金属催化非晶碳转化制备石墨烯方法的研究进展

doi:10.15541/jim20170527

无机材料学报 ›› 2018, Vol. 33 ›› Issue (6): 587-595.DOI: 10.15541/jim20170527 CSTR: 32189.14.10.15541/jim20170527

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金属催化非晶碳转化制备石墨烯方法的研究进展

李汉超^1,2,3, 刘盼盼¹, 孙丽丽¹, 柯培玲¹, 崔平^1,2, 汪爱英¹

1. 中国科学院宁波材料技术与工程研究所, 中国科学院海洋新材料与应用技术重点实验室, 浙江省海洋材料与防护技术重点实验室, 宁波 315201;
2. 上海科技大学物质科学与技术学院, 上海 201210;
3. 中国科学院大学, 北京 100049;

收稿日期:2017-11-09 修回日期:2017-12-25 出版日期:2018-06-20 网络出版日期:2018-05-24
作者简介:李汉超(1993-), 男, 博士研究生. E-mail: lihanchao@nimte.ac.cn
基金资助:
国家自然科学基金(51371187);浙江省重点研发计划(2017C01001);浙江省公益项目(2016C31121)

Recent Development of the Transformation from Amorphous Carbon to Graphene Method via Metal Catalyst

LI Han-Chao^1,2,3, LIU Pan-Pan¹, SUN Li-Li¹, KE Pei-Ling¹, CUI Ping^1,2, WANG Ai-Ying¹

1. Key Laboratory of Marine Materials and Related Technologies, Zhejiang Key Laboratory of Marine Materials and Protective Technologies, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China;
2. School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China;
3. University of Chinese Academy of Sciences, Beijing 100049, China;

Received:2017-11-09 Revised:2017-12-25 Published:2018-06-20 Online:2018-05-24
About author:LI Han-Chao. E-mail: lihanchao@nimte.ac.cn
Supported by:
National Natural Science Foundation of China (51371187);Zhejiang Key Research and Development Program (2017C01001);Public Projects of Zhejiang Province (2016C31121)

摘要/Abstract

摘要：

石墨烯自2004年被首次发现以来, 以其独特、优异的结构和特性引起了广泛关注。目前, 石墨烯的制备已取得了众多进展, 但在大尺寸、高质量、宏量石墨烯可控制备上仍存在挑战, 对制备技术仍需要进行更广泛地探索。非晶碳与石墨烯互为碳的同素异形体, 也可作为制备石墨烯的前驱体, 近些年利用非晶碳制备石墨烯的新颖方法引起了研究学者的兴趣。本文系统论述了利用非晶碳作为固体碳源, 通过金属催化制备大尺寸高质量石墨烯的技术优势, 并着重从金属种类、退火温度、碳源及金属含量比例等方面对石墨烯生成质量的影响进行了阐述。最后, 总结了该方法生长石墨烯的机理, 并对未来的发展方向进行了展望。

关键词: 非晶碳, 石墨烯, 固体碳源, 金属催化

Abstract:

Graphene has drawn wide attention owing to its excellent properties since the discovery in 2004. There are many methods to produce graphene so far but many challenges still exist in producing scalable and high quality graphene. Thus, preparation of graphene should be further explored. Amorphous carbon and graphene are two allotropes of carbon. As one kind of solid carbon source, amorphous carbon could also be used to produce graphene. The preparation of graphene from amorphous carbon via metal catalyst has aroused much interest. Here, the advantages of using amorphous carbon as solid carbon source, to get high quality and large size graphene via metal catalyst in recent years are summarized. Several influence factors, such as metal sort, annealing temperature, the ratio of amorphous carbon to metal, have been discussed elaborately. Meanwhile, transformation mechanism from amorphous carbon to graphene has been reviewed and summarized simultaneously. Finally, the prospect of this novel fabrication method for graphene was put forward.

Key words: amorphous carbon, graphene, solid carbon source, metal catalyst

中图分类号:

TQ127

李汉超, 刘盼盼, 孙丽丽, 柯培玲, 崔平, 汪爱英. 金属催化非晶碳转化制备石墨烯方法的研究进展[J]. 无机材料学报, 2018, 33(6): 587-595.

LI Han-Chao, LIU Pan-Pan, SUN Li-Li, KE Pei-Ling, CUI Ping, WANG Ai-Ying. Recent Development of the Transformation from Amorphous Carbon to Graphene Method via Metal Catalyst[J]. Journal of Inorganic Materials, 2018, 33(6): 587-595.

图/表 12

图1 激光照射下石墨烯形成原理图[30]

Fig. 1 Schematic of graphene synthesis mechanism[30](a) Local annealing of the Ni layer by laser irradiation; (b) Dissolution of a-C in the Ni layer; (c) Aggregation and retraction of the Ni layer; (d) Direct graphene synthesis on a SiO2 surface

图2 基底200℃、氢气气氛下激光辐照样品的拉曼光谱图[30]

Fig. 2 Raman spectrum for a sample irradiated with a laser in H2 atmosphere at a substrate temperature of 200℃[30]

图3 热退火方法金属催化非晶碳转化石墨烯示意图[31]

Fig. 3 Process schematic for the metal-catalyzed crystallization of a-C to graphene by thermal annealing[31]

图4 石墨烯生长方法示意图[32]

Fig. 4 Schematic illumination of the graphene growth method[32]

图5 (a) a-C(40 nm)和(b)Ni催化结晶后得到的石墨烯(Ni厚度~300 nm)的Raman光谱图, 激光发射波长632.8 nm[31]

Fig. 5 Raman spectra of (a) a-C (40 nm) and (b) the resulting graphene layer after Ni-catalyzed crystallization (Ni thickness ~300 nm) with excitation laser wavelength 632.8 nm[31]

表1 退火热处理非晶碳转化石墨烯的实验参数及结果

Table 1 Parameters and results of thermal annealing for the experiment of transformation of a-C to graphene

a-C method	T/℃	Annealing time/min	Gas	Catalyst	Pressure/Pa	Graphene morphology	Raman		Ref.
a-C method	T/℃	Annealing time/min	Gas	Catalyst	Pressure/Pa	Graphene morphology	I_D/I_G	I_2D/I_G	Ref.
EBE	650-950	15	Ar	Ni, Co	226	Single, double layer	0.09	-	[31]
FVAD	600-1000	5	-	Ni	-	Few layer	-	-	[32]
PAPD	700-1000	5	N₂	Co, Ni	-	Multilayer	0.59	1	[35]
LA	1000	30	-	Ga	1.33×10^-2	Few layer	-	-	[36]
FIB-CVD	900-1100	30, 60	-	Ga	-	Three, four layer	-	0.84	[37]
PLD	800	5	Ar	Co	0.1	Single, double layer	2.5	0.67-1.43	[39]
MS	750-800	5-10	-	Co, Ni	3.0×10^-4	Single, double layer	-	1.43	[40]
DCMS	1100	2	Ar	Ni	0.266	Single, double layer	-	2.5	[46]
PAPD	900	5	N₂	Ni	-	Multilayer	-	-	[42]
DCMS	900	30	-	Ni	2.66×10^-4	Single, double layer	0.03	4.8	[52]

图6 不同生长条件下拉曼分析结果[33]

Fig. 6 Raman spectroscopic analysis of graphene from different growth conditions[33](a) Raman spectra of graphene on the top of the nickel layer before and after UV-ozone exposure, and graphene on the substrate after UV-ozone exposure and nickel removal; (b) Raman spectra of PMMA-derived graphene by different metal catalysts

图7 不同厚度Si/SiO2/a-C/Ni(100 nm)样品在He气氛下加热至1000℃及冷却过程中原位XRD的(002)石墨峰强等高线图, 变温速率为3℃/s, 厚度(a) 3 nm、(b) 10 nm和(c) 30 nm。不同厚度a-C样品的等高线间隔不同[41]

Fig. 7 Contour maps of in situ XRD results showing the 002 graphite peak in Si/SiO2/a-C/Ni (100 nm) samples heated to and cooled from 1000℃ in He at a ramp rate of 3℃/s for a-C thicknesses of (a) 3 nm, (b) 10 nm, and (c) 30 nm. The contour lines have a linear intensity spacing that is different for each a-C thickness[41]

图8 (a)转移到Si/SiO2后的石墨烯AFM照片和(b)石墨烯厚度与原始a-C厚度的关系[31]

Fig. 8 (a) AFM image of a transferred graphene sheet on Si/SiO2 substrate; (b) Graphene (and graphite) thickness vs initial a-C thickness[31] Samples were annealed at 800?℃ for 15 min with a 300 nm Ni catalyst layer

图9 a-C和Ni厚度对石墨烯生长的影响[46]

Fig. 9 Influence of Ni and C film thicknesses on graphene growth[46](a) Raman spectra of RTP graphene grown with a 5 nm C film covered with a Ni film of different thicknesses; (b) ID/IG and I2D/IG Raman peak ratios of the RTP graphene as functions of Ni film thickness; (c) Raman spectra of RTP graphene grown with a 65 nm Ni film on top of a C film with different thicknesses; (d) ID/IG and I2D/IG Raman peak ratios of the RTP graphene as functions of C film thickness

图10 非晶碳上Ni的暗场STEM照片[25]

Fig. 10 Plan-view scanning transmission electron microscopy (STEM) dark-field images of Ni crystals on an amorphous carbon film at 400℃ (a), 600℃ (b) and 720℃ (c) [25](a) At 400℃, the coherent polycrystalline Ni film (bright) covers the C substrate entirely; holes in the C film appear black; (b) At 600℃, ripening of the metal crystals starts and uncovers areas of the amorphous carbon film (light gray contrast); (c) At 720℃, ripening continues and graphene areas appear (dark, marked with arrows)

图11 溶解析出形成石墨烯的示意图

Fig. 11 Schematic illustration of graphene formation via C dissolution-precipitation

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金属催化非晶碳转化制备石墨烯方法的研究进展

Recent Development of the Transformation from Amorphous Carbon to Graphene Method via Metal Catalyst

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