Carbon 37 (1999) 14491453

Mass-production of single-wall carbon nanotubes by arc discharge method 1

Zujin Shi a , Yongfu Lian a , Xihuang Zhou a , Zhennan Gu a , *, Yaogang Zhang b , Sumio Iijima b , Lixia Zhou c , Kwok To Yue c , Shulin Zhang c
b a Department of Chemistry, Peking University, Beijing 100871, People s Republic of China Fundamental Research Laboratories, NEC Corporation, 34 Miyukigaoka, Tsukuba, Ibaraki 305 -8501, Japan c Department of Physics, Peking University, Beijing 100871, People s Republic of China

Received 6 August 1998; accepted 23 December 1998

Abstract With a YNi alloy composite graphite rod as anode for d.c. arc discharge, a cloth-like soot was produced, containing about 40% single wall carbon nanotubes (SWCNTs). By characterization with high resolution transmission electron microscope (HREM) and Raman spectroscopy, it is found that the SWCNTs have nearly the same diameter of 1.3 nm and belong to armchair (n, n) type carbon nanotubes (n 58, 9, 10 and 11). It is also proposed that a large temperature gradient and the addition of YNi alloy in the anode are the two most important factors inuencing the formation of SWCNTs. 1999 Elsevier Science Ltd. All rights reserved.
Keywords: A. Carbon nanotubes

Since the discovery of multi-wall carbon nanotubes (MWCNTs) [1] and single-wall carbon nanotubes (SWCNTs) [2,3], a great deal of progress has been made in this area. With the success of high yield synthesis by laser ablation [4], it was proved that the single-wall carbon nanotubes are good quantum wires [5] and conductors [6]. Further studies and applications of this tiny tube, however, are impeded by the lack of mass-production in cheaper ways. By using the composite graphite rods containing metallic yttrium and nickel, C. Jounet et al. [7] found a high yield of single-wall carbon nanotubes in the small collar around the cathode deposit after arc-discharge. In this paper, instead of metallic yttrium and nickel mixture, YNi alloy was used and a much larger amount of singlewall carbon nanotubes was obtained in the soot produced by d.c. arc discharge at proper conditions. It is also shown that the SWCNTs have the same structure as those produced by laser ablation. In addition, it is proposed that

the driving force for the formation of SWCNTs is the high temperature gradient.

1. Experimental The single-wall carbon nanotubes were produced by d.c. arc discharge method. A f3370 mm hole was drilled in a f63300 mm spectrally pure graphite rod and lled with 1:1 molar ratio of graphite and YNi alloy (YNi 2 ) powder. It is desirable to synthesize SWCNT using YNi 2 instead of their metal mixture because YNi alloy is easily ground into powder and stable in the atmosphere. The cathode was a f10 mm graphite rod with a sharp end toward the anode in order to decrease the formation of cathode deposit. The arc was generated by a current of 40100 A in a helium atmosphere at a pressure of 100700 torr. When the discharge was running, the distance between two electrodes was maintained constant at |5 mm by continuously translating the anode. After arc discharge, the soot on the inner wall of the chamber was collected. The soot was extracted by CS 2 , washed with 1:1 hydrochloric acid and dried at 1008C to remove most of

*Corresponding author. This work was supported by the National Natural Science Foundation of China, No. 29671030.
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0008-6223 / 99 / $ see front matter 1999 Elsevier Science Ltd. All rights reserved. PII: S0008-6223( 99 )00007-X

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the fullerenes and catalysts. Finally, the sample was characterized by HREM (200 keV) and Raman spectrometer (Renishaw System 1000, excited with 632.8 and 514.5 nm radiation, respectively).

2. Results and discussion In our experiments, the arc discharge conditions were optimized for different current and helium pressure. Keeping the current intensity at 40 A, the arcs were generated under 100, 300, 500 and 700 torr helium pressure, respectively. It was found that the soot deposited on the wall of the chamber was loose with the helium pressure in the range of 100300 torr and from 300 torr on it became stickier with increasing helium pressure. For easy control of the discharge, 500 torr He pressure was chosen. At 500 torr He pressure, viscosity of the soot showed no obvious change as the current varied from 40 A to 100 A. Thus, 40 A d.c. and 500 torr He atmosphere were used. In this case, 1.5 gram of soot was produced after spending 5 cm anode rod and the soot thus obtained was cloth-like covering over the whole inner wall of the chamber. Fig. 1 are the HREM images of the sample. From these images, it can be found that most SWCNTs exist in bundles, each bundle consisting of tens of SWCNTs as the SWCNT rope obtained with the laser ablation [4]. The SWCNTs have nearly the same diameter of about 1.3 nm with length of several microns, being also the same as those with the laser ablation method. In addition, the directions of bundles are random. From Fig. 1a, it can be seen that there are two types of caps at the end of SWCNT, one being at in the central part of the image (A), and other being semi-spherical in the right part of the image (B). In Fig. 1b radial single-layer nanotubes can also be found as reported by Subramoney et al. [8]. These two radial single-wall carbon nanotubes are all composed of SWCNT bundles in different directions and the core is a carbon nanoparticle. These core nanoparticles are different from each other, however, being hollow in our case while lled with metal carbide in the case of Subramoneys. It can also be found that the radial SWCNT bundles are not grown up from the nanoparticle as the fringes of the nanoparticle are overlapped with SWCNT bundles. Therefore, it can be seen the core nanoparticle is not the core for the growth of SWCNTs. Fig. 2a is the Raman spectrum of SWCNT excited by 632.8 nm laser radiation, in which the dotted line is Raman spectrum of SWCNT produced by laser ablation [4]. From this gure, it can be found that two types of SWCNT have similar characteristics of Raman vibrations, i.e., their structures are similar. Fig. 2b is the amplication of Fig. 2a in the region from 120 to 200 cm 2 1 and the dotted lines are the result of Lorentzian t. Table 1 is the experimental and calculated results of Raman spectra. From Table 1, it can be found that almost all of the Raman peaks of our

sample are consistent with the results of theoretical calculation except for 175 cm 2 1 (174 cm 2 1 excited by 514.5 nm) which can not be assigned with armchair tubes. This indicates that the SWCNTs are armchair (n, n) type tubes with n 58, 9, 10 and 11 and there are probably other structure types of nanotubes in the sample. From Fig. 2, it can also be seen that the Raman peak corresponding to (10, 10) nanotubes is stronger than the others, indicating that the (10, 10) nanotube in the sample might be more abundant than the others. In addition, it was found during the experiment that the intensity ratio of peak 160 cm 2 1 and 186 cm 2 1 is different in different areas, which indicates the different abundance of tube (9, 9) or tube (10, 10) in different areas. Therefore, it can be conjectured that the tubes of the same structure have a tendency to aggregate with each other. It is estimated that the soot, produced by d.c. arc discharge with graphite rods containing YNi alloy and washed with CS 2 , hydrochloric acid successively, contains about 40% SWCNTs from HREM observation and Raman spectroscopy characterization. Therefore, a signicant amount of SWCNT can be produced in this way. In general, soot containing fullerenes [10] and cathode deposit containing carbon multi-wall nanotubes [1] were produced when the graphite anode was evaporated by d.c. arc discharge. If the composite rods containing some catalysts such as Co, Ni etc., single-wall carbon nanotubes can form in the soot besides fullerenes [2,3]. Therefore, fullerenes and SWCNTs form on the way from the arc center to the water cooled oven wall in a similar mechanism. In our former account on the multi-wall carbon nanotubes [11], it was mentioned that the direction of carbon nanotubes in the cathode deposit are not parallel to that of the electric eld so that it was suggested that the direct driving force for the growth of carbon nanotubes is the temperature gradient existing between the anode and the cathode instead of the electric eld. In case of SWCNTs, it can also be suggested that the direct driving force for the growth of carbon nanotubes is the temperature gradient existing between the electrodes and the oven wall. The temperature gradient as the driving force for the formation of SWCNTs can be rationally explained by the experiments mentioned above, where the amount of SWCNTs in the soot increase with the helium pressure and remain nearly constant with the change of electric current. So helium pressure has a pronounced inuence on the yield of SWCNTs. The temperature gradient between the electrodes and the oven wall increases with helium pressure. High helium pressure will help producing SWCNTs. At last, it should be pointed that yttrium and scandium are two metals of special interest in the formation of fullerenes. It is yttrium or scandium metallofullerenes [12,13] which can be prepared more easily and in higher yield than those of other elements. With the composite rods

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Fig. 1. HREM images of the sample in larger magnication, in which (a) the random SWCNT bundles and the SWCNTs with at (A) and semi-sphere cap (B), (b) radial SWCNT bundles together with a hole carbon nanoparticle can be found.

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Fig. 2. (a) Raman spectra (excited with 632.8 nm laser) of SWCNT produced by d.c. arc-discharge and laser ablation, (b) Raman spectrum amplied with Fig. 2a in the of low wavenumber (from 120 to 200 cm 2 1 ), dotted lines are the result of Lorentzian t.

Z. Shi et al. / Carbon 37 (1999) 1449 1453 Table 1 Raman wavenumbers (cm 2 1 ) and structures of SWCNT This sample (excited by 632.8nm) This sample (excited by 514.5nm) Theoretical calculation [9] Structure of SWCNT 130 143 150 130 (9, 9) 146 (8, 8) 150 (11, 11) 160 166 165 (10, 10) 176 174 186 185 183 (9, 9)

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206 206 (8, 8)

containing yttrium or scandium as anode, a much higher yield of MWCNT can be obtained in cathode deposit after d.c. arc discharge [11,14]. In the case of SWCNT, yttrium has also exhibited special property. Therefore, it will be worthwhile to study the behaviors of these elements further in fullerenes chemistry.

3. Conclusion With the composite graphite rods containing YNi alloy as anode in d.c. arc discharge, cloth-like soot containing about 40% SWCNTs was produced in a considerably larger amount. The SWCNTs have the nearly same diameter of 1.3 nm and belong to armchair (n, n) type carbon nanotubes (n 58, 9, 10 and 11). It is also suggested that the high temperature gradient between the electrodes and the oven wall and the use of YNi alloy are the critical factors for the formation of SWCNTs.

[3] Bethune DS, Kiang CH, de Vries MS et al. Nature 1993;363:605. [4] Thess A, Lee R, Nikolaev P et al. Science 1996;273:483. [5] Tans SJ, Devoret MH, Dai HJ et al. Nature 1997;386:474. [6] Collions PG, Zettl A, Bando H, Thess A, Smalley RE. Science 1997;278:100. [7] Journet C, Maser WK, Bernier P et al. Nature 1997;388:756. [8] Subramoney S, Rouff RS, Lorents DC, Malhotra R. Nature 1993;266:637. [9] Rao AM, Richter E, Bandow S et al. Science 1997;275:187. [10] Kratschmer W, Lamb LD, Fostiropolos K, Huffman DR. Nature 1990;347:354. [11] Shi ZJ, Zhou XH, Jin ZX et al. Solid State Communications 1996;97:371. [12] Shinohara H, Yamaguchi H, Hayashi N et al. Phys Chem 1993;97:4259. [13] Stevanson S, Dorn HC, Burbank P et al. Analytical Chemistry 1994;66:2675. [14] Ohkohchi M, Ando Y, Bandow S, Saito Y. Jpn J Appl Phys 1993;32:L1248.

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