度泛函理论(DFT)计算提出了其失效机理。结果表明,当两个不同取向的畴相遇时,会形成具有 558-N/B 结构的孪晶边界,对于相同取向或位于不同相邻单原子层中的 h-BN 畴,可以无缝拼接在一起。接下来,我们考虑了抗氧化剂的失效机制,并对铜箔上合成的 h-BN 进行了热氧化处理,发现 Cu2O/CuO 的生成诱导了 h-BN 与铜之间的解耦现象。进一步的 DFT 计算表明,孪晶边界和点缺陷的存在也能促进 O 原子的扩散,与 Cu(111) 钝化的 h-BN 相比,以 H 终止的 h-BN 边缘更能促进 O 原子的扩散以及 H2O 分子的扩散和分解,从而加速了 Cu 箔的氧化,导致 Cu2O/CuO 的形成。这一过程增加了 h-BN 与 Cu 之间的距离,减少了 h-BN 与 Cu 箔之间 B、N 和 Cu 原子的巴德转移和轨道杂化量,从而降低了 h-BN 与 Cu 箔之间的耦合。这项研究可为 h-BN 薄膜保护金属免受氧化的失效机制提供实验和理论解释。
Study on the Failure Mechanism of Antioxidant on Copper Foils with Growing Hexagonal Boron Nitride Films
Recently, hexagonal boron nitride (h-BN) films have been considered as an effective alternative material for preventing metal oxidation due to its electrical insulating properties and ultrathin thickness. However, there are some issues when using synthesized h-BN on metal protection, especially because its antioxidation performance will decrease after a period of time. To address this problem, the h-BN films were synthesized at commercial Cu foil by the chemical vapor deposition (CVD) method, and the failure mechanism is proposed by experimental and density functional theory (DFT) calculations. The results indicate that a twin boundary with 558-N/B structures would be formed when two different orientation domains meet, and the h-BN domains can seamlessly stitch together for the same orientations or h-BN domains located in the different adjacent single atomic layer. Next, the failure mechanism of the antioxidant is considered and the synthesized h-BN at the Cu foil was treated by thermal oxidation, and we found the generation of Cu2O/CuO induced the decoupling phenomenon between h-BN and Cu. Further DFT calculations indicate that the presence of twin boundaries and point defects can also facilitate the diffusion of the O atom, and h-BN edges terminated with H can promote the diffusion of the O atom and the diffusion and decomposition of H2O molecules more than Cu(111) passivated h-BN, which accelerates the oxidation of Cu foil, leading to the formation of Cu2O/CuO. This process increases the distance between h-BN and Cu and decreases the amount of Bader transfer and orbital hybridization of B, N, and Cu atoms between h-BN and Cu foil, thereby reducing the coupling between h-BN and Cu foil. This study can provide experimental and theoretical explanations for the failure mechanism of h-BN films in protecting metals from oxidation.
期刊介绍:
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.