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A one-step technique to prepare aligned arrays of carbon nanotubes

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2008 Nanotechnology 19 155602 (http://iopscience.iop.org/0957-4484/19/15/155602) View the table of contents for this issue, or go to the journal homepage for more

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IOP PUBLISHING Nanotechnology 19 (2008) 155602 (7pp)

NANOTECHNOLOGY doi:10.1088/0957-4484/19/15/155602

A one-step technique to prepare aligned arrays of carbon nanotubes

Pitamber Mahanandia1 and Karuna Kar Nanda2
1 2

Department of Physics, Indian Institute of Science, Bangalore 560012, India Materials Research Centre, Indian Institute of Science, Bangalore 560012, India

E-mail: pitam@physics.iisc.ernet.in

Received 22 November 2007, in nal form 5 February 2008 Published 11 March 2008 Online at stacks.iop.org/Nano/19/155602 Abstract A simple effective pyrolysis technique has been developed to synthesize aligned arrays of multi-walled carbon nanotubes (MWCNTs) without using any carrier gas in a single-stage furnace at 700 C. This technique eliminates nearly the entire complex and expensive machinery associated with other extensively used methods for preparation of CNTs such as chemical vapour deposition (CVD) and pyrolysis. Carbon source materials such as xylene, cyclohexane, camphor, hexane, toluene, pyridine and benzene have been pyrolyzed separately with the catalyst source material ferrocene to obtain aligned arrays of MWCNTs. The synthesized CNTs have been characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and Raman spectroscopy. In this technique, the need for the tedious and time-consuming preparation of metal catalysts and continuously fed carbon source material containing carrier gas can be avoided. This method is a single-step process where not many parameters are required to be monitored in order to prepare aligned MWCNTs. For the production of CNTs, the technique has great advantages such as low cost and easy operation. (Some gures in this article are in colour only in the electronic version)

1. Introduction
Since their discovery in 1991 [1], carbon nanotubes (CNTs) have been extensively investigated due to their unique physical, chemical, mechanical and electronic properties. Depending on their diameter and chirality, CNTs are predicted to be metallic or semiconducting [25]. The nature and quality of CNTs depend on the method of productionwhich controls the degree of graphitization, the helicity and the diameter. With exotic electronic structure, exible atomic conformation and intriguing physical properties, multi-wall carbon nanotubes (MWCNTs) promise many applications of great technological importance such as ctionalized molecules [6], conductive wires [7], bearers of rotational motors [8], eld emitters, hydrogen storage, sensors, polymer composites [9, 10], nanotube yarn [11] and nanotube lters [12]. A lot of work has been carried out in developing new and efcient synthesis routes for the production of CNTs in high quantities and in ordered layouts. The commonly used methods for the synthesis of CNTs are arc-discharge [1315], laser ablation [1619], high-pressure catalytic decomposition of carbon monoxide
0957-4484/08/155602+07$30.00

(HiPCO) [20, 21], electrophoretic deposition (EPD) [22], ame synthesis [23, 24], pyrolysis [25, 26], chemical vapour deposition (CVD) [27, 28], hot lament CVD [29, 30], plasmaenhanced CVD (PECVD) using direct current (DC) [31, 32], and radio-frequency (RF) [3335] and microwave (MW) power sources [3638]. Though nanotubes synthesized by arc-discharge and laser ablation processes are high on purity, scaling up this process to produce nanotubes on a larger scale is not very effective. Although many efforts have been made in the development of synthesis methods, CVD and PECVD have become more popular and are considered at the moment to be the best approach for low-cost and large-scale synthesis of high-quality entangled or aligned (single-walled or multi-walled) CNT materials in the temperature range of 7001200 C. Among them, CVD appears to be a simple and economic technique to synthesize CNTs. The CVD method is based on the thermal decomposition of hydrocarbon compounds (acetylene, ethylene, benzene, naphthalene, toluene, etc) over transition metal catalyst particles [27, 28]. PECVD is similar to CVD. The important difference is that in CVD thermal energy is
1
2008 IOP Publishing Ltd Printed in the UK

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Figure 1. (a) Photograph of the furnace. (b) The reaction quartz tube.

used to activate the gas, whereas in PECVD the molecules are activated by electron impact. The main purpose of using plasma enhancement is to reduce the activation energy for a deposition process. Though the scalable and selective synthesis of CNTs on a large scale is possible, rigorous control of parameters such as the furnace temperature, continuous supply of source materials, ratio of precursor materials and feed rate, total reaction time, ow rate of sweep gas and catalyst amount (thickness or concentrations) is required. In addition, the direct current (DC), radio-frequency (RF) and microwave (MW) power are crucial for PECVD. Moreover, complicated control, and expensive or unrenewable materials are unavoidable, which have put limitations on producing the same in large scale. Above all, the main disadvantage with these methods is the overall cost. Though there are many synthesis methods for potential application of CNTs in nanoscience and nanotechnology, a low-cost simple method is essential to produce good quality CNTs on a large scale. To prepare an aligned array of CNTs, here we describe a simplied one-step pyrolysis technique that eliminates nearly the entire complex and expensive machinery associated with the methods discussed above. By following this method, we have successfully synthesized entangled MWCNTs using uncommon carbon source materials [39, 40]. In order to check the efciency of this method, commonly used liquid carbon source materials were used. Amazingly aligned arrays of CNTs were prepared. In this technique carrier gas is not required unlike other CVD, PECVD and pyrolysis methods. Complicated control of parameters is not required because CNTs are prepared in one step. Moreover, in this technique, the need for the tedious and time-consuming preparation of metal catalysts and carrier gas can be avoided. Therefore, this technique not only avoids the limits of other preparation methods but also achieves remarkable reduction in production costs for the synthesis of CNTs.

(b)

(a)

Figure 2. (a) Schematic diagram of the single-stage pyrolysis set-up. (b) Calibrated temperature prole across the furnace.

2. Experimental procedure
Synthesis of CNTs have been carried out using a singlestep pyrolysis technique which consists of a single-stage furnace instead of the double hot zone in regular CVD and pyrolysis methods [2527]. A photograph of the singlestage furnace with the reaction quartz tube is shown in 2

gures 1(a) and (b). The schematic diagram of the furnace along with the temperature prole is shown in gures 2(a) and (b). A photograph of the CVD set-up extensively used by other researchers for the synthesis of single-walled CNTs and MWCNTs (entangled or aligned) is shown in gure 3. A major difference can be noticed when the experimental arrangement of the present technique is compared with CVD and pyrolysis. The detailed experimental procedure of the single-stage furnace pyrolysis set-up has been discussed elsewhere [40]. In brief, to synthesize aligned CNT arrays in the present technique, a mixture of 18 mg of catalyst source material ferrocene and 2 ml of carbon source material is taken in a quartz tube of diameter 1.0 cm and length 70 cm, closed at one end. The other end of the quartz tube is connected with a rubber bladder to collect the residual reacted gases. The whole assembly is placed inside the furnace and heated

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3. Results and discussion

The respective SEM images of aligned arrays of CNTs synthesized from xylene, cyclohexane, camphor, hexane, benzene, toluene and pyridine using ferrocene are shown in gures 4(a)(g). The aligned arrays of CNTs are seen along with a small quantity of impurity catalyst and amorphous carbon. From the SEM images it is clear that the amorphous carbon content is different for the CNTs prepared from different carbon source materials. Aligned arrays of nanotubes prepared from benzene and ferrocene were randomly chosen for purication and characterization. Neither amorphous nor catalyst particles are seen in the SEM image of puried CNTs (gure 4(h)). The x-ray spectroscopy measurement provides not only structural characterization of CNTs but also information about the presence of catalytic particles in the unpuried as well as in the puried samples [42]. The powder XRD pattern (Cu K = 1.5406 A) of as-synthesized and puried CNT samples prepared by the pyrolysis of benzene and ferrocene is shown in gures 5(a) and (b). The peaks for as-synthesized aligned CNT arrays are indexed to (002), (101) and (004) reections of hexagonal graphite and catalytic impurities (Fe) (gure 5(a)). The shift of the (002) reection from 2 = 26.4 for graphite to 25.7 for the as-synthesized CNTs shows an increase in the interlayer distance from 0.335 nm for graphite to 0.346 nm for the MWCNTs [43]. The higher interplanar distance observed in the MWNTs is attributed to the curved shape of their structures, which induce strain inside the graphene plane stacking [44]. The catalytic impurities are not seen in the XRD pattern of puried CNTs (gure 5(b)). This conrms the removal of catalytic impurities and amorphous carbon. TEM images of aligned arrays of CNTs prepared from xylene, cyclohexane, camphor, hexane, benzene, toluene and pyridine are shown in gures 6(a)(g). A good quality of nanotubes with a very small quantity of amorphous carbon and catalyst particles is seen. From the TEM images it is clear that the CNTs are well dispersed. The bamboo-shaped CNTs are obtained by pyrolysing pyridine and ferrocene and are shown in the TEM image (gure 6(f)). Sen et al [45] synthesized bamboo-shaped CNTs by pyrolysing pyridine over Co powder at 1000 C in an argon atmosphere. It is reported that the presence of nitrogen in the carbon source material is the cause of the formation of bamboo-shaped CNTs [4649]. The growth mechanism of bamboo-type CNTs has already been proposed by Lee and Park [50, 51]. The respective HRTEM images (gures 7(a)(f)) show that the tubes are multi-wall in nature. The TEM image of puried aligned CNTs synthesized from benzene and ferrocene is shown in gure 7(g). In this image neither catalyst nor amorphous carbon is observed, which has been removed by purication. Catalyst particles are also not seen in the core region of the nanotubes. The CNTs with open lumens are seen in almost all TEM images. A higher magnication TEM image is shown in gure 7(h), where open lumens are seen clearly. The HRTEM images show that the diameter of MWCNTs prepared from xylene, cyclohexane, 3

Figure 3. Photograph of the chemical vapour deposition (CVD) experimental set-up (gure adapted from the PhD Thesis of Kasper Grove-Rasmussen, Niels Bohr Institute, Nano-Science Center, Faculty of Science, University of Copenhagen, Denmark, 2006).

up to the desired pyrolysis temperature (700 C) at a heating rate of 20 C min1 . The reaction is continued for 30 min and then cooled down to room temperature. At room temperature the reaction quartz tube is taken out of the furnace. In order to avoid any effect from the reacted gases (which may be either CO or CO2 ), the reaction quartz tube is taken into the safety hood to remove the bladder. Around 7585 mg black materials are collected from the quartz tube. Following the present technique an aligned array of CNTs has also been prepared by pyrolysing the catalyst source material ferrocene separately with carbon source materials: xylene, cyclohexane, camphor, hexane, benzene, toluene or pyridine. To date, to prepare carbon nanostructures by CVD or pyrolysis, the use of carrier gas is inevitable. However, in this technique, neither predeposited metal catalyst nor carrier gas is used at any stage of sample preparation. The presence of amorphous carbon and catalyst particles in the as-synthesized samples in any synthesis method is inevitable. The degree of amorphous carbon and catalyst particles present in the as-synthesized materials depends on preparation conditions. In the present technique, the assynthesized samples contain mostly CNTs along with some amorphous carbon and catalyst particles. For many potential applications, CNTs free from amorphous carbon and catalyst impurities are required. Therefore, it is essential to purify the CNTs in order to remove the unwanted impurities of catalyst and amorphous carbon. The purication of the as-synthesized sample was done by following the standard oxidation and acid bath treatment method [40, 41]. To nd out the purity and the yield, 85 mg as-prepared aligned arrays of CNTs by the pyrolysis of benzene and ferrocene was selected to purify. After the purication process 54 mg of material was recovered. The as-synthesized and puried CNTs were characterized with the help of XRD, SEM, HRTEM and microRaman spectroscopy and thermogravimetric analysis (TGA).

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Figure 4. SEM images of as-prepared aligned arrays of CNTs prepared using ferrocene from (a) xylene, (b) camphor, (c) hexane, (d) cyclohexane, (e) toluene, (f) pyridine and (g) benzene. (h) The SEM image of CNTs prepared from benzene after purication.

Figure 6. TEM images of as-synthesized aligned arrays of CNTs prepared from (a) xylene, (b) camphor, (c) hexane, (d) cyclohexane, (e) toluene, (f) pyridine and (g) benzene. (h) TEM image of puried CNTs.

Figure 5. XRD pattern of (a) as-synthesized and (b) puried CNT arrays prepared from benzene.

hexane, benzene and toluene are 6575 nm with 7587 concentric layers, whereas the diameter of MWCNTs prepared from camphor is 1518 nm (with 1013 concentric layers) 4

and from pyridine is 3540 nm (with 1215 concentric layers). The information about the crystal structure and presence of amorphous/disorder in the CNT material is obtained by Raman spectroscopy characterization [52, 53]. Raman spectra also provide the information about removal of the amorphous and structural disorders from the nanotubes after purication [54]. Raman spectra of CNTs are based on the phonon dispersion relationship of two-dimensional graphite, and the method of folding of the Brillouin zone. The strong peak at 1578 cm1 (G band) (gure 8(a)) indicates high crystalline graphitic layers and is caused by the tangential stretching modes (graphitic lattice mode E2g ), whereas the 1345 cm1 (D band) (gure 8(b)) is the disorder-induced phonon mode, which is related to the mode of boundaries in the Brillouin zone [5557]. It is due to the disorder components and mainly originates from the phonon mode of the M -point and K -point of the hexagonal Brillouin zone. The appearance of the 1345 cm1 (D band) can be interpreted as the formation of nanometre-scale/turbostatic structure/amorphous carbon in

Nanotechnology 19 (2008) 155602

P Mahanandia and K K Nanda

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Figure 8. The Raman spectra of (a) as-synthesized and (b) puried aligned arrays of CNTs prepared from benzene.

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Figure 9. Thermogravimetry analysis (TGA) of (a) as-synthesized and (b) puried aligned arrays of CNTs prepared from benzene.

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Figure 7. The respective HRTEM images of CNTs prepared from (a) xylene, (b) camphor, (c) hexane, (d) cyclohexane, (e) toluene, (f) pyridine. (g) HRTEM image of puried CNT prepared from benzene. (h) Magnied TEM image of CNTs with open lumens.

the sample [57]. The Raman spectrum of the puried CNTs is shown in gure 6(b), which reveals the strong peak at 1578 cm1 (G band) appears along with a very weak peak at 1345 cm1 (D band). The reduced intensity peak of the 1342 cm1 (D band) indicates the removal of amorphous carbon by the purication process. TGA results carried out for the aligned arrays of CNTs prepared from benzene and ferrocene are shown in gure 9(a). The residual weight of iron oxide is 8 wt%, which implies that about 92% of the mass of the as-synthesized material is carbon. The residual weight for the puried aligned CNT bundles 2%, which implies that the purity of CNTs is 98% (gure 9(b)). 5

In the present case, the as-synthesized material with a reaction time of 30 min, a mass of about 85 mg of carbon deposit was found. This corresponds to a carbon yield of 364% over the weight of the catalysts. The yield of the carbon deposit formed during the reaction was calculated as follows: carbon yield (%) = 100(m tot m cat )/m cat , where m cat is the initial amount of catalyst and m tot is the total weight of the sample after reaction [42, 58]. The yield of puried CNTs being about 64% for aligned CNTs has been obtained from the formula, yield (%) = (m after /m before ) 100, where m before is the as-synthesized sample material before purication and m after is the CNT material after purication [54]. The yield of CNTs in the range of 30%70% has been reported by different research groups [54, 5963]. In the present case, the weight loss of 36% of as-synthesized material has been observed after purication. By following the same gas phase oxidation purication process, Chiang et al [60] bear 34% of material loss. This is attributed to the mass loss of amorphous carbon, catalyst particles and some CNTs during the purication procedure. Since carrier gas is not used, the vapours have got the freedom to move towards the high temperature reaction zone. At the reaction zone the catalyst and precursor materials get fragmented to yield active catalyst and carbon species. The

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using hydrogen as a carrier gas. It is believed that the proper ratio of thiophene not only helps in growing single-walled CNTs but also the growth rate [72]. Therefore, currently efforts are also underway to synthesize single-walled CNTs by mixing thiophene with carbon source materials in the proper ratio using the present technique.

4. Conclusions
In conclusion, we report a simple and effective pyrolysis technique to synthesize aligned arrays of MWCNTs. The technique is a one-step process in which carrier gas and predeposited metal catalysts are not required. We believe that this method is the simplest one so far compared to other methods (CVD, PECVD, and carrier gas assisted pyrolysis) to prepare aligned arrays of CNTs, which will remarkably reduce the production cost. The easy operation, which follows with one step, will certainly be an advantage for the growth of aligned CNTs.

Figure 10. SEM image of aligned CNTs on quartz substrate.

moment the catalyst particles come in contact with the active carbon species, CNTs start growing. Most of the existing models for CVD growth of CNTs, which were proposed by Baker et al [64], are based on surface and/or bulk diffusion of active carbon species at the catalysts. We believe the initiation of CNT formation, in the present technique, might be the diffusion of carbon at the catalysts [64]. The nucleation site densities given by the density of catalytic Fe particles which form on the inner wall of the reaction quartz tube is so high that simultaneous growth of the nanotubes can occur only normal to the inner wall of the reaction quartz tube as well as on the quartz substrate. Once initial CNT formation is established, growth will tend to continue in the same direction and may well be reinforced by the presence of surrounding nanotubes, where crowding will limit the nanotubes propagation in other directions [65]. This leads to the formation of aligned CNT bundles, which are held together by van der Waals forces. Even vertically aligned CNTs on quartz substrate have been prepared and shown in gure 10. Again, the base [66, 67] or tip [68, 69] type growth mechanism for vertically aligned CNTs is well established. In the tip-growth mode, catalytic particles are detached from the substrate and move upward at the top of the growing tubes. On the other hand, in the basegrowth mode, the CNTs are stuck on the substrate and catalyst particles remain at the root of the CNTs during growth. Ren et al [28] reported the successful synthesis of aligned carbon nanotubes on glass substrates, though the growth mechanism was not clear to them at that time. Wang et al [70] also synthesized pillars of bamboo-like MWNTs by pyrolysis of iron (II) phthalocyanine, but the growth mechanism of these patterns is yet to be claried. The nanotubes outer diameter is directly correlated to the catalyst particle size [68]. From the TEM observations it is clear that the diameters of CNTs prepared from different carbon source materials are different. Currently, work is under progress to establish the growth mechanism (base or tip), diameter as well as length of the CNTs and may appear in future work. Kim et al [71] have reported the synthesis of single-walled CNTs from the mixture of n -hexane, ferrocene and thiophene, which was injected into the horizontal furnace 6

Acknowledgments
CSIR and DST, Government of India are acknowledged for providing experimental facilities.

References
[1] Iijima S 1991 Nature 354 56 [2] Mintmire J W, Dunlap B I and White C T 1992 Phys. Rev. Lett. 68 631 [3] Hamada N, Sawada S and Oshiyama A 1992 Phys. Rev. Lett. 68 1579 [4] Saito R, Fujita M, Dresselhaus G and Dresselhaus M S 1992 Appl. Phys. Lett. 60 2204 [5] Saito R, Fujita M, Dresselhaus G and Dresselhaus M S 1992 Phys. Rev. B 46 1804 [6] Ge J J, Zhang D, Li Q, Hou H, Graham M J, Dai L, Harris F W and Cheng S Z D 2005 J. Am. Chem. Soc. 127 9984 [7] Li H J, Lu W G, Li J J, Bai X D and Gu C Z 2005 Phys. Rev. Lett. 95 086601 [8] Fennimore A M, Yuzvensky T D, Han W Q, Fuhrer M S, Cumings J and Zettl A 2003 Nature 424 408 [9] Baughman R H, Zakhidov A A and de Heer W A 2002 Science 297 787 [10] Ghosh S, Sood A K and Kumar N 2003 Science 299 1042 [11] Zhang M, Atkinson K R and Baughman R H 2004 Science 306 1358 [12] Srivastava A, Srivastava O N, Talapatra S, Vajtai R and Ajayan P M 2004 Nat. Mater. 3 610 [13] Bethune D S, Kiang C H, de Vries M S, Gorman G, Savoy R, Vazquez J and Beyers R 1993 Nature 363 605 [14] Ebbesen T W and Ajayan P M 1992 Nature 358 220 [15] Kroto H W, Heath J R, OBrien S C, Curl R F and Smalley R E 1985 Nature 318 162 [16] Eklund P C, Pradhan B K, Kim U J, Xiong Q, Fischer J E, Friedman A D, Holloway B C, Jordan K and Smith M W 2002 Nano Lett. 2 561 [17] Maser W K, Munoz E, Benito A M, Martinez M T, de la Fuente G F, Maniette Y, Anglaret E and Sauvajol J L 1998 Chem. Phys. Lett. 292 587 [18] Thess A et al 1996 Science 273 483 [19] Dai H, Rinzler A G, Nikolaev P, Thess A, Colbert D T and Smalley R E 1996 Chem. Phys. Lett. 260 471

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[20] Nikolaev P, Bronikowski M J, Bradley R K, Rohmund F, Colbert D T, Smith K A and Smalley R E 1999 Chem. Phys. Lett. 313 91 [21] Bronikowski M J, Willis P A, Colbert D T, Smith K A and Smalley R E 2001 J. Vac. Sci. Technol. A 19 1800 [22] Boccaccini A R, Cho J, Roether J A, Thomas B J C, Minay E J and Shaffer M S P 2006 Carbon 44 3149 [23] Yuan L, Saito K, Pan C, Williams F A and Gordon A S 2001 Chem. Phys. Lett. 340 237 [24] Yuan L, Saito K, Hu W and Chen Z 2001 Chem. Phys. Lett. 346 23 [25] Govindaraj A and Rao C N R 2002 Pure Appl. Chem. 74 1571 [26] Terrones M et al 1997 Nature 388 52 [27] Li W Z, Xie S S, Qian L X, Chang B H, Zou B S, Zhou W Y, Zhao R A and Wang G 1996 Science 274 1701 [28] Fan S, Chapline M G, Franklin N R, Tombler T W, Cassell A M and Dai H 1999 Science 283 512 [29] Ren Z F, Huang Z P, Xu J W, Wang J W, Bush P, Siegel M P and Provencio P N 1998 Science 282 1105 [30] Hayashi Y, Negishi T and Nishino S 2001 Vac. Sci. Technol. A 19 1796 [31] Merkulov V I, Melechko A V, Guillorm M A, Lowndes D H and Simpson M L 2001 Appl. Phys. Lett. 79 2970 [32] Teo K B K, Chhowalla M, Amaratunga G A J, Milne W I, Pirio G, Legagneux P, Pribat D and Hasko D G 2002 Appl. Phys. Lett. 80 2011 [33] Ishida H, Satake N, Jeong G-H, Abe Y, Hirata T, Hatakeyama R, Tohji K and Motomiya K 2002 Thin Solid Films 407 26 [34] Delzeit L, McAninch I, Cruden B A, Hash D, Chen B, Han J and Meyyappan M 2002 J. Appl. Phys. 91 6027 [35] Shiratori Y, Hiraoka H, Takeuchi Y, Itoh S and Yamamoto M 2003 Appl. Phys. Lett. 82 2485 [36] Kutel O M, Groening O, Emmenegger C and t Schlapbach L 1998 Appl. Phys. Lett. 73 2113 [37] Murakami H, Hirakawa M, Tanaka C and Yamakawa H 2000 Appl. Phys. Lett. 76 1776 [38] Wang N and Yao D 2001 Appl. Phys. Lett. 78 4028 [39] Mahanandia P, Vishwakarma P N, Nanda K K, Prasad V, Subramanyam S V, Dev S K and Satyam P V 2006 Mater. Res. Bull. 41 2311 [40] Mahanandia P, Vishwakarma P N, Nanda K K, Prasad V, Barai K, Mondal A K, Sarangi S, Dey G K and Subramanyam S V 2008 Solid State Commun. 145 143 [41] Yanga C M, Kanekob K, Yudasakaa M and Iijima S 2002 Physica B 323 140 [42] Shaijumon M M, Rajalakshmi N, Ryu H and Ramaprabhu S 2005 Nanotechnology 16 518 [43] Chen P, Wu X, Sun X, Lin J, Li W and Tan K L 1999 Phys. Rev. Lett. 82 2548 [44] Ajayan P M 1999 Chem. Rev. 99 1797

[45] Sen R, Satishkumar B C, Govindaraj A, Harikumar K R, Raina G, Zhang J-P, Cheetham A K and Rao C N R 1998 Chem. Phys. Lett. 287 671 [46] Suenaga K, Johansson M P, Hellgren N, Broitman E, Wallenberg L R, Colliex C, Sundgren J-E and Hultman L 1999 Chem. Phys. Lett. 300 695 [47] Terrones M et al 1999 Appl. Phys. Lett. 75 3932 [48] Terrones M et al 1999 Adv. Mater. 11 655 [49] Han W-Q et al 2000 Appl. Phys. Lett. 77 1807 [50] Lee C J and Park J 2001 J. Phys. Chem. B 105 2365 [51] Lee C J and Park J 2000 Appl. Phys. Lett. 77 3397 [52] Li W Z, Zhang H, Wang C Y, Zang Y, Xu L W and Zhu K 1997 Appl. Phys. Lett. 70 2684 [53] Eklund P C, Holden J M and Jishi R A 1995 Carbon 33 959 [54] Li Y et al 2004 Nanotechnology 15 1645 [55] Tuinstra F and Koening J L 1970 J. Chem. Phys. 53 1126 [56] Souza Filho A G, Jorio A, Samsonidze G G, Dresselhaus G, Saito R and Dresselhaus M S 2003 Nanotechnology 14 1130 [57] Xie S S, Li W Z, Pan Z W, Chang B H and Sun L F 1999 Eur. Phys. J. D 9 85 [58] Louis B, Gulino G, Vieira R, Amadou J, Dintzer T, Galvagno S, Centi G, Ledoux M J and Huu C P 2005 Catal. Today 102 23 [59] Moon J M, An K H, Lee Y H, Park Y S, Bae D J and Park G S 2001 J. Phys. Chem. B 105 5677 [60] Chiang I W, Brinson B E, Huang A Y, Willis P A, Bronikowski M J, Margrave J L, Smalley R E and Hauge R H 2001 J. Phys. Chem. B 105 8297 [61] Xu Y Q, Peng H, Hauge R H and Smalley R E 2005 Nano Lett. 5 163 [62] Park Y S, Choi Y C, Kim K S, Chung D C, Bae D J, An K H, Lim S C, Zhu X Y and Lee Y H 2001 Carbon 39 655 [63] Wang Y, Liu Y Q, Wei D C, Cao L C, Fu L, Li X L, Kajiura H, Lib Y M and Nodab K 2007 J. Mater. Chem. 17 357 [64] Baker R T, Barber M A, Harris P S, Feates F S and Waite R J 1972 J. Catal. 26 51 [65] Fan S S, Chapline M G, Franklin N R, Tombler T W, Cassell A M and Dai H J 1999 Science 283 512 [66] Bower C, Zhu W, Jin S, Werder D J and Zhou O 2000 Appl. Phys. Lett. 77 830 [67] Bower C, Zhou O, Zhu W, Werder D J and Jin S 2000 Appl. Phys. Lett. 77 2767 [68] Sinnott S B, Andrews R, Qian D, Rao A M, Mao Z, Dickey E C and Derbyshire F 1999 Chem. Phys. Lett. 315 25 [69] Han J et al 2002 J. Appl. Phys. 91 483 [70] Wang X, Liu Y and Zhu D 2000 Chem. Commun. 751 [71] Quy N V, Cho Y S, Choi G S, Song I K, Yu W J and Kim D 2005 Nanotechnology 16 386 [72] Cheng H M, Li F, Su G, Pan H Y, He L L, Sun X and Dresselhaus M S 1998 Appl. Phys. Lett. 72 3282