APPLIED PHYSICS LETTERS 86, 023110 (2005)

Interwall support in double-walled carbon nanotubes studied by scanning tunneling microscopy

Min Hwan Park, Jae Won Jang, and Cheol Eui Leea)
Department of Physics and Institute for Nano Science, Korea University, Seoul 136-701, Korea

Cheol Jin Lee

Department of Nanotechnology, Hanyang University, Seoul 133-791, Korea

(Received 23 August 2004; accepted 16 November 2004; published online 5 January 2005) Atomically resolved room temperature scanning tunneling microscopy images of carbon nanotubes were obtained, and actual values of the nanotube dimensions were estimated from a line prole tting analysis. It was found that the cross sectional deformation induced by the van der Waals forces between the CNTs and the substrate is much smaller in the double-walled carbon nanotubes than in the single-walled nanotubes. 2005 American Institute of Physics. [DOI: 10.1063/1.1851615] Carbon nanotubes (CNTs) have been actively studied because of their unique structure and extraordinary physical properties since the discovery.1 While studies of the multiwalled carbon nanotubes (MWNTs) as well as the singlewalled nanotubes (SWNTs) are being actively carried out, in order to fully elucidate the properties of the CNTs, it is necessary to investigate the CNTs with precisely controlled number of walls. In this regard, double-walled carbon nanotubes (DWNTs) have been studied by many workers, for example, by Raman spectroscopy, for identication of the radial breathing modes associated with both inner and outer tubes.2,3 The structural properties of DWNTs were studied by electron diffraction,4 x-ray diffraction,5 and theoretical calculation,68 which showed that the interlayer distance of the DWNTs is 0.33 0.41 nm and that their properties depend primarily not on the interaction between the inner and outer tubes, but on the chirality pairs. The electrical properties dependent on the chiral indices were also reported.9 Recent scanning tunneling microscopy (STM) investigations of SWNTs and MWNTs have revealed a direct relation between their geometric structure and electrical properties. The electrical properties, depending on the diameter and deformation of the CNTs, can be either metallic or semiconducting.1014 In this letter, we report STM measurements of SWNTs and DWNTs. Deformation in both SWNTs and DWNTs was examined for actual diameters and heights, which were obtained from tting of the STM image measurements. Besides, the diameter dependent deformation in SWNTs and DWNTs was comparatively discussed. The SWNT and DWNT samples were synthesized using the arc discharge method. The as-grown CNTs were sonicated in ethyl alcohol for 30 min, then a droplet of the dispersed solution was deposited on highly oriented pyrolytic graphite (HOPG) in ambient conditions for the STM measurements. Measurements of SWNTs and DWNTs were carried out by the atomically resolved STM in ambient conditions (SPA400, Seiko Instruments Inc.), using very sharp, mechanically polished Pt tips. The images were obtained with a constant current mode.
a)

Figure 1 shows the atomically resolved room temperature STM image of a DWNT, as well as a schematic diagram of the cross sectional STM images. As displayed in Fig. 1, the apparent height H and diameter D of the CNT may differ considerably from the actual ones.1517 The main factors of such a discrepancy are the geometrical convolution between the CNTs and the STM tip shape, and the different tunneling gaps between the STM tip and the CNT or the HOPG substrate. In the imaging of a ne CNT with a blunt spherical tip, a major lateral experimental error occurs in the cross sectional line prole of the CNT. For example, a CNT

Author to whom correspondence should be addressed; electronic mail: rscel@korea.ac.kr

FIG. 1. (a) The atomically resolved STM image of DWNT. Inset: the schematic diagram of the STM image. In Region 1 the tunneling current only ows to the CNT and in Region 2 the tunneling current ows to the HOPG substrate and the CNT at the same time, whereas in Region 3 the tunneling current ows only to the HOPG substrate. (b) Schematic diagram of the cross sectional STM image, with the deformed CNT lying on a HOPG substrate in the xy plane with tube axis denoted as the x direction.

0003-6951/2005/86(2)/023110/3/$22.50 86, 023110-1 2005 American Institute of Physics Downloaded 09 Jan 2005 to 166.104.127.71. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp

023110-2

Park et al.

Appl. Phys. Lett. 86, 023110 (2005)

observed by extremely blunt tip may have an apparent diameter, as much as several tens times greater than the apparent height. In fact, the aspect ratio of the STM tip plays an important role on the accuracy of the tube geometry determination. If the tip is sharp enough, one can obtain nearly the actual CNT sizes. In practice, lateral tip-CNT forces may lead to compression of CNTs during the scanning. Therefore, the topmost surface of a CNT may be distorted by the scanning STM tip,18 and lateral tip-CNT forces may disrupt the binding between the CNT and the HOPG substrate. In order to minimize this effect, high-resolution images were taken with the fast scan direction nearly parallel to the CNT axis. The determination of the diameter and the height also involves careful consideration of different tunneling gaps between the STM tip and CNTs with different local density of states for the electronic structures.19 The tunneling gaps change with the tunneling bias between the tip and the CNT or the HOPG substrate,20 and different tunneling gaps between the CNTs and the HOPG substrate seriously hamper the determination of the height of CNTs. We now consider a deformed CNT lying on a HOPG substrate in the xy plane with the tube axis denoted as the x direction [Fig. 1(b)]. The compression rate of a CNT is generally indicated by the ratio of the perpendicular and horizontal lengths, 1 + h / r , where r is the CNT radius and h is the tunneling gap between the tip and CNT. For example, if a typical tunneling gap between the STM tip and the CNT is 0.4 nm and the tube radius is 0.7 nm, the lattice is distorted by 60%.21 When the tip is sharp enough to obtain nearly the actual diameter of the CNT, the main errors in the apparent height arise from the mechanical deformation of the CNTs. Thus, it is in general not easy to obtain the real diameter and height of the CNT after deposition on the substrate. It is necessary to consider the angle in Fig. 1(b) in order to nd the actual diameter and the height of the CNTs by tting methods. In the inset of Fig. 1(a), the tunneling current ows only to the CNT in Region 1 and only to the HOPG substrate in Region 3, whereas in Region 2 it ows to the CNT and the HOPG substrate at the same time. The tunneling gap between the tip and CNT is kept constant while the STM tip is in Region 3 with a constant current. The angle will then represent Region 1. The regional boundaries can easily be distinguished from the atomic image of the CNTs. The scanning path of the STM tip closely reects the outer wall of the CNT while the tip is in the angle . It is assumed that is representative of the whole shape obtained by tting. By tting the scan line of the STM tip corresponding to , the whole shape can be reconstructed by a perforated line as seen in Fig. 1(b). The outermost shape of the CNT corresponds to the line tted from , because the tunneling gap is kept constant during the scanning in the region of . Thus, if a CNT has an elliptic shape deformed by the van der Waals force, the tted gure will also be an elliptic shape. In determining the angle with tting, we can also determine the A, B, a and b values as denoted in Fig. 1(b). Using the simple relation B + b = Th + H, as indicated in Fig. 1(b), we may easily obtain the b value. Here, Th is the constant tunneling gap between the tip and the HOPG substrate and can be estimated, with some errors, to be about 1 nm in the experimental condition. The b value will of course be slightly greater than that of b due to the asymmetric deformation [Fig. 1(b)], with an error range of the b and

FIG. 2. (a) The horizontal radius a and the perpendicular radius b for the samples of SWNTs and DWNTs. The dashed line corresponds to a = b. (b) The horizontal radii and the perpendicular radii before (D / 2 and H) and after (a and b) the tting procedure obtained in a single DWNT. Inset: The STM image of the DWNT, with lines of measurement, , , , in the order of thickness. The dashed line corresponds to a = b.

Downloaded 09 Jan 2005 to 166.104.127.71. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp

Th values. In turn, we may calculate the a value from the relation B / A = b / a. The ratios of B / A or b / a will not be affected seriously as the A and B values are also determined by tting. The ratios b / a or B / A can then represent the degree of the CNT deformation. These values smaller than 1 indicate that the CNTs are deformed by the van der Waals force between the tube and the HOPG substrate.22 Figure 2 shows the a and b values obtained from the tting procedure described above. It is seen that the b value does not increase linearly with the a value. In view of the above discussion, we can assume that 2a is nearly equal to the actual diameter of deformed CNT. Thus, it is seen that the cross-sectional deformation induced by the van der Waals interactions between the substrate and the CNT increases in proportion to the diameter of CNTs.22 Besides, the SWNTs show smaller b / a ratios in comparison with the DWNTs, indicating that the DWNTs are deformed less in the substrate direction in comparison with the SWNTs [Fig. 2(a)]. This result obviously shows that the addition of the inner wall gave rise to the rigidity of the DWNTs.22 In other words, the DWNTs are deformed less in the substrate direction in comparison to the SWNTs with the same diameter, an obvious evidence of the interwall support. Figure 2(b) shows the a and b values obtained from tting of the proles of the cross sectional STM image, whereas D / 2 and H refer to the values before tting. In Fig. 2(b), it is shown that the ratios of the a and b values, indicating the radial deformation to the substrate axis, are shown to be different even in the same CNT. Here, it is also seen that a larger a value gives rise to a smaller b / a ratio, indicative of a greater cross sectional deformation induced by the van der Waals forces.

023110-3

Park et al.
6

Appl. Phys. Lett. 86, 023110 (2005) R. Saito, G. Dresselhaus, and M. S. Dresselhaus, J. Appl. Phys. 73, 494 (1993). 7 J.-C. Charlier and J.-P. Michenaud, Phys. Rev. Lett. 70, 1858 (1993). 8 R. Saito, R. Matsuo, T. Kimura, G. Dresselhaus, and M. S. Dresselhaus, Chem. Phys. Lett. 348, 187 (2001). 9 M. Kociak, K. Suenaga, K. Hirahara, Y. Saito, T. Nakahira, and S. Iijima, Phys. Rev. Lett. 89, 155501 (2002). 10 J. Wildoer, L. Venema, A. Rinzler, R. Smalley, and C. Dekker, Nature (London) 391, 59 (1998). 11 T. Odom, J.-L. Huang, P. Kim, and C. Lieber, Nature (London) 391, 62 (1998). 12 A. Rochefort, P. Avouris, F. Lesage, and D. R. Salahub, Phys. Rev. B 60, 13824 (1999). 13 J. W. Janssen, S. G. Lemay, L. P. Kouwenhoven, and C. Dekker, Phys. Rev. B 65, 115423 (2002). 14 P. E. Lammert, P. Zhang, and V. H. Crespi, Phys. Rev. Lett. 84, 2453 (2000). 15 L. P. Biro, S. Lazarescu, Ph. Lambin, P. A. Thiry, A. Fonseca, J. B. Nagy, and A. A. Lucas, Phys. Rev. B 56, 12490 (1997). 16 L. P. Biro, J. Gyulai, Ph. Lambin, J. B. Nagy, S. Lazarescu, G. I. Mark, A. Fonseca, P. R. Surjan, Zs. Szekeres, P. A. Thiry, and A. A. Lucas, Carbon 36, 689 (1998). 17 F.-X. Zha, R. Czerw, D. L. Carroll, Ph. Kohler-Redlich, B.-Q. Wei, A. Loiseau, and S. Roth, Phys. Rev. B 61, 4884 (2000). 18 G. I. Mark, L. P. Biro, J. Gyulai, P. A. Thiry, A. A. Lucas, and Ph. Lambin, Phys. Rev. B 62, 2797 (2000). 19 J. Tersff and D. R. Hamann, Phys. Rev. Lett. 50, 1998 (1983). 20 F.-X. Zha, D. L. Carroll, R. Czerw, A. Loiseau, H. Pascard, W. Clauss, and S. Roth, Phys. Rev. B 63, 165432 (2001). 21 L. C. Venema, V. Meunier, Ph. Lambin, and C. Dekker, Phys. Rev. B 61, 2991 (2000). 22 T. Fertel, R. E. Walkup, and P. Avouris, Phys. Rev. B 58, 13870 (1998).

In summary, we have used high-resolution STM to elucidate the three-dimensional structure of individual SWNTs and DWNTs. The actual diameters and heights of CNTs were estimated from a line prole. The cross sectional deformation induced by the van der Waals force between the CNTs and substrate was investigated for the DWNTs and the SWNTs with different diameters. Much smaller deformation in the DWNTs than in the SWNTs with same diameters can be taken to be evidence of the interwall support. Thus, it was found that addition of the inner walls will give rise to greater rigidity of the multi-walled CNTs. This work was supported by the KISTEP (National Research Laboratory and Grant No. M102KS010001-02K190101814) and the Korea Research Foundation (Brain Korea 21 Project in 2004 and Grant No. KRF-2004-005-C00060). C.J.L. was supported by the Center for Nanotubes and Nanostructured Composites at Sungkyunkwan University.
1 2

S. Iijima, Nature (London) 354, 56 (1991). S. Bandow, M. Takizawa, K. Hirahara, M. Yudasaka, and S. Iijima, Chem. Phys. Lett. 337, 48 (2001). 3 J. Wei, B. Jiang, X. Zhang, H. Zhu, and D. Wu, Chem. Phys. Lett. 376, 753 (2003). 4 J. M. Zuo, I. Vartanyants, M. Gao, R. Zhang, and L. A. Nagahara, Science 300, 1419 (2003). 5 M. Abe, H. Kataura, H. Kira, T. Kodama, S. Suzuki, Y. Achiba, K. Kato, M. Takata, A. Fujiwara, K. Matsuda, and Y. Maniwa, Phys. Rev. B 68, 041405(R) (2003).

Downloaded 09 Jan 2005 to 166.104.127.71. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp