Physica B 323 (2002) 15

Carbon nanotubes: past, present, and future

Sumio Iijima*
Department of Materials Science and Engineering, Meijo University, NEC, and JST-ICORP, Japan Science and Technology Cooperation, 1-501 Shiogamaguchi Tempaku, Nagoya 468-8502, Japan

Abstract Carbon nanotubes have drawn tremendous interest from elds ranging from condensed-matter physics to chemistry, and from both academia and industry, because of the unique properties enabled by their nanoscale structure. In this paper, I briey outline the earlier studies concerning carbon nanotubes, and then discuss recent studies done in our laboratories. r 2002 Published by Elsevier Science B.V.
Keywords: Nanotubes; Peapod; C60; Nanohorn

In 1991, I discovered microtubules of graphitic carbon with outer diameters of 430 nm and a length of up to 1 mm (Fig. 1) [1]. These tubules consisted of two or more seamless graphene cylinders concentrically arranged. The innermost tubes of the tubules had diameters as small as 2.2 nm in some of my observations. Electron diffraction analysis showed that the crystal axis of the graphene sheets in some of the tubes had a helical arrangement relative to the tube axis. I called these tubes multi-wall carbon nanotubes (MWNT) because the tube diameters belonged to the nanometer order. The unique properties of these structures promised unimaginable applicability and thus attracted a great deal of interest that continues to this day. For example, superhigh-quality MWNTs have recently been produced by carbon evaporation using a high-frequency plasma [2]. These nanotubes had a purity of over 95% and were uniform in structure with an inside diameter of 0.4 nm, an outside diameter of about
*Tel./fax: +81-52-834-4001. E-mail address: iijimas@ccmfs.meijo-u.ac.jp (S. Iijima).

5 nm, a cone angle at the tips of 191, and a length on the micrometer order. Their walls are highly graphitized. These super-high-quality MWNTs are thus close to the ultimate in MWNTs. Single-wall carbon nanotube (SWNT), which are seamless cylinders each made of a single graphene sheet (Fig. 2), were rst reported in 1993 [3,4]. Their diameters range from 0.4 to 23 nm, and their length is usually of the micrometer order. SWNTs usually come together to form bundles. In a bundle, the SWNTs are hexagonally arranged to form a crystal-like structure [5]. These unique structures lead to unique SWNT propertiesmechanical strength greater than that of Fe, density lower than that of Al, and thermal stability at 14001C in a vacuum. The SWNTs emit electrons from their tips when exposed to a low electric eld, enabling their application in at-panel displays. Their thin needle-like structure allows them to be used as probe tips in scanning tunneling microscopy and atomic force microscopy. The nanometer-scale spaces inside and among the SWNTs should provide large gasadsorption capacities, which are especially exciting

0921-4526/02/$ - see front matter r 2002 Published by Elsevier Science B.V. PII: S 0 9 2 1 - 4 5 2 6 ( 0 2 ) 0 0 8 6 9 - 4

S. Iijima / Physica B 323 (2002) 15

Fig. 2. Computer-generated images of single-wall carbon nanotubes: (a) (11,11) armchair type, (b) (18,0) zig-zag type, and (c) (14,7) helical type. The numbers in parentheses are the chiral indices.1

Fig. 1. Multi-wall carbon nanotubes discovered in 1991 [1].

when we consider hydrogen adsorption. A practical means of storing hydrogen will be a boon for fuel-cell development and an important step towards achieving a source of clean energy that can be widely applied. A recent report has claimed that 10-wt% hydrogen uptake by SWNTs is possible [6]. Elsewhere, SWNTs with a diameter of about 0.4 nmthe thinnest yethave been made [7,8], and such ne SWNTs raise new possibilities for electrical superconductivity [9]

that could have a great impact as the critical temperature for superconductivity becomes higher. Another intriguing possibility is that we can use the hollow space inside SWNTs as one-dimensional elds for applications in physics, chemistry, and, perhaps in the future, biology. This idea sprung from an examination of the C60 molecules incorporated inside the SWNTs, which are called peapods because of their shape [10]. A particular type of SWNT, the single-wall carbon nanohorn (SWNH), is likely to be used in fuel cells within a few years. SWNHs are efcient carriers of the Pt particles used as a catalyst in the fuel-cell reaction [11] and of adsorbed methane used as the fuel [12]. Thus, carbon nanotubes clearly have wide ranging properties and structures that we are still in the process of discovering, and a delicious variety of potential applications. In this review article, I will focus on two especially fertile research areasfullerene-incorporated nanotubes and the gas-adsorption phenomena of SWNHs. Fullerene-incorporated nanotubes were rst discovered by Smith and Luzzi in 1998 [10]. A means of producing this structure on a large scale was later developed by Bandow et al. [13,14]. A transmission electron microscopy (TEM) image of the peapods formed by Bandow et al., is shown in Fig. 3, where almost all the SWNTs are lled with
1 All computer-generated graphics appearing in Figs. 4, 5 and 6 were presented by K. Hirahara.

S. Iijima / Physica B 323 (2002) 15

Fig. 3. TEM image taken for metallofullerene (Sc2@C84) encapsulated SWNTS.

the fullerene molecules and which appear to follow a regular arrangement. The average distance between the adjacent fullerene molecules such as C60, estimated by electron diffraction analysis, was about 0.97 nm [15]. This distance is about 3% shorter than the C60C60 distance in C60 crystals, and this shortened distance indicates that the interaction between the C60 molecules was inuenced by the SWNT walls. Corresponding to this phenomenon, a certain selectivity concerning the SWNT diameter has been observed when fullerene molecules are incorporated into SWNTs [13]. Specically, if the fullerene molecules have a diameter small enough to keep themselves off from the SWNT wall by a distance exceeding 0.34 nm, the fullerene molecules are not stabilized inside the SWNTs. In contrast, when the fullerene diameter is a close t to the SWNT diameter, the C60 molecules will not come out of the SWNT even at 8001C under a high vacuum [16]. This strong interaction energy has been estimated to correspond to a compressing pressure of 0.1 GPa [17]. Peapods offer fascinating possibilities in chemistry and physics. When peapods are heated to 100012001C, the C60 molecules coalesce and change into a new SWNT, thus resulting in a double-wall carbon nanotube (Fig. 4). As is well known, when C60 molecules are heated to such a high temperature, they usually coalesce and form

Fig. 4. Computer-generated image (top) and TEM image (bottom) of double-wall carbon nanotubes formed by heat treatment of peapods in a vacuum (106 Torr at 12001C for 10 h). The wall-to-wall distance estimated from the TEM image was 0.36 nm [16].

Fig. 5. TEM (top) [15] and computer-generated (bottom) images of Gd@C82 peapods.

amorphous carbon. The transformation from peapods to double-wall carbon nanotubes proves that the hollow inside of an SWNT can act as a one-dimensional reaction eld where only SWNTs can form. Like C60, metallofullerenes such as Gd@C82 can also form peapods (Fig. 5) [13]. Since the Gd atoms have an electron spin, the order of the spins in this conned dimension is of great interest. Regrettably, this ordering has yet to be

S. Iijima / Physica B 323 (2002) 15

observed. The spin ordering inside the peapods, though, could have a considerable impact on the development of future memory devices. The challenge now is to devise a way to mass produce SWNTs of high purity and to control the length, diameter, and chirality. Unfortunately, it may be some time before this is realized. We have obtained SWNHsSWNTs that had long coneshaped caps with an angle of about 191, a diameter of 24 nm, and a length of about 50 nm. They came together to form a spherical aggregate, and at their center the SWNHs coalesced (Fig. 6) [18]. Since the SWNH tubes coalesced at the aggregation center, the aggregates cannot be separated into individual pieces. These SWNH aggregates were obtained at a rate of 1050 g/h and a yield of 7080%. The purity was 90% or higher by CO2 laser ablation of graphite at room temperature [18]. SWNHs are closed in their as-grown state with a surface area of about 300 m2/g, but windows can be opened by treating the SWNHs in an oxygen atmosphere [19,20], and the window size can be controlled through the oxygen-treatment conditions. When we heated SWNHs to 4201C in 760Torr oxygen gas, the surface area became about 1000 m2/g. Since the wall of a SWNH is a single graphene sheet and the adjacent wall-to-wall

distance is about 0.34 nm [21], the adsorption phenomena of the SWNH aggregates are unique. For example, the molecular sieving effect has been observed for various gases [22]. This molecular sieving effect occurs because the SWNHs are each made of a single graphene sheet. If they had thick walls of graphite or amorphous carbon, we would not be able to control the window diameters simply by means of treatment in oxygen gas. This gas-adsorption phenomenon exemplies the many potential ways we can take advantage of the SWNT gas-adsorption phenomena. In this article, I have briey touched upon only a few of the ambitious studies and application possibilities regarding the unique nanometer-scale space inside SWNTs and the special behavior that arises from the ultimately thin wall of a single graphene sheet. New phenomena are still being discovered 10 years after the discovery of carbon nanotubes [1], and I feel certain there are many more attractive phenomena hidden within the tiny, mysterious world that exists inside the carbon nanotube.

References
[1] S. Iijima, Nature 354 (1991) 56. [2] A. Koshio, M. Yudasaka, S. Iijima, Chem. Phys. Lett., submitted for publication. [3] S. Iijima, T. Ichihashi, Nature 363 (1993) 603. [4] D.S. Bethune, C.H. Kiang, M.D. de Vries, G. Gorman, R. Savoy, J. Vazquez, R. Beyers, Nature 363 (1993) 605. [5] A. Thess, R. Lee, P. Nikolaev, H. Dai, P. Petit, J. Robert, C. Xu, Y.H. Lee, S.G. Kim, A.G. Rinzler, D.T. Colbert, G.E. Scuaeria, D. Tomanek, J.E. Fisher, R. Smalley, Science 273 (1996) 483. [6] A.C. Dillon, K.M. Jones, T.A. Bekkedahl, C.H. Kiang, D.S. Bethune, M.J. Heben, Nature 386 (1997) 377. [7] L.C. Qin, X. Zhao, K. Hirahara, Y. Miyamoto, Y. Ando, S. Iijima, Nature 408 (2000) 50. [8] N. Wang, Z.K. Tang, G.D. Li, J.S. Chen, Nature 408 (2000) 51. [9] Z.K. Tang, L. Zhang, N. Wang, X.X. Zhang, G.H. Wen, G.D. Li, J.N. Wang, C.T. Chan, P. Sheng, Science 292 (2001) 2462. [10] B.W. Smith, M. Monthioux, D.E. Luzzi, Nature 396 (1998) 323. [11] T. Yoshitake, Y. Shimakawa, S. Kuroshima, H. Kimura, T. Ichihashi, Y. Kubo, D. Kasuya, Y. Takahashi, F. Kokai, M. Yudasaka, S. Iijima, Physica B, this issue.

Fig. 6. TEM (top) [18] and computer-generated (bottom) images of single-wall carbon nanohorns.

S. Iijima / Physica B 323 (2002) 15 [12] K. Murata, J. Miyawaki, K. Kaneko, W.A. Steele, D. Kasuya, T. Takahashi, F. Kokai, M. Yudasaka, S. Iijima, Science, submitted for publication. [13] K. Hirahara, K. Suenaga, S. Bandow, H. Kato, T. Okazaki, H. Shinohara, S. Iijima, Phys. Rev. Lett. 85 (2000) 5384. [14] H. Kataura, Y. Maniwa, T. Kodama, K. Kikuchi, K. Hirahara, K. Suenaga, S. Iijima, S. Suzuki, Y. Achiba, W. Kraetschmer, Syn. Met. 121 (2001) 1195. [15] K. Hirahara, S. Bandow, K. Suenaga, H. Kato, T. Okazaki, H. Shinohara, S. Iijima, Phys. Rev. B 64 (2001) 115420. [16] S. Bandow, M. Takizawa, K. Hirahara, M. Yudasaka, S. Iijima, Chem. Phys. Lett. 337 (2001) 48. [17] D. Tomanek, private communication.

[18] S. Iijima, M. Yudasaka, R. Yamada, S. Bandow, K. Suenaga, F. Kokai, K. Takahashi, Chem. Phys. Lett. 309 (1999) 165. [19] K. Murata, K. Kaneko, W.A. Steele, F. Kokai, T. Takahashi, D. Kasuya, M. Yudasaka, S. Iijima, Nano Lett. 1 (2001) 197. [20] K. Murata, K. Kaneko, W.A. Steele, F. Kokai, T. Takahashi, D. Kasuya, K. Hirahara, M. Yudasaka, S. Iijima, J. Chem. Phys. B 105 (2001) 10210. [21] S. Bandow, F. Kokai, K. Takahashi, M. Yudasaka, L.C. Qin, S. Iijima, Chem. Phys. Lett. 321 (2000) 514. [22] K. Murata, K. Kaneko, W.A. Steele, D. Kasuya, K. Hirahara, K. Takahashi, F. Kokai, M. Yudasaka, S. Iijima, Science, submitted for publication.