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ISSN 1063 7745, Crystallography Reports, 2011, Vol. 56, No. 2, pp. 310314. Pleiades Publishing, Inc., 2011.

. Original Russian Text R.R. Ismagilov, P.V. Shvets, A.Yu. Kharin, A.N. Obraztsov, 2011, published in Kristallografiya, 2011, Vol. 56, No. 2, pp. 336341.

NANOMATERIALS, CERAMICS

Noncatalytic Synthesis of Carbon Nanotubes by Chemical Vapor Deposition


R. R. Ismagilov, P. V. Shvets, A. Yu. Kharin, and A. N. Obraztsov
Moscow State University, Moscow, 119992 Russia e mail: ismagil@polly.phys.msu.ru
Received April 8, 2010

AbstractA new method is proposed to obtain uniform arrays of multiwall carbon nanotubes without cata lysts. Nanotubes have been formed by carbon condensation from a hydrogenmethane gas mixture activated by a dc discharge. Structural and morphological investigations of the obtained material were performed by Raman spectroscopy, scanning and transmission electron microscopy, energy dispersive X ray analysis, and electron energy loss spectroscopy. It is shown that the obtained nanotubes contain no impurities that could act as catalysts. Based on these experimental data, it is concluded that the nanotube synthesis under study is noncatalytic. Possible mechanisms of this synthesis are considered. DOI: 10.1134/S1063774511010123

INTRODUCTION Nanocarbon films are of great interest for different fields of research and technology. These materials are produced in various ways. In particular, one of the most effective methods is carbon deposition on sub strates from a gas medium activated by a dc glow dis charge [1, 2]. It has been previously shown that this chemical vapor deposition can be used to obtain both polycrystalline diamond films and films composed of graphite like material in the form of graphite nanoc rystallites or carbon nanotubes (CNTs) [13]. The lat ter, especially in the form of CNT arrays on a sub strate, are of special interest because of the uniqueness of their structural properties and the many prospects of their application in various fields [4]. Currently, some methods have been developed for obtaining CNT arrays using catalysts. These methods generally include several technological stages: sub strate preparation, the deposition of metal catalyst on the substrate, the provision of conditions for synthe sizing nanotubes, and the removal of catalyst particles [5]. The existence of several stages (involving signifi cantly different technologies), changes in the struc tural and morphological characteristics of the materi als during catalyst removal, and some other problems significantly hinder the use of catalyst aided tech niques in a number of potential applications. These problems can be solved, in particular, by developing noncatalytic methods of nanotube synthesis. However, the known implementations of noncatalytic processes lead to a significant decrease in the degree of array ordering and the structural quality of nanotubes in the arrays [5, 6]. In this paper we present a new method for fabricating CNT arrays without catalysts.

EXPERIMENTAL Samples of CNT arrays were prepared on square (25 25 mm2 in size) silicon substrates by chemical vapor deposition (CVD) from a methanehydrogen gas mixture activated by a dc discharge. The CVD sys tem was described in [1, 2]. In contrast to previous investigations, in this study the substrate was not in direct contact with the gas discharge plasma. A 4 mm thick niobium metal plate with through holes (3 mm in diameter) was mounted above the substrate on a water cooled base (Fig. 1). The plate with holes had an electric contact with the substrate base. This design made it possible to ignite and maintain a gas discharge in the gap between the upper water cooled electrode (cathode) and the niobium plate (anode). The deposition conditions were similar to those used in [1, 2]: a gas mixture pressure of about 9.5 kPa, a methane concentration in the range of 115%, and a discharge current density of about 0.3 A/cm2. How ever, due to the absence of direct contact with plasma, the substrate temperature decreased during the depo sition (to 650, according to thermocouple mea surements). Deposition was performed in two stages. In the first stage, the reaction chamber was filled with pure hydrogen in which a discharge was ignited. The dis charge parameters were settled as follows: gas pressure 9.5 kPa, discharge current 9 A, and substrate tempera ture 650. The niobium plate temperature (mea sured by an optical pyrometer) was 1100. The sys tem was kept under these conditions for 15 min, after which methane was introduced into the chamber in a specified ratio and the film was grown for 10 min. After the power supply was switched off, the reaction cham ber was pumped; after cooling the substrate and nio

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NONCATALYTIC SYNTHESIS OF CARBON NANOTUBES Water cooled cathode Plasma Plate with holes Substrate Water cooled base (anode)

311

Fig. 1. Photograph and scheme demonstrating the arrangement of electrodes, plate with holes, and substrate during carbon film deposition from gas discharge plasma.

bium plate to room temperature, atmospheric air was leaked in and the deposited films were extracted from the chamber. A structural and morphological study of the sam ples was conducted using a Leo 1550 Gemini scanning electron microscope (SEM) (accelerating voltage 5 kV), a Jeol JEM 2100 transmission electron micro scope (TEM) (accelerating voltage 200 kV), and a Ramanor U1000 Raman spectrometer (Jobin Yvon) (excitation wavelength 514.5 nm). The elemental composition of the CNT arrays was determined by an energy dispersive X ray (EDX) analysis using an INCA 300 attachment for the Leo 1550 Gemini and by electron energy loss spectroscopy (EELS) using an LEO 912 AV Omega TEM, which was equipped with an electron spectrometer with an omega filter. The TEM samples were prepared by deposing fragments of carbon material, which were mechanically separated from the films, on a copper micropore mesh. RESULTS AND DISCUSSION During the experiments it was established that dif ferent types of carbon materials (including nanodia mond and nanographite films) can be obtained under the above mentioned conditions, depending on the methane concentration. The fabrication and study of these materials is beyond the scope of this study. Homogeneous dull black films were obtained at meth ane concentrations in the gas mixture in the range of 67%. A SEM study revealed that they are CNT arrays, uniformly covering the entire surface of silicon substrate. Characteristic SEM images of these films are shown in Fig. 2. One can see that the nanotubes forming a film have a preferred perpendicular to the substrate surface orientation. The CNT array thick ness, as determined from the SEM images of trans verse cross sections, was about 15 m. The SEM images obtained with the maximum resolution (Fig. 2b) revealed that nanotubes are spaced by a dis
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tance of about 20 nm and have a diameter of about 5 nm. A characteristic Raman spectrum of CNT samples is shown in Fig. 3. The lines at 1580 cm1 (G line due to the vibrational mode of atoms in the hexagonal graphite plane) and 1350 cm1 (D line indicating the presence of particles with a graphite like atomic nano structure) correspond to graphite like carbon material and are typical of multiwall CNTs [8, 9].

(a)

20 m (b)

20 nm

2 m

(c) (a)

10 m
Fig. 2. SEM images of the ordered CNT array: (a) uniform coating of silicon substrate surface and (b, c) mainly per pendicular orientation of nanotubes with respect to the substrate plane.

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The CNT samples were investigated by TEM to determine the structural features of individual nano tubes. In particular, the analysis of the TEM images shows that these nanotubes are cylinders with open ends consisting of well ordered atomic layers (a small amount of disordered carbon was detected on the outer surface of only a few nanotubes). One character istic image of these nanotubes is shown in Fig. 4.
I, rel. units 1350 cm1 1580 cm1

1200

1400 1600 Raman shift, cm1

Fig. 3. Characteristic Raman spectrum of ordered CNT array.

(a)

5 nm

According to the TEM data, the external CNT diam eter varies from 4 to 6 nm, whereas the number of cylindrical layers, which are spaced by 0.34 nm (like in conventional graphite), changes from 4 to 7. Special attention was paid to detecting foreign impurities in the CNT composition that could be unintentionally introduced (since the synthesis was performed without catalysts). A detailed analysis of the TEM images of CNTs did not reveal any objects characteristic for metal particles. These conclusions were confirmed by the EDX and EELS data. A typical EDX spectrum of the CNT samples is shown in Fig. 5. The spectra are superpositions of only expected peaks: a strong carbon peak (0.277 keV), which agrees with the carbon nature of nanotubes; a strong silicon peak (1.741.84 keV), which is due to the Si substrate; and a weak oxygen peak (0.525 keV). The latter can be due to the presence of silicon particles with native oxide or the adsorption of gas molecules during sample storage in air (the oxygen concentration, determined from this peak intensity, did not exceed several weight percent). No impurities that could correspond to catalytically active metals were found by EDX analysis in the sam ples. The characteristic EELS spectrum of the CNT samples in the energy range of 250350 eV is shown in Fig. 6. The sharp decrease in the intensity near 280 eV corresponds to the absorption edge of carbon atoms, where the electron energy is resonantly absorbed by atoms, giving rise to electronic transitions from the internal K shell to higher energy shells. The features of the fine structure of the spectrum in this range make it possible to determine the type of interatomic bonding characteristic of a given carbon modification. The fine structure of the recorded spectra is similar to that in the spectra of other carbon materials with graphite like interatomic bonds, including multiwall CNTs [9]. Note that a detailed analysis of the spectra in this range
I, rel. units

5 nm

(b)

Fig. 4. TEM image of an individual multiwall CNT: (a) longitudinal and (b) transverse projections.

Si

O 0 0.5 1.0 1.5 2.0 2.5 keV 250 260 270 280 290 300 310 320 330 340 350 Electron energy loss, eV
Fig. 6. Characteristic electron energy loss spectrum of a multiwall CNT sample. CRYSTALLOGRAPHY REPORTS Vol. 56 No. 2 2011

Fig. 5. Typical EDX spectrum of a multiwall CNT film.

NONCATALYTIC SYNTHESIS OF CARBON NANOTUBES a1 a2

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20 nm b1

2 m b2

200 nm

100 nm
Fig. 7. SEM image of high density pores formed on a sili con substrate as a result of interaction with hydrogen plasma at a 9 A discharge current. The pore density and size correspond to the CVD parameters at which an ordered multiwall CNT array is synthesized.

1 m c1 c2

200 nm

of electron energy losses and other ranges, including the regions of interband transitions and plasmons peaks, indicated the complete absence of any noncar bon impurities in the samples obtained. The mechanism of CNT formation in terms of the above described method is not completely clear. However, based on our experimental results and the data of other researchers, we can make certain sugges tions about a possible growth mechanism. In particu lar, the possibility of synthesizing multiwall CNTs by CVD on porous carbon material CB BP2000, as well as on pores formed in previously prepared CNTs by their moderate oxidation, was shown in [10]. Under these conditions, the growth of CNTs with a diameter equal to the pore diameter was observed. In [11], CNTs were synthesized on silicon and germanium nanoparticles deposited on a silicon substrate; the nanotube diameter was close to the nanoparticle size. In all these examples the key role in CNT synthesis belongs not to the catalytic activity of the materials used but to their topological features, which provide nanoscale masks for deposing carbon from the gas phase and growing nanotubes. A series of substrates were treated in hydrogen plasma to study the formation of ordered multiwall CNT arrays in more detail. These samples differed in regards to discharge current, which varied near the value corresponding to CNT growth; the other process parameters (gas flow, pressure, etc.) remained the same. The basic SEM data for these samples are shown in Figs. 7 and 8. It was found that a small variation in
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2 m d2 e2

200 nm

200 nm

200 nm

Fig. 8. SEM images of the surfaces of silicon substrates processed in hydrogen plasma at different discharge cur rents: (a1, a2) 9.2 A, (b1, b2) 9.4, (c1, c2) 8.8 A, (d2) 8.6 A, and (e2) 8.4 A. The other process parameters were main tained at the same level as in case presented in Fig. 7. The carbon material was formed as nanographite or nanodia mond films on the substrates with this morphology.

only one parameter (discharge current) led to a signif icant change in the silicon substrate morphology in the first deposition stage, which eventually determined the type of the final carbon material. It was found that CNT array formed only when high density nanopores arose on the substrate surface as a result of contacting with hydrogen plasma (Fig. 7). The formation of nanocarbon or (rarely) nanodiamond films (Fig. 8)

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was observed at the process parameters at which pores were not formed on substrate. The type of the depos ited carbon material was determined by Raman spec troscopy [13]. There is a similar result when pores are formed, but either their density or size is much lower than the optimal value corresponding to the CNT growth. Our data suggest that the observed noncatalytic CNT synthesis is related to the formation of high den sity nanopores on the substrate. The presence of meth ane in the plasma activated gas mixture leads to the formation of chemically active carbon dimers [1, 2], which then condense on the substrate surface. In the presence of nanopores, carbon condenses on their inner surface; as a result, ring carbon structures are formed to initiate the gradual growth of vertically ori ented multiwall CNTs. According to this mechanism, the pore diameter and density should correspond to the diameter and density of the nanotubes. This corre spondence is indeed observed (Figs. 2b, 7). CONCLUSIONS We demonstrated the possibility of noncatalytic synthesis of uniform array of multiwall CNTs on sili con substrates from a hydrogenmethane gas mixture activated by a dc discharge. The absence of noncarbon (metal) impurities in amounts corresponding to the presence of catalytically active particles is shown by EDX analysis and EELS. A mechanism is proposed to explain the noncatalytic growth of multiwall CNTs, according to which the hydrogen plasma induced formation of nanopores in silicon substrate plays an important role in the formation of nanotubes. The inner pore surface serves as a mask during nanotube growth.

ACKNOWLEDGMENTS We are grateful to S.S. Abramchuk and A.V. Gar shev (Moscow State University) and Hua Jiang (Hels inki Technological University, Finland) for their help in the SEM and TEM studies. This study was supported by the Russian Founda tion for Basic Research, project no. 08 02 91755 and 09 01 12024 ofi_m. REFERENCES
1. A. A. Zolotukhin, A. N. Obraztsov, A. O. Ustinov, and A. R. Volkov, Zh. Eksp. Teor. Fiz. 124, 1291 (2003). 2. A. N. Obraztsov, A. P. Volkov, K. S. Nagovitsyn, et al., J. Phys. D: Appl. Phys. 35, 357 (2002). 3. R. R. Ismagilov, A. P. Volkov, P. V. Shvets, and A. N. Obraztsov, Fiz. Khim. Poverkh. Zashchita Mater. 45 (6), 570 (2009). 4. R. H. Baughman, A. A. Zakhidov, and W. A. de Heer, Science 297, 787 (2002). 5. Z. F. Ren, Z. P. Huang, J. W. Xu, et al., Science 282, 1105 (1998). 6. J. Hahn, S. B. Heo, and J. S. Suh, Carbon 43, 2638 (2005). 7. Z. G. Cambaz, G. Yushin, S. Osswald, et al., Carbon 46, 841 (2008). 8. W. Li, H. Zhang, C. Wang, Yu. Zhang, et al., Appl. Phys. Lett. 70, 2684 (1997). 9. M. S. Dresselhaus, G. Dresselhaus, R. Saito, and A. Jorio, Phys. Rep. 409, 47 (2005). 10. J. H. Lin, C. S. Chen, H. L. Ma, et al., Carbon 46, 1619 (2008). 11. D. Takagi, H. Hibino, S. Suzuki, et al., Nano Lett. 7, 2272 (2007).

Translated by A. Grudtsov

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2011

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