Research Progress in Controllable Preparation of Graphene Nanoribbons

doi:10.6023/A22120513

Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (4): 406-419.DOI: 10.6023/A22120513 Previous Articles Next Articles

Review

石墨烯纳米带的可控制备研究进展

宁聪聪^a, 杨倩^b^,^*(), 毛阿敏^a, 唐梓嘉^a, 金燕^a, 胡宝山^a^,^*()

a 重庆大学化学化工学院重庆 401331
b 重庆科技学院冶金与材料工程学院重庆 401331

投稿日期:2022-12-28 发布日期:2023-03-16

作者简介:

宁聪聪, 重庆大学2020级在读硕士生. 2020年毕业于江南大学, 获得学士学位. 主要从事石墨烯纳米带的生长及性质研究, 发表SCI论文1篇.

杨倩, 博士, 助理研究员, 硕士生导师. 2013年毕业于重庆大学获学士学位, 2018年毕业于重庆大学获博士学位. 2018年~2020年在北京大学化学与分子工程学院从事博士后研究, 2021年加入重庆科技学院工作. 研究方向为二维材料的制备及其应用. 主持国家自然科学基金1项, 发表SCI论文10余篇.

毛阿敏, 重庆大学2020级在读硕士生. 2020年毕业于重庆大学, 获得学士学位. 主要从事石墨烯的可控制备及性质应用研究.

唐梓嘉, 重庆大学2021级在读硕士生. 2021年毕业于武汉理工大学, 获得学士学位. 主要从事石墨烯条带的可控制备及其性质研究.

金燕, 重庆大学化学化工学院实验师, 主要从事石墨烯及其复合材料的控制制备及其应用研究, 发表SCI论文10余篇.

胡宝山, 重庆大学化学化工学院副院长, 副教授, 重庆市引进高层次人才. 主要研究方向为碳纳米材料控制制备、功能化及其应用. 主持多个国家级和省部级项目, 发表SCI论文50余篇.

基金资助:
重庆市教委科技攻关项目(KJZD-M202000102); 国家自然科学基金(22005040); 中央高校科研业务专项基金(2021CDJQY-005)

Research Progress in Controllable Preparation of Graphene Nanoribbons

Congcong Ning^a, Qian Yang^b^,^*(), Amin Mao^a, Zijia Tang^a, Yan Jin^a, Baoshan Hu^a^,^*()

a School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331
b School of Metallurgy and Materials Engineering, Chongqing University of Science and Technology, Chongqing 401331

Received:2022-12-28 Published:2023-03-16
Contact: * E-mail: qianyang@cqust.edu.cn; hubaoshan@cqu.edu.cn
Supported by:
Science and Technology Research Project of Chongqing Education Commission(KJZD-M202000102); National Natural Science Foundation of China(22005040); Fundamental Research Funds for the Central Universities(2021CDJQY-005)

Graphene nanoribbons (GNRs) are the ribbons of graphene with a width of nanoscale. According to the different edge configurations, the GNRs can be classified into Zigzag-edge graphene nanoribbons (ZGNRs) and Armchair-edge graphene nanoribbons (AGNRs), strongly affecting electronic structure and properties of GNRs. The triggered quantum confinement and edge effects by rationalizing the structural design can open the bandgap of GNRs. Besides, GNRs have huge length-to-width ratio and proportion of edge atoms, which provide infinite possibilities for realizing functional customization through structure tailoring. These geometric and electronic structural properties make graphene nanoribbons have more application potential than graphene in many fields such as electronic devices. Therefore, the related research of graphene nanoribbons has been a hot spot in the field of nanomaterials. This review introduces the structures and properties of graphene nanoribbons firstly, and then provides a comprehensive picture of the preparation approaches of GNRs, and the corresponding preparation methods can be divided into two parts: (1) Top-down categories: The GNRs are obtained by the etching and cutting of graphene, as well as carbon nanotubes (CNTs), with utilizing the plasma, ion beam, scanning tunneling microscope and metal nanoparticles. However, these methods are still in the stage of laboratory research, and fabrication of high quality GNRs is difficult because of lacking the processing accuracy. (2) Bottom-up categories: The GNRs can be synthesized using carbon containing precursors, e.g. organic compounds, hydrocarbon gas and SiC. The bottom-up method facilitates to prepare several nanometers-width GNRs with a certain degree of controllability, among which ultra-narrow GNRs can be fabricated using organic synthesis, and the chemical vapor deposition (CVD) method is expected to achieve the industrial production of high-quality GNRs with low-cost preparation. Finally, we discuss the challenges and prospects of the research of GNRs. We believe that GNRs will become a new structural and functional material with great application potential in numerous fields, as is catalyzed by innovative development of materials and techniques.

Key words: graphene nanoribbons, preparation, structure, property, functionalization

Cite this article

Congcong Ning, Qian Yang, Amin Mao, Zijia Tang, Yan Jin, Baoshan Hu. Research Progress in Controllable Preparation of Graphene Nanoribbons[J]. Acta Chimica Sinica, 2023, 81(4): 406-419.

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Fig. & Tab. 8

Figure 1. Structure illustration of graphene nanoribbons. (a) Zigzag-edge graphene nanoribbons; (b) Armchair-edge graphene nanoribbons; (c) GNRs with edge vacancy; (d) GNRs with ZGNRs-AGNRs alternate edge

Figure 2. Preparation of graphene nanoribbons by cutting graphene with mask. (a) AFM image of GNRs covered by a protective HSQ etch mask[21]; (b) SEM of fabricated parallel GNRs with different widths[21]; (c) SEM image of a device containing GNR [21]; (d, e) SEM images and cross sections of FETs before (d) and after (e) oxygen plasma etched graphene[24]; (f) schematic fabrication process to obtain GNRs by oxygen plasma etch with a nanowire etch mask[27]; (g) Schematic illustration of the nanowire-masked O2 plasma etching process[29]; (h~l) wrinkle engineering for fabricating GNRs array[30]

Figure 3. Preparation of graphene nanoribbons by cutting graphene without mask. (a) Scheme of GNR arrays fabricated by helium ion beam lithography[35]; (b, c) drawing and AFM image of a nanoribbon created by a nanoparticle, forming two angles of 120o (b) and one angle of 60o (c) [38]

Figure 4. Preparation of graphene nanoribbons by cutting carbon nanotubes. (a) TEM images of the gradual unzipping of one wall of a carbon nanotube to form a nanoribbon[44]; (b, c) SEM images of MWCNTs cut with Ni nanoparticles[46]; (d) schematic diagram representing different stages of cutting MWCNTs along their axes with Ni or Co metal nanoparticles[46]; (e) making GNRs from MWCNTs which are partially embedded in PMMA[47]; (f) molecular dynamics simulation of making GNRs by unzipping CNTs [48]

Figure 5. Preparation of graphene nanoribbons by organic synthesis. (a) Reaction scheme for the formation of linear graphene nanoribbons as reported by Cai and co-workers[53]; (b) syntheses of NGs and nanoribbons by a bottom-up approach[58]; (c) experimental setup of RP-CVD with an illustration of the presumed GNRs growth mechanism when using DBBA as a monomer[59]; (d) schematic illustration of the synthesis for GNRs with DBTT precursors on Au(111) under atmospheric pressure[60]; (e) STM images of undecameric (left) and dodecameric (right) polymer [60]

Figure 6. Preparation of graphene nanoribbons by SiC epitaxial growth method. (a) AFM image of the SiC sidewall[66]; (b) STM topography image of the ladder-pattern in part (a) [66]; (c) zoomed-in image of part (b) with the armchair edges superimposed[66]; (d) schematic illustration of graphene epitaxially grown on the SiC sidewall[66]; (e) schematic illustration of preparation GNRs by SiC epitaxial growth method [68]

Figure 7. Preparation of graphene nanoribbons with the CVD method. (a~d) Graphene islands as growth seeds (a) and GNR arrays (b) on Ge(001) with schematic illustrations (a, b) and SEM images (c, d)[82]; (e) schematic illustration of growth of GNR array on liquid Cu[85]; (f) schematic diagram of the templated CVD growth of the GNRs[86]; (g) SEM images of the ZnS/G ribbons[86]; (h) schematic illustration of the direct conversion process of Ni nanobar to grow graphene nanoribbon[87]; (i) AFM image of zigzag trench on h-BN with width and depth as labelled[89]; (j) AFM image of a GNR embedded in trench with width as labelled[89]; (k) the schematic diagram for trapezoidal grooves and CVD growth of the GNR arrays[90]; (l~n) the variable temperature Raman spectra of stacked G＋G (l), NG＋G (m) and NG＋NG (n) samples [90]

制备方法		优点	缺点
切割石墨烯	掩模刻蚀法^{[24⇓⇓⇓⇓⇓-30]}	大面积、可控图案化制备	加工精度低、边缘结构不规则、掩模去除困难
切割石墨烯	无掩模刻蚀法^{[32⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓-43]}	加工精度高、边缘结构可控、制备质量高	生产成本高、生产规模小
切割碳纳米管	氧化反应切割法^[44-45]	原料成本低	提纯工艺复杂
	纳米粒子切割法^[46]	条带缺陷少、边缘平直且洁净	切割方向难控制、边缘结构不规则
	等离子体切割法^[47]	条带宽度低至数十纳米	边缘结构不规则
有机合成法	真空表面合成法^{[53⇓⇓⇓⇓-58]}	条带宽度低至数纳米	条带较短、对设备要求高、成本高
	常压表面合成法^[59⇓-61]	效率高、条带宽度窄	生产规模小
	溶液合成法^{[62⇓⇓-65]}	反应条件温和、无需贵金属催化剂	提纯复杂、产率低、制备过程复杂
SiC外延生长法^{[66⇓⇓⇓-70]}	—	无需转移、条带质量高	生产规模小
CVD生长法	选区直接生长法^{[77⇓⇓⇓⇓⇓⇓⇓-85]}	条带质量高、大面积可控制备	条带长宽比较小
	模板生长法^[86⇓-88]	条带较长、质量高	条带长宽比较小
	限域生长法^[89-90]	条带较长、质量高、可控图案化制备	条带宽度控制困难

Table 1. Reported advantages and disadvantages for GNRs prepared with various processes

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石墨烯纳米带的可控制备研究进展

Research Progress in Controllable Preparation of Graphene Nanoribbons

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