A Review on the Controlled Growth of Single-Wall Carbon Nanotubes from Metal Catalysts

doi:10.11900/0412.1961.2018.00423

Acta Metall Sin

2018, Vol. 54

Issue (11): 1665-1682 DOI: 10.11900/0412.1961.2018.00423

Materials and Processes

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A Review on the Controlled Growth of Single-Wall Carbon Nanotubes from Metal Catalysts

Zhonghai JI^1,², Lili ZHANG^1,², Daiming TANG^1,²(

), Chang LIU^1,², Huiming CHENG^1,³

1 Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2 School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
3 Tsinghua-Berkeley Shenzhen Institute, Shenzhen 518055, China

Cite this article:

Zhonghai JI, Lili ZHANG, Daiming TANG, Chang LIU, Huiming CHENG. A Review on the Controlled Growth of Single-Wall Carbon Nanotubes from Metal Catalysts. Acta Metall Sin, 2018, 54(11): 1665-1682.

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Abstract

Single-wall carbon nanotubes (SWCNTs) with a unique tubular structure have exhibited excellent electrical, thermal and mechanical properties. However, their attractive applications in microelectronic devices and sensors are still pending due to the lack of high-quality, structure-defined SWCNTs. It is still a great challenge to grow pure and ordered SWCNTs with designated structures and properties. The key of breakthrough is to understand the fundamental nucleation and growth mechanism of SWCNTs under reaction conditions. In this article, we analyze the influences of physical and chemical properties, such as electronic structure, melting point, carbon solubility, and diffusivity, of catalyst nanoparticles on the productivity, purity, and fine structures of grown SWCNTs. The progress, current situation, and challenges on the controlled growth of SWCNTs are summarized. Finally, perspectives on future directions are presented and a strategy of structure-controlled production of SWCNTs is proposed.

Key words: metal catalyst single-wall carbon nanotube structure control growth mechanism

Received: 08 September 2018

Fund: Supported by National Natural Science Foundation of China (Nos.51522210, 51802316, 51521091, 51625203), National Key Research and Development Program of China (No.2016YFA0200101) and Hundred Talents Program of Chinese Academy of Sciences

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	Zhonghai JI
	Lili ZHANG
	Daiming TANG
	Chang LIU
	Huiming CHENG

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https://www.ams.org.cn/EN/10.11900/0412.1961.2018.00423 OR https://www.ams.org.cn/EN/Y2018/V54/I11/1665

Fig.1 A schematic showing the catalytic reaction, transport, nucleation and growth process of single-wall carbon nanotubes (SWCNTs)

Fig.2 In-situ TEM observations of the nucleation and growth of individual CNTs from Co (a), Fe (b), Au (c) and SiO_x (d) catalyst nanoparticles (DWCNT—double-wall carbon nanotube, C'_sup(t)—active carbon supply rate, C'_inc(t)—carbon incorporation rate, t—time)^[31,32,33]

Fig.3 Metal-carbon phase diagrams (T—temperature)^[64,77]
(a) Ni-C eutectic phase diagram, red arrows represent vapor-liquid-solid (VLS) growth mechanism; green arrows represent vapor-solid-solid (VSS) growth mechanism
(b) nanoscale Ni-C phase diagram. The melting and eutectic points are dramatically lowered. The carbon solubility is increased and a new phase with fluctuation surface structures appears (x_c—atomic fraction of carbon)
(c) Cu-C phase diagram. Carbon solubility is almost 0% in the solid phase
(d) W-C phase diagram, including stable W₂C and WC phases. The melting and eutectic points are higher than 2500 ℃, much higher than the growth temperature of CNTs

Fig.4 Types of metal catalysts for SWCNT growth. The melting points are represented by the filled color of the blocks, with blue and red for low and high melting points, respectively. The types of the catalyst are marked by the colors of the frames: Fe group metals (green), Pt group metals (blue), coin metals (red), carbide formation metals (black) and oxide formation metals (purple)^[90]

Table 1 Property and Characteristics of Metal Catalyst for SWCNTs^{[35,68,71,91~94]}

Fig.5 SWCNTs grown from Fe group metals catalysts^{[12,21,100,101]}
(a) vertical array
(b) horizontal array
(c) semiconductor-enriched SWCNTs
(d) isolated SWCNTs films

Fig.6 SWCNTs grown by coin metals (Au, Cu)^[49,51,78]
(a) TEM and SEM images of Au nanoparticles and grown SWCNTs, and PL spectra of SWCNTs grown at different temperatures
(b) growth of SWCNTs network and horizontal array from Cu nanoparticles

Fig.7 SWCNTs grown from bi-metallic catalysts^[27,145,146]
(a) growth rates of metallic nanotubes on Ni, Cu and Ni-Cu catalysts
(b) selective growth of (6, 5) and (7, 5) SWCNTs from Co-Mo catalyst
(c) chirality-specific growth of SWCNTs from Co-W catalyst

Fig.8 SWCNTs grown from metal compound catalysts^[150,151]
(a) selective growth of metallic or semiconducting SWCNTs by SiO_x catalyst. (a1, b1) heating SiO_x thin films to form nanoparticles; (c1, d1) relationship between O/Si ratios of SiO_x nanoparticles and percentage of grown semiconducting or metallic SWCNTs; (e1, f1) Raman spectra and transistor performance based on metallic and semiconducting SWCNTs
(b) growth of semiconducting SWCNTs by Mo₂C (a2), SEM image, Raman spectra, AFM analysis and diameter distribution of Mo₂C catalyzed SWCNT arrays (b2~e2)

Table 2 Structure controlled growth of SWCNTs from different catalysts^{[11,13,14,21,29,30,32,51,78,89,100,102,104,107,116,133,139,140,149~152,155~163]}

Fig.9 Properties of metal catalysts: melting points, catalytic activity, carbon solubility and diffusion rate
(a) comparison of properties of different catalyst systems
(b) comparison of the properties of Co and Co alloys. Design strategy of multiple alloy catalyst for optimized growth yield, quality and structural control

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