Sunteți pe pagina 1din 7

Ultra-Long CNT Growth and Characterization

Austin Lane, Nie Jingqi

I. Abstract
A study of the synthesis of ultra-long carbon nanotubes by CVD was performed, and the effect of different reaction gas flow rates was observed. In the course of gathering data, experience was gained in the processes behind observing the CNTs with different analytical devices and characterizing their structures. A greater appreciation for scientific research, and reading and writing scientific publications was also obtained through the course of these experiments.

II. Introduction
In the past two decades, carbon nanotubes (CNTs) have been the focus of extensive research in the scientific community. Thousands of papers on CNTs are published annually, on topics ranging from synthesis to applications in electronics, composite materials, hydrogen storage, and other media [1]. A carbon nanotubes potential use is a direct result of how it is synthesized. In particular, superlong CNTs have unique properties that would make them very suitable for creating FETs (field-effect transistors) on a single tube [2]. In the past two years, various papers have been published on the synthesis of these ultra-long nanotubes, which involve the use of CVD [2-4]. Efforts in this field began as early as 2004, with the growth of SWNTs measuring 4 cm long [5]. Presently, that number has been extended to 18.5 cm, with reported growth rates reaching 80-90 m/s [3]. Besides augmenting their length, many researchers are looking for ways to enhance the selectivity of CNT growth, namely by the preferential growth of semiconducting CNTs or the preferential destruction of metallic CNTs [6],[7]. This summer, I was able to work with a researcher in this field, Nie Jing-Qi, and her colleagues at the Beijing Key Laboratory of Green Chemical Reaction at Tsinghua University, China. There, I studied the synthesis of ultra-long carbon nanotubes by CVD, and the various ways to characterize their structure; in particular, SEM, TEM, light microscopy, and Raman spectroscopy.

III. Methods
A. CVD 1. Theory There are various methods available for the synthesis of carbon nanotubes; namely, the arc discharge method, laser ablation, and chemical vapor deposition, or CVD. Of these three, CVD offers the most control over the structure of the product, and also lends itself to industrial scale-up [8]. However, there are still problems with this method that prevent its scale-up, namely the lack of control over semiconducting vs. metallic nanotubes and poor catalytic efficiency. Many scientists agree that if control over CNT chirality could be established while maintaining the alignment and length of existing CVD methods, it would remove a major obstacle from the commercial use of CNTs to produce the next generation of electronic devices [9],[10]. The mechanism of CVD growth involves a metal catalyst, usually Fe, Co, or Ni, and a gaseous carbon precursor, usually CH4, C2H4, or CH3OH. The catalyst allows for CNT growth by providing a location for the carbon precursor to decompose into elements. There, elemental carbon deposits and can form a nanotube. The exact mechanism of this method is still highly debated, but it can be inferred

from experimental data that growth happens either one of two ways; either the catalytic particle remains stationary while the tube grows around and on top of it, called a root growth mechanism, or the catalyst particle stays at the front on the tube and moves with the growth, called a tip-growth mechanism [8]. The growth of super long CNTs has been illuminated by many papers and most of them agree with the kite mechanism (tip-growth) [3],[11]. Amorphous carbon can also accumulate on the metal surface, deactivating the catalyst over time. The size of the catalyst particle is critical to CNT growth, as it correlates to the diameter of the nanotube. If the particle is too small, it will tend to agglomerate with other particles in order to reduce free surface energy, thereby increasing the size of the CNT. If the particle is too large, it will deactivate itself by adsorbing too much amorphous carbon onto its surface, preventing CNT growth. Other reaction parameters, such as temperature, time, carbon precursor, use of water, etc. also have an important effect on a nanotubes morphology [8]. 2. Experiment Details In this report, the substrate was a Si wafer with a thermally grown layer of SiO2 on the surface. A solution of FeCl3 and ethanol served as the catalyst. A piece of silicone was used to dab one end of the Si wafer with catalyst solution, and the substrate was subsequently reduced in H2 for 20 minutes at a temperature of 910 oC inside a quartz tube furnace. A mixture of CH4 (25 mL/min) and H2 bubbled through liquid water (10 mL/min), along with an additional hydrogen flow (25 30 mL/min), were then fed into the tube at a reaction temperature of 1000 oC for 20 50 minutes, depending on the length of the substrate. Finally, the furnace was cooled under Ar and H2 protection for 30 minutes. In this report, there were two sets of experiments, which differed only by the amount of H2 present in the tube during the reaction. A visual representation of the process can be seen in Fig. 1.

1000

Ar + H2

H2 + CH4+ H2O

Ar + H2

Temperature ( C)

H2 + CH4
900

200 0 20 40 60 80 100

Time (min)

Figure 1. A Temperature vs. Time graph of the CNT reaction.

B. SEM 1. Theory SEM (Scanning Electron Microscopy) works by shooting a beam of electrons at an electricallyconductive target, then collecting the resulting emitted radiation to form a picture. Carbon nanotubes are intrinsically conductive, which increase their apparent size in an SEM. This is due to charge build-up as the CNT is bombarded with electrons. 2. Experiment Details The main purpose of the SEM characterization was to determine the length, alignment, and overall catalytic efficiency of the CNT products. The CNTs could be directly observed on the Si substrate from a low-mag. setting (x25), due to the charging effect mentioned above. Each picture taken of the CNTs could be pieced together to reveal the overall length of the nanotube, as seen in Fig. 3. SEM images were the clearest when taken on the day of the CNT growth, as impurities tend to accumulate on the surface of CNTs over time. SEM pictures were taken by a JSM 7401F scanning electron microscope, operating at an accelerating voltage of 1.0 kV. C. TEM 1. Theory TEM (Transmission Electron Microscopy) works by a similar mechanism to SEM, but it forms a picture of a specimen based on the effect of the specimen on the electrons passing through it, rather than simply colliding with it. This is accomplished by using a much higher voltage than in SEM. A picture can be formed on a phosphorous plate at the base of microscope, which can then be lifted to view the image on a computer. 2. Experiment Details The main purpose of TEM characterization is to view the morphology and internal structure of as-grown nanotubes. To accomplish this, the CNTs had to be transferred from the Si substrate to a copper TEM grid by a method previously unpublished. Unfortunately, no CNTs could be found on the grid after the transfer, so no images or information about the morphology of the long CNTs are available. TEM characterization was performed using a JEOL JEM 2100 transmission electron microscope with an accelerating voltage of 120 kV. D. Light Microscope 1. Theory The purpose of using a light microscope for CNT characterization is to examine the physical structure of the CNT, and determine its degree of continuity. This is not easily seen by SEM, as CNTs in the gaps of the substrate are not visible. 2. Experiment Details Before observing the CNT with a light microscope or Raman spectrometer, TiO2 particles had to be deposited on the surface of the CNT. To accomplish this, liquid TiCl4 was mixed with H2O to form solid TiO2 pigment particles and HCl gas, according to this reaction: TiCl4 (l) + H2O (l) TiO2 (s) + HCl (g)

After depositing the TiO2 on the surface, the CNTs can be viewed by a light microscope, as seen by the picture in Fig. 2a. E. Raman Spectroscopy 1. Theory Raman spectroscopy is used for the characterization of CNTs because it provides useful information about their structure and quality. The theory of Raman spectroscopy involves principles of quantum mechanics. A specimen is fired upon by a laser with a specific wavelength, and thus a specific energy. In the case of a carbon nanotube, if the induced phonons and excited electronic states are of the same energy, large peaks can be observed in a Raman spectrum as a result of this resonance (Fig. 4) [12]. In a typical CNT Raman spectrum, there are 3 peaks of significant importance. The RBM (Radial Breathing Mode) peak, as seen in Fig. 4a, provides detailed structural information about the CNT. The frequency of the RBM peak (RBM) is inversely proportional to the diameter of the nanotube, as given by the equation RBM = /d, where d is the diameter of the nanotube and is an experimentally determined constant, with a value of 248 nm cm-1 [12]. The other two important peaks can be seen in Fig. 4b. The G band (right) represents the Raman shift given by sp2 graphite, and its shape can indicate if a nanotube is metallic or semiconducting. The D band (left) is caused by imperfections in the CNT. The ratio of intensities of the two peaks (ID/IG) is a measure of the degree of graphitization of the nanotube. 2. Experiment Details The TiO2 pretreatment is important for the Raman spectrometer, because the spot of the laser must be precisely placed on the structure you want to analyze. The position of the carbon nanotube can be inferred from the position of the TiO2 spheres, as described in Fig. 2b. Raman spectroscopy was performed using a JY HR800 Raman spectrometer. A 633 nm laser was used with a 1 m size spot. The range of the spectrometer is 60 3000 cm-1.

(a)

(b)

Figure 2. The physical structure of the CNT can be viewed as a result of the deposited TiO 2 particles. (a) As
viewed by a light microscope. (b) As viewed by Raman video feed. The position of the CNT can be inferred by drawing a straight line through the center of two adjacent spheres, as demonstrated by the red dashed line.

IV. Results and Discussions


A. SEM Images As mentioned in section III.A.2, there were two sets of experiments in this report. The first set used a H2 flow rate of approximately 30 mL/min, which yielded a sparse amount of short CNTs. The catalyst region of these wafers had many short, randomly-dispersed CNT structures as well. However, when the H2 flow was reduced to 25 mL/min in the second set, the CNTs growth was greatly improved, yielding long, well-aligned structures as seen in Fig. 3.

Figure 3. Growth of long CNTs on Si/SiO2 substrate. Pictures were taken


individually at low magnification (x25) and spliced together.

The longest CNTs measured 32 mm, and grew over the edge of the substrate, indicating they might have continued growing if the substrate had been longer. The stark difference in growth as a result of varying the H2 flow rate may be explained by the need for a certain CH4/H2 ratio when synthesizing ultra-long CNTs. The CH4 flow rate was not changed during this study, which means the same amount of carbonaceous material was present in both experimental sets. However, the presence of too much H2 may lead to a choking effect, where a growing CNT is essentially starved of elemental carbon because of the excess of H2 molecules surrounding it. This would explain the stunted growth of the CNTs that managed to escape the catalyst region. The H2O present in the reaction gas also seemed to have an effect on the product. In this report, no trials were performed without the presence of water, but based on findings in other studies [3],[13], the presence of water in the reaction reduces the build-up of amorphous carbon on the surface of the substrate. This theory applied to our findings as well, as no amorphous carbon was observed on the substrate within the growth area for any test. This result can be seen in Fig. 3. Also, the catalyst region was relatively clean for all tests, another finding reported by said studies. Analysis by the light microscope revealed that CNTs are indeed able to grow across gaps in the Si substrate [3]. Examples like the one in Fig. 2a were seen in multiple tests. The nanotube appears to sag down into these gaps, and does not stretch tightly across. This could be a result of the added mass from the TiO2 particles on the tubes surface, or this could just be the natural way in which the CNT grows. If the latter case is true, perhaps some aspect of the CNT growth mechanism could be deduced from the degree of bending from an unadulterated nanotube. Broken nanotubes could also be seen within the substrate gaps. This indicates that, although CNTs are intrinsically very strong, they are quite fragile when isolated. Some basic information could be gathered from the Raman spectrum of a single CNT. The RMB peak in Fig. 4a is located at approximately 126 cm-1, and by using the formula given in section III.E.1, the

estimated diameter of the nanotube is 1.97 nm. This is only a rough calculation, as the formula is meant for SWNTs only. The exact structure of the examined CNT is unknown, but it can be inferred that it is a MWNT, due to its straightness and rigidity. The strong G band and almost non-existent D band seen in Fig. 4b indicates a CNT with a high degree of graphitization and few defects. This is to be expected, however. Strong D bands are typically only seen when analyzing bulk CNT material, where van der Waals interactions between nanotubes may lead to a higher degree of imperfections.
(a)
633 nm laser

(b)
633 nm laser

Intensity (a.u.)

RMB peak

Intensity (a.u.)

G Band

D Band

100

150

200

250

300

350

1200

1400

1600
-1

1800

Raman Shift (cm )

-1

Raman Shift (cm )

Figure 4. Portions of Raman spectrum of single carbon nanotube. (a) RMB band. (b) G and D band.

V. Conclusion
In summary, the results of these experiments with the growth and characterization of superlong CNTs led to a greater understanding of their structure and properties. Namely, ultra-long carbon nanotubes are sensitive to the conditions they are grown in, specifically the ratio of CH4/H2 flow rates. Also, these experiments gave me a greater understanding of scientific research in general, and the effort that is placed into obtaining data and extrapolating results from it. I also received hands-on experience with numerous types of scientific equipment, which I think will prove invaluable in coming years. It is one thing to read about CNT synthesis and understand the theory behind a certain process, but it is quite another to actually perform a real experiment. As a result of this study, I have also improved my understanding of scientific papers and the way they are written, by both reading papers and writing my own, with the guidance of Nie Jing-Qi.

VI. References
[1] R. H. Baughman, A. A. Zakhidov, W. A. de Heer, Science 2002, 297, 787. [2] X. S. Wang, Q. Q. Li, J. Xie, Z. Jin, J. Y. Wang, Y. Li, K. L. Jiang, S. S. Fan, Nano Lett. 2009, 9, 3137-3141. [3] Q. Wen, R. Zhang, W. Qian, Y. Wang, P. Tan, J. Nie, F. Wei, Chem. Mater. 2010, 22, 1294-1296. [4] Q. Wen, W. Qian, J. Nie, A. Cao, G. Ning, Y. Wang, L. Hu, Q. Zhang, J. Huang, F. Wei, Adv. Mater. 2010, 22, 1867-1871. [5] L. X. Zheng, M. J. OConnell, S. K. Doorn, X. Z. Liao, Y. H. Zhao, E. A. Akhadov, M. A. Hoffbauer, B. J. Roop, Q. X. Jia, R. C. Dye, D. E. Peterson, S. M. Huang, J. Liu, Y. T. Zhu, Nature 2004, 3, 673-676. [6] Y. Li, S. Peng, D. Mann, J. Cao, R. Tu, K. J. Cho, H. Dai, J. Phys. Chem. B 2005, 109, 6968-6971. [7] Y. Zhang, Y. Zhang, X. Xian, J. Zhang, Z. Liu, J. Phys. Chem. C 2008, 112, 3849-3856.

[8] A. Loiseau, P. Launois, P. Petit, S. Roche, J.-P. Salvetat: Understanding Carbon Nanotubes: from Basics to Applications, Springer-Verlag, Berlin Heidelberg 2006. [9] E. Joselevich, C. M. Lieber, Nano Lett. 2002, 2, 1137-1141. [10] L. Ding, A. Tselev, J. Wang, D. Yuan, H. Chu, T. P. McNicholas, Y. Li, J. Liu, Nano Lett. 2009, 9, 800805. [11] M. Hofmann, D. Nezich, A. Reina, J. Kong, Nano Lett. 2008, 8, 4122-4127. [12] M.S. Dresselhaus, G. Dresselhaus, A. Jorio, A.G. Souza Filho, R. Saito, Carbon 2002, 40, 2043-2061. [13] K. Hata, D. N. Futaba, K. Mizuno, T. Namai, M. Yumura, S. Iijima, Science 2004, 306, 1362-1365.

S-ar putea să vă placă și