METALS AND MATERIALS International, Vol. 14, No. 2 (2008), pp. 269~273 doi: 10.3365/met.mat.2008.04.

269 Published 26 April 2008

Effects of Ammonia in Catalytic Chemical Vapor Deposition in the Synthesis of Carbon Nanotubes
Hao Zhang , Yanfang Chen Sung-Soo Kim and Yun-Soo Lim
1 1 2 3 1,2,*

Dept. of Nano Science and Engineering, Myongji University, San 38-2, Nam-dong, Cheoin-gu, Yongin-si, Gyeonggi 449-728, Korea 2 Dept. of Materials Science and Engineering, Myongji University, Gyeonggi 449-728, Korea 3 Dept. of Materials Science and Engineering, Chungbuk National University, San 48, Gaesin-dong, Heungdeok-gu, Cheongju-si, Chungbuk 361-763 Korea
Chemical vapor deposition with xylene as the carbon resource, a nitrate iron solution as the catalyst, and ammonia gas as the reduction gas was used to investigate the different parameters that influence carbon nanotubes. Different concentrations of the ammonia gas and different substrates affect the morphology and properties of carbon nanotubes fabricated using the method involving ammonia gas and a quartz plate. This method yields a large quantity of vertically aligned carbon nanotubes with a typical bamboo-like inner layer structure. In the synthesis of this type of carbon nanotube, the ammonia etches the catalyst surface through the catalyst agglomeration. Keywords: carbon nanotube, chemical vapor deposition, ammonia, bamboo-like structure

1. INTRODUCTION
Since the discovery of carbon nanotubes (CNTs) by Iijima in 1991[1], researchers have focused considerable attention on CNTs due to their high strength, uniform structure, and hollow tube [2-4], as well as other properties that have led to CNTs being applied in areas of electron emission [5] C-C composites [6] hydrogen storage [7] and so on [8,9]. Chemical vapor deposition (CVD) [10,11], laser ablation [12] and arc-discharge [13,14] have become the most popular methods to fabricate CNTs. However, CVD has more advantages than the other methods: for instance, it can produce large quantities of uniform, vertically aligned CNTs, and the catalyst and low temperature can be easily controlled [15,16]. Typical bamboo-like CNT was synthesized by the CVD method with a certain concentration of ammonia gas. The fact that different concentrations of ammonia gas affect the morphology and structure of CNTs indicates that ammonia gas plays an important role in the synthesis of CNTs. Researchers have reported various mechanisms of bamboolike CNT growth. Jung et al proposed that the nitrogen from the decomposition of ammonia gas enhances the formation of the graphitic layer and improves the kinetics for the separation of the graphitic layer from the catalyst [17]. The
*Corresponding author: yslim@mju.ac.kr

research groups of Ma et al [18] and Lin et al [19] suggested that nitrogen can enhance the bamboo-like structure of CNTs. In addition, other researchers have reported that the particle shape, bulk diffusion of carbon in the catalyst, and movement of the catalyst may also affect the bamboo-like structure of CNTs [20-22]. When the ammonia gas etches the surface of the catalyst, the resultant catalytic metal particles act as a nucleation seed for the growth of CNTs [21-23]. The CNT fabrication process is well-known and various mechanisms have been suggested as the basis for the bamboo-like structure of CNTs; however, the growth mechanism of the bamboo-like CNTs still is not yet completely understood.

2. EXPERIMENTAL PROCEDURE
In the present study, xylene was used as the carbon resource and stored in a syringe. In addition, a quartz plate (10 mm × 10 mm), a silicon wafer (6 mm × 6 mm) and an alumina boat were employed to collect the CNT products. The substrates were washed in acetone with an ultrasound cleaner for 5 min. Then an iron nitrate solution of 0.005 M was uniformly sprayed onto the quartz plate and silicon wafer. The substrates were placed in the middle of the alumina boat, and the boat was placed in the center of the furnace system. Argon was used as the carrier gas, and the

the xylene was dispensed into the tube at a flow rate of 0. 2(c)). Then. In contrast. RESULTS AND DISCUSSION To study the effects of the ammonia concentration on the CNT yield and morphology. (c) Q20. Then. and (d) Q30. Substrate Gas Concentration Symbol and Time 0% Q00 10 % Q10 Quartz Plate 20 % Q20 30 % Q30 40 min at Ar/NH3 900 °C 0% S00 10 % S10 Silicon Wafer 20 % S20 30 % S30 scanning electron microscopy (SEM). The CNTs on the quartz plate had an average diameter of 80 nm and a high level of purity. For the pretreatment. Experimental conditions Hao Zhang et al. the amorphous carbon resembled carbon black more than a CNT.270 Table 1. 3. 1(c)) and the silicon wafer (Fig. the temperature was maintained at 800 oC for 10 min. CNTs and large quantities of amorphous carbon were obtained on the quartz plate (Fig. 1(b)) and on the silicon wafer (Fig. The CNTs were well aligned vertically on the quartz plate in lengths of 15 μm to 17 μm. the CNTs were rarely found in either the quartz plate (Fig. There was also an amorphous carbon layer on the top surface before the purification. The two gases mixed and maintained a constant flow rate of 500 sccm but with different concentrations. but those on the silicon wafer had a larger diameter of 120 nm. until the temperature reached 800 oC. 2(a)): the primary product was amorphous carbon with a 2 μm diameter spherical morphology.5 ml/min for 40 min. 1(a)) or the silicon wafer (Fig. As shown in Figs. the furnace temperature was o increased to a reaction temperature of 900 C. when the ammonia gas was used as the reduction gas. 1(d) and 2(d). The ammonia was maintained at a concentration of 0 % and cooled to room temperature with the flowing argon. respectively. When the concentration of ammonia gas was increased to 20 %. 1. After the pretreatment. 2(b)). The subsequent products were characterized using Fig. When the ammonia concentration was 0 %. When the concentration of the ammonia gas was increased to 10 %. transmission electron microscopy (TEM). a specific concentration of the ammonia was flowed into a quartz tube of the electrical furnace (Note that a series of experiments were conducted to investigate the effect of ammonia and the details are shown in Table 1). The initial concentration of the ammonia gas was 0 %. (b) Q10. SEM images of CNTs grown on a quartz plate with ammonia concentrations of (a) Q00. . Ammonia Specimen Reaction Temp. it was found that a large amount of CNTs had grown on both of the quartz plate (Fig. as shown in Figs. and X-ray diffraction (XRD). 1(a) and 2(a). a series of experiments were performed with different ammonia concentrations.

3. The fabricated CNTs are typical bamboo-like CNTs with a uniformly distributed diameter of 50 nm to 70 nm. Thus. Fig. ammonia concentration was increased to 30 %. (b) S10.Effects of Ammonia in Catalytic Chemical Vapor Deposition in the Synthesis of Carbon Nanotubes 271 Fig. When treated with different ammonia concentrations. TEM images of CNTs grown on (a) the quartz plate and (b) the silicon wafer with ammonia concentration of (a) Q20 and (b) S20. 2. A sticky brown oily fluid was also found on the furnace tube. SEM images of CNTs grown on a silicon wafer with the ammonia concentrations of (a) S00. The diameter of the carbon products was 300 nm. the CNTs on the silicon wafer had similar characteristics to the CNTs on the quartz plate. (c) S20. a tube wall thickness of approximately 10 nm to 20 nm. and the length was only 1 μm. and (d) S30. the carbon products were barely recognizable as CNTs. it can be deduced that the ammonia concentration is related to the corresponding carbon product and that the optimum ammonia concentration is 20 %. (a) shows a TEM image of the Q20 CNTs synthesized on the quartz plate with an ammonia concentration of 20 %. and a . Figure 3.

A higher concentration of ammonia gas (30 %) yields fewer CNTs. In addition. which in turn yields larger quantities CNTs. crystalline carbon was developed in the S20 sample rather than in the Q20 sample. the size of the catalyst must be relatively large. Essentially. Thus. when fabricating bamboo-like CNTs. From the XRD results. it can be seen that the CNTS were mixed with crystalline carbon and amorphous carbon. 4(a)) confirms the presence of amorphous carbon in the Q20 sample. Also. the volume of the catalyst increases rapidly. 4(b). Figure 3(b) shows an image of the S20 CNTs synthesized on the silicon wafer with an ammonia concentration of 20 %. The primary function of the ammonia gas is to facilitate the catalyst agglomeration. Compared with the CNTs on the quartz plate. the fact that a low concentration of ammonia yields large quantities of amorphous carbon with the CNTs suggests the low concentration is incapable of agglomerating a suitable amount of the catalyst. If an excessive concentration of ammonia gas flows into the tube. the ammonia gas may help to form CNTs by enhancing the catalyst activity as well as the catalyst acceptance properties of the silicon wafer. CONCLUSIONS Ammonia gas is important for the synthesis of CNTs. as evidenced by the sharp peak at 2Θଔ26° in the S20 sample shown in Fig.272 Hao Zhang et al. The CNTs produced with a 30 % ammonia concentration have a larger diameter then those produced with a 20 % ammonia concentration. it is suggested that ammonia gas favors the catalyst agglomeration. If the catalyst is too small. conical compartment. ACKNOWLEDGMENTS Fig. and changes their morphology: a brown oil can also be found on the tube wall. XRD profiles of CNTs grown with the ammonia concentrations of (a) Q20 and (b) S20. the carbon layer needs to be separated. However. To explain this phenomenon.9. the agglomeration may also be excessive. When the concentration is increased to 20 %. Note also that the tip of the CNT is hollow. vertically well-aligned CNTs grow on the quartz plate and on the silicon plates. causing an overly large amount of the catalyst. Figure 4 shows the XRD profiles of the CNTs grown on the quartz plate and the silicon wafer. causing the CNTs to become surface diffusion dominated. The CNTs that grow on a silicon wafer have a different morphology from those that grow on a quartz plate. The XRD analysis was performed with a Cu Kα source and operated at 40 kV and 20 mA. 4. a major function of the ammonia gas is to facilitate the catalyst agglomeration. and a relatively low intensity peak at 2Θଔ26° appeared in the Q20 sample. without any catalyst and that the root is open. The absence of ammonia gas resulted in very few CNTs on either of the substrates used in this study. the CNTs on the silicon wafer have a larger diameter ranging from 150 nm to 200 nm. the function of the ammonia gas is to facilitate the catalyst agglomeration [17. As the concentration of the ammonia gas is increased.23]. a suitable amount of the catalyst can be produced. and a more irregular compartment shape. the absence of ammonia gas results in few CNTs with some amorphous carbons. 4. Because bamboo-like CNTs are made with bulk diffusion dominating. Moreover. This work was supported by a grant (No. The sharp peak at near 2Θଔ21° (as shown in Fig. In addition. thus. Pretreatment with ammonia gas can activate the catalyst and clean its surface. R01-2006-00010482-0) from the Basic Research Program of the Korea Science and Engineering Foundation and by a grant from the . the vertically well-aligned CNTs obtained with a specific ammonia concentration indicate that the ammonia gas is important in the synthesis of CNTs. and pretreatment with ammonia gas can activate the catalyst and clean its surface.

Y. Langlois. 1023 (2001). Sci Technol. and R. Hafner and C. Klang. R. M. 603 (1993). J. C. L. 49 (1998). T. H. A. 150 (2001). C. T. W. London (1998). Forro. 105. and M. Yuan. S. Dai. C. Lee. H. 2003 (1889). 245 (1999). T. Lo. 66. K. Martinez. Chuang. 5. Xu. Chen. Science 283. P. A. D. Appl. S. J. 91. Wang. Maniette. Vazquez. and K. A. Gibson. Chatelaine. M. A 69. L. Baik. E. Anglaret. H. . Perez. Y. H. J. Lefrant. 307 (1998). Fischer. 292. J. M. 3. Carbon 43. Jung. 14. H. A. L. 4. Kuo. Park. Y. W. Carbon 41. Phys. and C. Appl. D. Vac. Eun. Phys. Bonard. R. J. and E. Lee and J. L. Petit. M. Tans. D. 3034 (2005). J. A. Fran. Master. Y. A. H. which is funded by the Korean government (MOEHRD. F. 483 (1996). Chem. Process. B 19. Chem. Cheung. Saito. M. C. Cassen. Park. C. J. Z. Hare. and W. J. Beyers. A. 18. Verschueren. 10. A. M. W. Physical Properties of Carbon Nanotubes. S. Bernier. Lee. 6. 560 (2000). N. Nature 354. T. Hsu. S. Hsu. Phys. E. E. Terrones. Phys. S. G. Lee. Stockli. Savoy. 77. M. H. Lin. J. Ma. Valles. S. Chang. Dresselhaus. P. Y. and A. M. KRF-2007-211-00054). S. Munoz. Thin Solid Films 398-399. Y. W. Phys. S. X. Yuan. Bethune. 23. and R. Martinez. R. J. 1851 (2003). M. P. Benito. and J. Thess. Imperial College Press. M. Kwo. Phys.Effects of Ammonia in Catalytic Chemical Vapor Deposition in the Synthesis of Carbon Nanotubes 273 Korea Research Foundation. Dresslhaus. and J. 512 (1999). Poncharal. E. de la Fuente. J. E. Science 273. P. Appl. A. Treacy. X. C. and J. M. J. L. N. N. Saito. M. J. 323. S. K. Nature 381. Lamy de la Chapelle. A: Mater. M. J. M. G. Sauvajol. REFERENCES 1. 20. G. 12. J. Nature 363. T. 678 (1996). Kim. Master. Chapline. Ma. 8. J. E. 19. 17. Loiseau. Journet. 3397 (2000). Y. C. G. Phys. S. Schilder. Maser. Robert. Gan. 3105 (1999). Tombler. Phys. and I. P. Lin. 9324 (2002). J. H. and J. Gorman. T. Nikolaev. and H. and J. T. R. 56 (1991). Deng. W. Franklin. 16. Iijima. and S. Wang. Salvetat. Lee. R. 7. Ebbesen. B. Wang. Shin. 15. Lee. 605 (1993). 21. Smalley. K. M. F. Lett. Science 280. Ichihashi. Zhong. 22. D. L. 2. 11. K. P. Li. Scuseria. Park. J. P. J. Terrones. G. Sci. M. Appl. Sauvajol. Diamond Relat Mater. 75. Appl. Fisher. de Vries. Dai. Nature 388. K. 1744 (1998). Dekker. L. A De Heer. S. S. M. Chem. Nature 363. 13. K. 12. 756 (1997). 587 (1998). and C. Benito. K. Xu. C. Yokoyama. Deniard. Lee. Lett. Basic Research Promotion Fund. C. M. Nature 393. Lett. Grobert. C. 743 (2001). G. Tomanek. R. Lett. W. Iijima and T. Jefferson. T. Zhang. G. J. 9. R.