NANO LETTERS

Structural Characterizations of Long Single-Walled Carbon Nanotube Strands

Bingqing Wei,* Robert Vajtai, Yoon Young Choi, and Pulickel M. Ajayan
Department of Materials Science and Engineering, Rensselaer Polytechnic Institute, Troy, New York 12180

2002 Vol. 2, No. 10 1105-1107

Hongwei Zhu, Cailu Xu, and Dehai Wu

Department of Mechanical Engineering, Tsinghua UniVersity, Beijing 100084, China
Received July 23, 2002

ABSTRACT
Centimeter long single-walled carbon nanotube strands synthesized using chemical vapor deposition method were characterized using microscopy, micro-Raman spectroscopy, and small-angle X-ray diffraction techniques. The strands are large collections of well-aligned nanotube bundles, which consist of well-arranged single-walled nanotubes in a two-dimensional triangular lattice. The diameter of the single-walled nanotubes varies from 1.1 to 1.7 nm, with domination of the 1.1 nm tubes and the corresponding lattice constant of 1.42 nm.

The ability to control the structure and arrangement of carbon nanotubes (CNTs) is a prerequisite to realizing many practical applications. Single-walled carbon nanotubes (SWNTs), for all their remarkable and promising properties, will never totally fulfill their potential until an efficient way is found to manipulate and organize them into ordered arrays. Recent advances in SWNT growth by chemical vapor deposition (CVD) approaches have been achieved in producing high quality SWNT materials at large scale and in bridging SWNT networks on patterned substrates in a controllable manner.1-5 Our new approach for producing macroscopic SWNT strands enables us to test the bulk properties of nanotube structures.6 The materials synthesis and in part the characterizations have been published.6 Here, detailed results on structural characterizations of the SWNT strands are presented to reveal the inner symmetry and length scale of the alignment in the strands. Synthesis of long strands of ordered single-walled carbon nanotubes have been accomplished by an optimized catalytic CVD technique using a floating catalyst method in a vertical furnace where n-hexane is catalytically pyrolyzed when a sulfur-containing compound and hydrogen are added to the process.6 The n-hexane (carbon source) solution with a given composition of ferrocene (catalyst, 0.018 g/mL) and thiophene (sulfur additive, 0.4 wt %) is introduced into a vertical CVD furnace at a flow rate of 0.5 mL/min after heating the furnace to the pyrolysis temperature (1423 K) with hydrogen as the carrier gas flowing at a rate of 250 mL/min. Macroscopically
* Corresponding author: email weib@rpi.edu 10.1021/nl025719e CCC: $22.00 Published on Web 09/12/2002 2002 American Chemical Society

Figure 1. Micrographs of a typical single-walled nanotube strand. (a) SEM image of the strand consisting of thousands of nanotube bundles; approximately 15 m in diameter. (b) HRTEM image of a cross sectional view of single-walled nanotube bundles showing their two-dimensional triangular lattice.

long single-walled nanotube strands as long as 20 centimeters are formed during this continuous process.6 Because the nanotube strands are of macroscopic lengths and can be manipulated quite easily, direct structural characterizations can be performed on individual strands. For Raman and X-ray measurements, the samples were used asgrown, several cm long, and a few hundred micrometers in diameter; while for microscopic observations, the strands were first separated mechanically with a tweezers into several smaller strands having diameters from about 5 to 20 m and then observed using field emission scanning electronic microscopy (FESEM) and high-resolution transmission electronic microscopy (HRTEM). The high-resolution SEM view along single strands indicates that the strands consist of thousands of well-aligned bundles of SWNTs (Figure 1a). Each of the bundles is

Figure 2. Raman spectrum of long aligned single-walled nanotube strands. Nanotubes having 1.1 nm in diameters in the strands (corresponding to the peak at 215.3 cm-1) dominate as derived from the radial breathing mode peak calculations. Splittings of the E2g mode (peaks turn to shoulders) observed for the sample are characteristic of SWNTs. Excitation energy: 1.96 eV (632.8 nm).

composed of SWNTs forming a two-dimensional triangular lattice in their cross-sectional view as shown in the HRTEM image (Figure 1b). Raman spectra were excited with the 632.8 nm line (1.96 eV) of a He/Ne laser in the backscattering configuration with a micro-Raman spectrometer (Renishaw 2000) fitted with a 50 objective at room temperature. Total power to the sample was filtered down to 10 mW over the approximately 3-5 m diameter laser spot. The SWNT strands were adhered to a polished silicon wafer surface by a drop of water to prevent their vibration. The Raman spectra taken from different areas along the strands are very similar to each other, indicating a good homogeneity along the strands. Two peaks (1311.1, 1585.3 cm-1) can be observed in the range of 1200-1700 cm-1 in a typical Raman spectrum, as shown in Figure 2. The peak centered at 1585.3 cm-1, which has been assigned to the E2g (stretching) mode of graphite, is the strongest peak in the spectrum, indicating a good arrangement of the hexagonal lattice of graphite, i.e., only a few structural defects along the nanotube wall. The diameter of SWNTs can be determined by the frequency of the radial breathing modes from 100 to 300 cm-1.7 There are three clear peaks of the radial breathing mode observed in Figure 2. According to the expression ) 224/d (nm) + 14,8 nanotubes with diameter of 1.1, 1.2, and 1.7 nm are present in the strands. However, the sharp and intense Raman peak at 215.3 cm-1 suggests that there is a dominant diameter of 1.1 nm for the nanotubes in the strands. This is also confirmed by HRTEM observations. From the diameter dependence of the allowed optical distribution,9,10 we can also conclude that semiconducting (around 146.7 cm-1) and metallic (around 197 and 215.3 cm-1) SWNTs coexist in the samples. To carry out characterizations of symmetry and alignment, further optical and X-ray diffraction methods were published;11,12 we used X-ray diffractometry with Cu KR ( ) 1.542) line in an X-ray diffractometer (Scintag, model XDS 2000) operated at 45 kV and 40 mA. The sample holder used has a rectangular hole with a size of 1.5 cm 2.5 cm.
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Figure 3. (a) Schematic of X-ray measurements of the long nanotube strands. Small angle scans (2 from 4 to 10) and angular scans (at Q ) 0.51) were performed. A typical result is shown in (b) and in its inset. Identical peak (1,0) of the triangular lattice is at about Q ) 0.51. Sharp peaks at 90 and 270 in the angular scans (inset) indicate a good alignment of nanotube bundles in the strands.

The SWNT strands were vertically mounted across the center of the hole with both ends of the strands attached to the sample holder as shown schematically in Figure 3a. The X-ray diffraction studies on the strands were focused on the low-frequency regions (the scanning angle of 2 was 4-10), and we obtain a well-defined peak at Q ) 0.51 -1 (2 ) 7.3, scattering vector Q ) 4 sin /) corresponding to d (1,0) of the nanotube triangular lattice as shown in Figure 3b.12,13 By fixing Q ) 0.51 -1, an angular scan was performed to get information on the alignment of nanotube bundles in the strands. The sample was rotated clockwise from 0 to 360 (note: the angle along the scan is defined as 0 along the strand axis) and the intensity was collected at every 5 for 100 seconds. The peak at Q ) 0.51 -1 in Figure 3b is one of the feature peaks of the triangular structural distribution of SWNT bundles. The corresponding lattice parameter calculated from this peak position is 1.42 nm, which is very near to the lattice parameter12,14 of an ideal lattice assembled from 1.1 nm diameter nanotubes. The small difference from the calculated value is fully explainable by taking into account the signal superposition from finite crystallites made of nanotubes with different diameters.15 These results also
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In conclusion, the long nanotube strands, consisting of bundle-like single-walled nanotubes, are self-assembled during the CVD growth process and are well ordered into two-dimensional triangular structures. These very long crystalline strands of single-walled carbon nanotubes could be handled and manipulated easily and macroscopically, suggesting that these are not as brittle as most other nanotube aggregates prepared by other techniques. Acknowledgment. We gratefully acknowledge financial support from the NSF-NSEC, at RPI, for the directed assembly of nanostructures. References
Figure 4. Photographs of two samples of similar mass (one commercially available HiPCO sample (left) and the other nanotube strand prepared by our technique (right)) ultrasonicated for 10 min each in ethanol solutions. Arrow points to the tangled SWNT strand in the solution. The strand does not break up during sonication, compared to the normal SWNT samples (left) which break up easily into smaller fragments.
(1) Cassell, A.; Raymakers, J.; Kong, J.; Dai, H. J. Phys. Chem. 1999, 103, 6484. (2) Nikolaev, P.; Bronikowski, M. J.; Bradley, R. K.; Rohmund, F.; Colbert, D. T.; Smith, K. A.; Smalley, R. E. Chem. Phys. Lett. 1999, 313, 91. (3) Su, M.; Zheng, B.; Liu, J. Chem. Phys. Lett. 2000, 322, 321. (4) Zhang, Y.; Chang, A.; Cao, J.; Wang, Q.; Kim, W.; Li, Y.; Morris, N.; Yenilmez, E.; Kong, J.; Dai, H. Appl. Phys. Lett. 2001, 79, 3155. (5) Cao, A.; Zhang, X.; Xu, C. Liang, J.; Wu, D.; Chen, X.; Wei, B. Q.; Ajayan, P. M. Appl. Phys. Lett. 2001, 79, 1252. (6) Zhu, H. W.; Xu, C. L.; Wu, D. H.; Wei, B. Q.; Vajtai, R.; Ajayan, P. M. Science 2002, 296, 884. (7) Bandow, S.; Asaka, S.; Saito, Y.; Rao, A. M.; Grigorian, L.; Richter, E.; Eklund, P. C. Phys. ReV. Lett. 1998, 80, 3779. (8) Rao, A. M.; Chen, J.; Richter, E.; Schlecht, U.; Eklund, P. C.; Haddon, R. C.; Venkateswaran, U. D.; Kwon, Y. K.; Tomanek, D. Phys. ReV. Lett. 2001, 86, 3895. (9) Brown, S. D. M.; Corrio, P.; Macucci, A.; Dresslhaus, M. S.; Pimenta, M. A.; Kneipp, K. Phys. ReV. B 2000, 61, R5137. (10) Alvarez, L.; Righi, A.; Rols, S.; Anglaret, E.; Sauvajol, J. L.; Mun oz, E.; Maser, W. K.; Benito, A. M.; Martnez, M. T.; de la Fuente, G. F. Phys. ReV. B 2001, 63, 153401. (11) de Herr, W. A.; Bacsa, W. S.; Chatelain, A.; Gerfin, T.; Humphrey Baker, R.; Forro, L.; Ugarte, D. Science 1995, 268, 845. (12) Thess, A.; Lee, R.; Nikolaev, P.; Dai, H.; Petit, P.; Robert, J.; Xu, C.; Lee, Y. H.; Kim, S. G.; Rinzler, A. G.; Colbert, D. T.; Scuseria, G. E.; Tomanek, D.; Fischer, J. E.; Smalley, R. E. Science 1996, 273, 483. (13) Launois, P.; Marucci, A.; Vigolo, B.; Bernier, P.; Derre, A.; Poulin, P. J. Nanosci. Nanotechnol. 2001, 1, 125. (14) Charlier, J. C.; Gonze, X.; Michenaud, J. P. Europhys. Lett. 1995, 29, 43. (15) Rols, S.; Almairac, R.; Henrard, L.; Anglaret, E.; Sauvajol, J. L Euro. Phys. J. 1999, B 10, 263. (16) Poulin, P.; Vigolo, B.; Launois, P. Carbon 2002, 40, 1741. (17) Smith, B. W.; Benes, Z.; Luzzi, D. E.; Fisher, J. E.; Walters, D. A.; Casavant, M. J.; Schmidt, J.; Smalley, R. E. Appl. Phys. Lett. 2000, 77, 663. (18) Liu, J.; Rinzler, A. G.; Dai, H. J.; Hafner, J. H.; Bradley, R. K.; Boul, P. J.; Lu, A.; Iverson, T.; Shelimov, K.; Huffman, C. B.; Rodriguez-Macias, F.; Shon, Y. S.; Lee, T. R.; Colbert, D. T.; Smalley, R. E. Science 1998, 280, 1253. 280 (5367): 1253-1256 MAY 22 1998 (19) Shimoda, H.; Oh, S. J.; Geng, H. Z.; Walker, R. J.; Zhang, X. B.; McNeil, L. E.; Zhou, O. AdV. Mater. 2002, 14, 899.

confirm the results from Raman measurements that 1.1 nm tubes dominate the strands. The fwhm of the peaks at 90 and 270 in the angular scans (inset of Figure 3b) is about 44, almost half of that in the nanotube fibers (the fwhm is about 75 in the fibers),13,16 indicating a good alignment of nanotube bundles in the strands. Note that the peak signals were collected from cm long SWNT strands, not from m area,17 indicating that the good alignment is along the whole strand. The strong peaks obtained demonstrate once again that single-walled nanotubes with 1.1 nm in diameter are dominant. Another interesting observation is worth mentioning here. We attempted to break up and disperse the nanotube strands by ultrasonication in ethanol solution for up to several tens of minutes. We did not observe any breakup or dissolution of the strands, unlike SWNT samples prepared by the arcmethod or obtained commercially (HiPCO). The nanotube strands simply get tangled and form ball-like structures that can not be broken up and dispersed. Figure 4 shows this effect in comparison to the dispersion of conventional SWNT samples. As published previously, shortened SWNTs have solubility in some solvents and can form stable homogeneous suspensions in solution.18,19 The formation of the ball-like structures of SWNTs in our experiment, in contrast, demonstrates that the nanotubes in the strands are continuous and can not be broken up unless individual nanotubes break or exfoliate from the strands.

NL025719E

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