六方氮化硼表面石墨烯纳米带生长与物性研究

陈令修; 王慧山; 姜程鑫; 陈晨; 王浩敏

doi:10.7498/aps.68.20191036

摘要

石墨烯作为二维原子晶体家族的典型代表, 由于其优异的物理与化学特性而受到学术界与工业界的广泛关注. 石墨烯纳米带是宽度仅有几纳米到几十纳米的石墨烯. 纳米带不但继承了石墨烯大部分优异的性能, 而且具备可调控带隙、自旋极化边界态等石墨烯所不具有的新奇物理特性. 这些特性使石墨烯纳米带成为未来探索石墨烯电子学应用所需要重点研究的对象. 利用与石墨烯晶格结构相似的六方氮化硼(h-BN)作为绝缘介质衬底进行石墨烯及石墨烯纳米带制备, 不仅可以有效地保持它们优异的本征性质, 还可以开发出与主流半导体工艺相兼容的电子器件工艺与应用. 本文回顾了近几年h-BN表面石墨烯及石墨烯纳米带研究的发展历程, 详细阐述了最近的材料制备和物性研究的进展, 并对高质量h-BN衬底制备的最新进展进行介绍, 以期为未来实现高质量h-BN表面石墨烯纳米带的规模化制备并最终实现电子器件应用奠定基础. 最后本文对h-BN表面石墨烯及石墨烯纳米带的未来研究方向进行了展望.

关键词:

Abstract

Graphene, as a typical representative of the two-dimensional material family, has received a wide attention due to its excellent physical and chemical properties. Graphene nanoribbon (GNR) is graphene in a width of several to a few tens of nanometers. GNRs not only inherit most of the excellent properties of graphene, but also have their own specific properties such as band gap opening and spin-polarized edge states, which make it the potential candidate in graphene based electronics in the future. Hexagonal boron nitride (h-BN), which has similar lattice constant with graphene, normally serves as an ideal substrate for graphene and GNRs. It can not only effectively preserve their intrinsic properties, but also benefit for the fabrication of electrical devices via popular semiconductor processes. In this paper, we reviewed the development history of research of graphene and GNRs on h-BN in recent years. The recent progress of physical properties is also discussed. In order to realize the large scale production of graphene and GNRs on h-BN, high quality h-BN multilayer is necessary. In addition, recent progresses about h-BN preparation methods are presented, and the progresses could pave the way for the further application of GNRs in the electronics. Finally, the research direction of graphene and GNRs on h-BN in the future is discussed.

Keywords:

作者及机构信息

1.
中国科学院上海微系统与信息技术研究所, 信息功能材料国家重点实验室, 上海　200050

2.
中国科学院大学材料科学与光电技术学院, 北京　100049

3.
上海科技大学物质学院, 上海　200031

通信作者: 王浩敏, hmwang@mail.sim.ac.cn

基金项目: 国家重点研发计划(批准号: 2017YFF0206106)、国家自然科学基金(批准号: 51772317)、中国科学院战略性先导科技专项(B类)(批准号: XDB30000000)、上海市科学技术委员会(批准号: 16ZR1442700)和上海市“超级博士后”和中国博士后科学基金(批准号: 2019T120366, 2019M651620)资助的课题.

Authors and contacts

1.
State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050, China

2.
College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China

3.
School of Physical Science and Technology, ShanghaiTech University, Shanghai 200031, China

Corresponding author: Wang Hao-Min, hmwang@mail.sim.ac.cn

Funds: Project supported by the National Key R&D program (Grant No. 2017YFF0206106), the National Natural Science Foundation of China (Grant No. 51772317), the Strategic Priority Research Program (B) of Chinese Academy of Sciences (Grant No. XDB30000000), the Science and Technology Commission of Shanghai Municipality, China (Grant No. 16ZR1442700), and Shanghai “Super Postdoctor” Program and the China Postdoctoral Science Foundation, China (Grant Nos. 2019T120366, 2019M651620).

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施引文献

图 1 石墨烯纳米带制备研究发展历程

Fig. 1. Evolutionary overview on graphene nanoribbons (GNRs) fabrication.

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图 2 h-BN表面石墨烯制备　(a) h-BN表面点缺陷处形核得到的石墨烯晶畴^[18]; (b) h-BN表面台阶处形核得到的石墨烯条带; (c) h-BN表面气相催化石墨烯生长示意图; (d)不同气相催化剂对石墨烯生长的加速作用^[51]; (e)扶手椅型边界的石墨烯的AFM摩擦力图像; (f)锯齿型边界的石墨烯的AFM摩擦力图像^[55]

Fig. 2. Synthesis of high-quality graphene on h-BN: (a) Graphene domains nucleated at defects of h-BN surface^[18]; (b) graphene ribbon grown at the step-edge of h-BN; (c) schematic of the gaseous catalyst-assisted graphene growth on h-BN^[51]; (d) the growth duration dependence of the domain size for graphene in the presence of silane or germane gaseous catalysts; (e), (f) AFM friction images of grapheneedge alongarmchair (e) and zigzag (f) direction^[55].

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图 3 h-BN表面石墨烯制备的不同方案　(a), (b)等离子体辅助CVD方法制备高质量石墨烯^[17]; (c)−(e)采用分子束外延法实现h-BN表面石墨烯晶畴制备^[54]; (f)通过金属催化在h-BN表面制备石墨烯^[52]

Fig. 3. Different methods for the synthesis of graphene on h-BN: (a), (b) Synthesis of high-quality graphene on h-BN by plasma enhanced CVD^[17]; (c)−(e) synthesis of graphene on h-BN by molecular beam epitaxy^[54]; (f) synthesis of graphene on h-BN by proximity-catalytic process^[52].

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图 4 石墨烯/h-BN异质结物理性质　(a)摩尔条纹示意图^[12]; (b)石墨烯与h-BN之间不同晶格常数差异和偏转角对摩尔条纹的影响关系^[14]; (c)摩尔条纹图像及超晶格狄拉克点^[13]; (d)霍夫斯塔特蝴蝶效应^[56]; (e)公度-非公度转变^[57]

Fig. 4. Physical properties of graphene/h-BN heterostructure: (a) Schematic of Moiré pattern^[12]; (b) Moiré pattern wavelength and its rotation angle with respect to the h-BN as a function of mis-orientation angle between graphene and h-BN^[14]; (c) the existence of moiré pattern and superlattice Dirac points^[13]; (d) hofstadter butterfly effect^[56]; (e) commensurate-incommensurate transitions^[57].

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图 5 h-BN石墨烯纳米带的制备方法　(a)氢等离子各向异性刻蚀法制备石墨烯纳米带^[59]; (b), (c) h-BN台阶外延生长的扶手椅型边界(b)和锯齿型边界(c)的石墨烯纳米带^[55]; (d)−(i) h-BN表面模板法制备石墨烯纳米带: (d) h-BN的平整表面, (e) h-BN表面镍金属颗粒辅助刻蚀出的纳米沟槽, (f) h-BN纳米沟槽内模板法制备石墨烯纳米带, (g)−(i)与图(d)−(f)相对应的AFM摩擦力图像

Fig. 5. Different methods for the fabrication of GNRs on h-BN. (a) Fabrication of GNRs on h-BN by anisotropic etching^[59]; (b), (c) GNRs with AC-oriented (b) and ZZ-oriented (c) edges are grown from oriented step-edges on h-BN^[55]; (d)−(i) formation of GNRs in h-BN trenches: (d) Smooth surface of the h-BN; (e) synthesis of nano-trenches on h-BN by Ni particle-assisted etching; (f) in-plane epitaxial template growth of GNRs via CVD; (g)−(i) AFM friction images corresponding to the schematics shown in (d)−(f).

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图 6 (a)−(c)模板法制备的锯齿型石墨烯纳米带的输运特性: (a)宽度为5 nm的石墨烯纳米带在不同温度条件下电导随背栅电压的转移曲线, (b)实验提取得到的石墨烯纳米带带隙与宽度的变化关系^[48], (c)温度为2 K时, 宽度为9 nm的锯齿型石墨烯纳米带在不同磁场条件下电导随背栅电压的转移曲线; (d)氢等离子体各向异性刻蚀法制备的约68 nm宽的锯齿型石墨烯纳米带不同磁场条件下的转移曲线^[29]

Fig. 6. (a)−(c) Electronic transport through embedded ZGNR devices: (a) Conductance (G) of a typical ZGNR device with a width of ~5 nm as a function of the back gate voltage (V_gate) at different temperatures, (b) band gap E_g extracted from experimentaldata for ZGNRs versus their width (w)^[48], (c) transfer curves of a ~9 nm ZGNR sample at different magnetic field; (d) thetypical transfer curves at several B from a ZGNR/h-BN device with a width of ~68 nm fabricated by hydrogen-plasma-etching (~3 kΩ contactresistance was subtracted)^[29].

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图 7 (a)不同结构氮化硼的相图^[61]; (b) h-BN单晶的光镜照片^[62]

Fig. 7. (a) Phase diagram of boron nitride with different structures^[61]; (b) optical image of h-BN crystal^[62].

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图 8 CVD方法制备h-BN晶畴　(a)在铜镍合金上生长h-BN的示意图; (b)−(e) 分别对应着铜镍合金衬底上不同生长时间下h-BN的扫描电镜图像, 标尺为20 μm, 图(b)中插图的标尺是2 μm^[64]; (f)铜(110)面h-BN形核及生长示意图; (g)铜(110)面生长的h-BN晶畴具有相同取向, 插图是得到的均匀h-BN连续膜^[65]

Fig. 8. Synthesis of h-BN by CVD: (a) Schematic illustration showing the procedure of h-BN growth; (b)−(e) SEM images of h-BN grains grown on Cu-Ni alloy for 10, 30, 60 and 90 min, respectively, the scale bars are 20 μm, and in inset in (b) is 2 μm^[64]; (f) schematic diagrams of unidirectional growth of h-BN domains grown on Cu(110) surface; (g) SEM image of unidirectionally aligned h-BN domains on Cu(110), inset is the as-grown h-BN films^[65].

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