Solid-state synthesis of multiwalled carbon nanotubes

S.P. Doherty and D.B. Buchholz

Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208

B-J. Li
Materials Research Laboratories, Industrial Technology Research Institute, 195-5 Chung Hsing Road, Section 4 Chutung, Hsinchu, Taiwan

R.P.H. Changa)
Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208 (Received 23 July 2002; accepted 27 January 2003)

A modified high-temperature arc furnace was used to produce carbon nanotubes from carbon black by a solid-state transformation without a catalyst. The layer of carbon nanotubes thus formed was nearly pure with only a minor amount of carbon black particles. The properties of these nanotubes were found to be very similar to those produced by the conventional arc synthesis. Based on this process, a mechanism for the growth of these nanotubes is proposed. In addition, field-emission properties of these nanotubes were comparable to the properties of arc-grown carbon nanotubes.

I. INTRODUCTION

The discovery of carbon nanotubes (CNTs) by Iijima in 19911 has created a great amount of interest due to their remarkable mechanical2 and electrical3 properties. Nanotubes have already been widely used as field emitters4 and scanning microscope probe tips.5 In addition, nanotubes have potential applications in hydrogen storage,6 electronic devices,7,8 and composite materials.9 The most significant challenge for the industrial use of CNTs is the ability to produce large-scale quantities of high-crystalline nanotubes. This requires the development of rapid, efficient, and low-cost processing methods. The three most common production techniques for CNTs are arc discharge, laser ablation, and chemical vapor deposition (CVD). During the production of CNTs by arc discharge between a pair of graphite electrodes, graphitic species are evaporated from the anode as a result of high-temperature heating by the arc and deposited by rapid solidification on the water-cooled cathode.10 The resulting condensed material contains highly crystalline multiwall nanotubes (MWNTs) along with multilayered polyhedral graphitic particles. Single-wall nanotubes (SWNTs) can be produced by adding a metal catalyst to the system. Laser ablation uses an intense

a)

Address all correspondence to this author. e-mail: r-chang@northwestern.edu This author was an editor of this journal during the review and decision stage. For the JMR policy on review and publication of manuscripts authored by editors, please refer to http:// www.mrs.org/publications/jmr/policy.html.
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laser pulse to ablate a graphite target containing a catalyst.11 During laser ablation, the evaporated carbon species flow downstream in an oven and condense on a cold finger where carbon nanotubes are formed. The CVD method involves flowing a hydrocarbon gas over a heated layer of catalyst particles.12 The carbon nanotubes grow on the catalyst particles by a vapor-liquid-solid (VLS) formation process. All of these synthesis methods rely on the formation of nanotubes from a carbon vapor source. Each method has its own set of parameters that determines the type and quality of the nanotubes produced. Using microscopy studies, Thein-Nga et al. have reported that high-temperature processes give much better overall CNT properties.13 Recently, several authors have indicated that the production of nanotubes using a condensed phase process is possible. Setlur et al. used a high-temperature oven to heat different carbon precursors in an attempt to produce carbon MWNTs.14 It was found that nongraphitizable carbon precursors, including pyrolyzed sucrose and fullerene soot, can be transformed into nanotubes at high temperatures (about 2200 C), while other graphitizable precursors, including pyrolyzed Saran, did not form nanotubes under the same conditions. Since the oven temperature was below the evaporation point of the precursors, the nanotubes must have formed by a solid-state transformation. Calderon-Moreno et al. have grown MWNTs under hydrothermal conditions at 800 C and 100 MPa of pressure.15,16 SWNTs have been produced by annealing soot that was produced by ablating composite targets comprised of graphite, nickel, and cobalt.17,18 MWNTs have been produced by ion-beam sputtering graphite and iron, followed by a rapid thermal processing treatment. 19 Nanotubes have also been
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S.P. Doherty et al.: Solid-state synthesis of multiwalled carbon nanotubes

produced by the decomposition of C60 in the presence of metallic particles20,21 and by ball milling of graphite.22,23 While all of these processes did not require a carbon vapor to produce nanotubes, most required catalysts for the reactions to occur. We have been continuing the work of Setlur et al.14 by heating nongraphitizable carbon precursors without catalysts to higher temperatures, around 3000 C. Carbon black has been an important technological material for decades. It has been used in applications such as reinforcement filler for rubber24 and conductive polymer additives.25 Due to the myriad technological applications, the structure of carbon black has been under extensive study for decades. Carbon black is a type of soot, which is a class of solid carbons that can be described as closed many-layer carbon particles. Along with other soot and fullerenes, carbon black is composed of fragments of carbon networks, either single layers (bent, curved, or flat) or small, assembled packs. There is not a commonly accepted concept for the formation and structure of carbon black, although there have been a number of theories presented.2629 Initial theories proposed that carbon black particles were composed of graphitelike microcrystallites. These crystallites were composed of several fragments of graphene sheets, randomly oriented compared to the rest of the particle. This proposed structure contained all hexagonal carbon rings and had no pentagons or other curved structures incorporated.26 Later theories have proposed that the microcrystallites were more ordered around the outside of the particle, ordered into a helical shape, or surrounding a dense core. Another theory described the carbon black as an icosohedral carbon layer curled into a helical fullerene shell.27 None of these theories have been universally accepted. A new understanding of carbon black began with the discovery of fullerenes in 1985.30 The discovery of fullerenes introduced the concept of graphene sheets that could contain a pentagonal or heptagonal ring. When it was discovered that fullerene and carbon soot could be produced in similar processes, it was concluded that fullerenelike structures must be present in the formed soot and carbon black. This understanding led to the modern theory of carbon black formation and structure.28,29 According to the modern theory, carbon black forms in a two-stage process. First, a nucleus of fullerenelike structures is created from the decomposition of the hydrocarbon precursors. This core includes pentagon, and possibly heptagon, defects in the multiple graphene layers. After the cores form, they are coated by graphitic layers, which aggregate to form larger particles. Since formation and aggregation occur simultaneously, the carbon black has a grapelike structure to it. Figure 1 shows the proposed structure of a carbon black particle.
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FIG. 1. Proposed structural model of a carbon black particle.

As the graphitic sheets coat the nuclei, defects will be incorporated into the structures as five-membered and seven-membered rings. This structure suggests that carbon black would be an ideal precursor for a solid-state nanotube formation process. Since this type of structure would include five-membered rings in the hexagonal graphene lattice, they could also act as the seed for the formation of carbon nanotubes.
II. EXPERIMENTAL A. Nanotube growth process

We have created a high-temperature arc furnace by modifying the operation of our plasma arc system. The basic system was comprised primarily of two watercooled electrodes, an anode fabricated from a 3/8 diameter rod of randomly oriented graphite (ROG) with a hole of 3/16 diameter by 3/8 deep and a cathode comprised of a solid 3/8 diameter ROG rod. Figure 2 shows a cross-section schematic of the electrode setup and a view of the anode surface. The difference between this setup and a traditional arc-discharge setup is the use of a hollow anode instead of a solid graphite anode. In this setup, the hole in the anode cup was filled with a tightly compacted carbon precursor slug. For our experiment,

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S.P. Doherty et al.: Solid-state synthesis of multiwalled carbon nanotubes

black in the anode cup was uniformly heated to a temperature around 3000 C as measured by an Accufiber M100 (Santa Clara, CA) optical pyrometer with a spatial resolution of 5 mm. We controlled the anode temperature using the electrode spacing, so there was little evaporation of the carbon black. The synthesis time ranged from 10 s to 5 min in either a pure helium or hydrogen/helium atmosphere. After each run, the surface materials on the electrodes were analyzed using a scanning electron microscopy (SEM; Hitachi S-4500) (Pleasanton, CA) and a transmission electron microscopy (TEM; Hitachi H-8100, HF-2000). Samples for TEM were prepared by scraping appropriate regions of the electrodes and dispersing the powdered materials onto a holey carbon grid.
B. Field-emission measurements

FIG. 2. Schematic of the high-temperature arc furnace: (a) view of the anode surface with carbon precursor in the center, (b) cross section of the two electrodes showing the path of the current between the cathode to the anode.

we have used both carbon black and graphite powder. As we have described above, carbon black has both fiveand seven-membered rings, while graphite has only six-membered rings. Thus, we do not expect carbon nanotubes to be formed using the graphite precursor. The carbon black (Alfa Aesar, 200 mesh, 99.99%, Ward Hill, MA) was a pyrolyzed acetylene and was compressed into the anode using a steel rod with a force of 10 N/cm2. The carbon black powder had to be compressed in several stages to form the loose powder into a dense slug. The anodes filled with graphite powder were prepared in a similar fashion to the carbon black ones to compare graphitizable carbon with nongraphitizable carbon. The operating conditions were optimized to minimize the erosion of the anode and the vaporization of the carbon black. The arc oven was run at a pressure of about 100 torr under an environment of pure helium or a mixture of helium and hydrogen. The plasma was generated by a direct current power supply at 100 A. A radio frequency component was used to start the discharge so that a set spacing between the electrodes could be maintained. In this configuration, the arc current from the cathode was carried through the rim of the anode cup since the graphite electrode has a much lower resistivity than the carbon black (1.47 m cm versus 450 m cm). Figure 2 shows the path of the current from the cathode to the graphite rim of the anode. A plasma was produced by the arc oven uniformly across the entire anode surface including the carbon black. At the same time, the carbon

The carbon nanotubes were mixed with silver paste and printed onto a stainless steel strip. A surface rubbing process removed the silver on the uppermost surface, allowing the CNTs to protrude from the top surface. Measurements of field emission from the carbon nanotubes were performed in a vacuum chamber equipped with electrical feedthroughs using a highvoltage power supply operated up to 1100 V, and precision multimeters interfaced with a computer. The anode probe was a platinum ball, 4 mm in diameter, mounted on a precision linear feedthrough with an accuracy of 1 m. The typical spacing from the tip of the carbon nanotubes to the anode was 100 m. The distance between the sample and the anode probe was set prior to the emission measurement and the zero spacing distance was determined by moving the anode probe until electrical contact was observed. All of the measurements were performed under vacuum with a pressure of 106 torr.
III. RESULTS A. Carbon black characteristics

First, to verify the structure of the carbon black, we examined the material using TEM. We found that the material (Fig. 3) closely resembled the proposed structure in Fig. 1. High-resolution TEM of carbon black showed that the center of the structure was comprised of highly bent graphene sheets with the outer layers consisting of multiple graphene layers wrapped around the core.
B. Nanotube formation

Figure 4 shows a schematic illustration of the electrodes after a 1-min run of carbon black in pure helium. The carbon black slug was covered by a gray-black layer, different in appearance from the original carbon black or the surrounding graphite anode. The layer covered the
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FIG. 3. TEM micrograph of raw carbon black. Inset shows grapelike structure similar to structural model in Fig. 1.

entire surface of the carbon black and was about 300 m thick. This layer could be removed from the surface, thus exposing the darker carbon black below. No layer was formed on the portion of the anode rim made of solid graphite. The surface had eroded several millimeters, but the erosion was not uniform. The center region containing the carbon black slug had eroded more than the surrounding anode rim. The rod itself was less eroded around its edge. On the cathode, a small deposit of material was formed on the cathode surface during the run. This deposit was about a millimeter in thickness and covered the entire surface of the cathode. The deposit looked similar to ones created during an arc run using two solid graphite electrodes. The outer edge of the deposit was hard, brittle, shiny, and gray in color. The interior portion of the deposit contained a soft, black material, which was typically where nanotubes mixed with other graphitic particles were found in the conventional arc setup. To determine if a similar nanotube layer could be formed using graphitizing carbon, we tried a 1-min run in pure helium using graphite powder. We found that the surface of the graphite-filled anode was eroded in a similar fashion to the carbon black case, but we did not observe any layer formed on the graphite powder surface. The exposed graphite powder surface appeared unchanged. To confirm that no layer had been formed on the graphite powder surface, we looked at the surface under an electron microscope. Electron microcopy on the graphite-filled anodes found no nanotubes on the surface of the graphite powder or on the surrounding graphite anode. SEM was also conduced on the anode filled with carbon black. Observations of the carbon black layer revealed that the layer was primarily composed of carbon
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FIG. 4. Schematic of the high-temperature arc furnace after a oneminute run of carbon black in pure helium.

nanotubes. Examination of the surface of the layer showed a very high concentration of nanotubes with a low concentration of other carbonaceous particles. Based on visual observations of the nanotube layers, we estimated the purity of the carbon nanotubes in the nanotube layer to be about 90% with the remainder of the material comprised of other graphitic particles including unreacted carbon black. In addition, the carbon nanotubes in the layer were long (about 100 m) and tangled with each other (Fig. 5), but not in bundles like MWNTs formed by the arc-plasma setup. Looking at the side of the nanotube layer showed that the nanotubes were orientated preferentially normal to the carbon black surface and becoming more tangled near the top of the layer (Fig. 6). This new nanotube layer was uniform in structure across its entire surface. In addition, no nanotubes were found on the graphite surface of the anode, only on the carbon black surface. TEM of the nanotube layer revealed the structure of the nanotubes formed. The nanotubes were MWNTs; most were composed of 20 to 40 walls with narrow,

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S.P. Doherty et al.: Solid-state synthesis of multiwalled carbon nanotubes

hollow centers. These nanotubes had smaller inner diameters and more layers than nanotubes typically grown at the cathode using a conventional arc-plasma process using two graphite electrodes. The nanotubes were near defect free, based on the continuous lattice fringes, and had closed ends. However, some of the nanotubes had small, graphitic structures on their sidewalls, or a layer of amorphous graphite on their surface (Fig. 7). While the nanotube structure was of high quality, purification was required to improve the overall quality of the nanotubes. To understand the growth mechanism in our process, we examined the evolution of the nanotube layer growth over time. A series of experiments were run for different time intervals starting from 10 s up to several minutes of

FIG. 5. SEM micrograph showing top view of nanotubes grown from carbon black after 1 min of synthesis.

total synthesis time. Figure 8 shows micrographs of each time interval at multiple magnifications. For runs less than 1 min, the nanotube layer did not cover the entire carbon black surface. However, the carbon black and graphite surfaces changed noticeably after only 10 s. Both surfaces had eroded and the surface of the carbon black had changed. Small fissures and cracks formed in the carbon black, creating small islands of material on the surface [Figs. 8(a)8(d)]. On these islands, some nanotubes had already formed [Fig. 8(d)]. After 20 and 30 s, the number of nanotubes increased and they began to cover the tops of the carbon black islands [Figs. 8(e) 8(l)]. By 40 s, the nanotubes had begun to form a layer. As the number of nanotubes increased, they formed into small patches of tangled nanotubes, and as the patches (or islands with nanotubes) grew larger, they coalesced into larger patches (or islands) [Figs. 8(m)8(p)]. By 50 s, the layer of nanotubes covered most of the carbon black surface, with only a few regions of exposed carbon black remaining [Figs. 8(q)8(t)]. We tried to determine if the nanotube layer would continue to grow once the nanotube layer covered the entire surface of the carbon black, which occurred after approximately 1 min of processing. To determine this, layers were collected for runs of 1, 2, 3, 4, and 5 min duration. These layers were weighed to determine the change in the mass of the layer. There was some variability in the weights of layers grown at identical times, but there was a systematic increase in layer mass of about 30% from 1 to 5 min. The amount of growth increase between 1 and 5 min was significantly less than the amount of growth in the first minute of the synthesis. Based on these measurements, we concluded that the growth of the nanotube layer saturated after the layer covered all of the exposed carbon black. Because the nanotubes produced with a pure helium atmosphere had carbonaceous particles on their surface, we modified the gas composition to see if we could produce cleaner nanotubes. Prior work had shown that using

FIG. 6. SEM micrograph of showing oriented growth of nanotubes from side view of layer.

FIG. 7. High-resolution TEM micrograph showing the end of the nanotube grown from carbon black after 1 min of synthesis.
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S.P. Doherty et al.: Solid-state synthesis of multiwalled carbon nanotubes

FIG. 8. Surface of carbon black slug at different magnifications and run times: (ad) after 10 s of synthesis, (eh) after 20 s of synthesis, (il) after 30 s of synthesis, (mp) after 40 s of synthesis, (qt) after 50 s of synthesis.

hydrogen, either in pure form or as a mixture with helium, can improve the purity of the nanotube produced in an arc system.31,32 One-minute runs were conducted using gas mixtures of 10, 20, 30, 40, and 50% hydrogen, with the remainder of the 100 torr atmosphere composed of helium. Additionally, a run was conducted with a pure hydrogen atmosphere. Because the gas composition altered the conductivity of the plasma, the spacing between the electrodes was altered to maintain similar power levels to the pure helium runs. In these cases, the electrode spacing was smaller than the spacing used for pure helium runs and the spacing was reduced as the concentration of hydrogen was increased. After each run, the anode surface was examined using SEM and TEM to determine the effects of the presence of hydrogen on the nanotube formation. During the run under a pure hydrogen environment, the anode electrode eroded at a faster rate than for the helium runs. Both the carbon black and ROG of the anode eroded 5 mm during the run, and a similarly sized
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deposit formed on the cathode. The carbon black did not have any nanotubes on the surface. Gas mixtures with high hydrogen concentrations formed partially complete nanotube layers. At 50% hydrogen, only a small patch of nanotubes was found on the carbon black surface, while the 40% hydrogen run had a larger region of nanotubes. For the lower concentrations of hydrogen, the nanotube layers were almost complete. They were similar in nature to pure helium runs at 40 and 50 s. Because the hydrogen plasma is more reactive with the carbon than the helium, there was less nanotube formation for the similarly timed runs. TEM analysis of these samples found that some the nanotubes had less amorphous carbon material on their sidewalls, but were still not completely free of impurities. Thus we concluded that the addition of hydrogen gas to our process was not effective at producing cleaner MWNTs. As an alternate approach to reduce the amount of excess graphitic material on the nanotubes, the nanotubes were treated in a hydrogen plasma after growth. The

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hydrogen plasma was produced by a microwave generator operated at 2.45 GHz in a quartz chamber under gas pressure of 1 torr. The power of the microwave was set to 240 W, which kept the temperature of the sample under 500 C. Nanotubes that had been grown in a pure helium arc process for 40 s were treated in a hydrogen plasma for 5 min. After treatment, the nanotubes were examined under TEM to determine the effects of the plasma. Nanotubes treated in the hydrogen plasma were found to have little to no carbonaceous deposit on their surfaces (Fig. 9). In addition, there was no damage to the nanotube walls by the hydrogen. At higher power levels, some of the tips of the nanotube were damaged by the plasma treatment.
C. Field-emission properties

FIG. 10. I-V characteristics of carbon nanotubes grown for 1 min, measured five times.

To examine the electrical properties of these nanotubes, field-emission measurements were made on a sample of nanotubes grown in pure helium for 1 min. It was found that contact between the emitter and the anode probe did not degrade the emission properties of the carbon nanotube. The emission-current density was calculated by dividing the measured emission current by the hemispherical surface area of the anode probe. We characterized each specimen for five test runs. However, since each specimen was not uniform, the measurements were taken at the best regions of the 8 8 mm specimen. Currentvoltage characteristics of the sample show typical field-emission behavior, which was expected for field emission from carbon nanotubes. For the first test run, shown in Fig. 10, the current increased slightly at 4 V/ m and dropped immediately, followed by a sharp exponential increase that occurred at the bias of 4.5 V/ m. The second to fifth test runs showed good reliability using a lower voltage of about 3 V/ m to turn on the current. Turn-on voltage, determined from the I-V data plotted in the FowlerNordheim coordinates [log (J/E2) versus 1/E], was defined as the linear limit of the plot and was demonstrated to be 2.6 V/ m. According to the FowlerNordheim equation, the field enhancement

factor ( ) can be calculated from the slope, provided that the work function of the emitter is known. Assuming a carbon nanotube work function of 5 eV, the same as for graphite, the field-enhancement factor was about 1200, similar to that of an aligned carbon nanotube.
IV. DISCUSSION

FIG. 9. High-resolution TEM micrograph showing the end of the nanotube grown from carbon black after 40 s of synthesis and a 5 min hydrogen plasma cleaning.

Most of the current theories on the formation of carbon nanotubes are not applicable to the solid-state transformation that takes place in our setup. One set of theories focus on the transformation of carbon precursors into nanotubes in the presence of a catalyst.3335 According to this theory, carbon precursors react with a nanoscale metal particle, which acts as a catalyst for a VLS reaction. The precursors are dissolved in the metal particles, then the nanotubes grow out from the surface of the particle. Since there is no catalyst material present in our system, the VLS theory is not applicable. For systems that do not have catalytic particles present, such as the arc process, most theories rely on the formation of carbon nanotubes from small carbon structures, including carbon atoms, ions, and molecules, formed by the vaporization of carbon precursors.3638 A similar model proposed by our group for the formation of nanotubes at the cathode states that the nanotube formation is based on polycyclic aromatic hydrocarbons,39,40 which are small graphene fragments and are larger than molecular carbon. In both models, the carbon structures are evaporated, travel through the plasma, and are redeposited onto the cathode and rapidly solidified as carbon nanotubes. The nanotubes are formed as each carbon structure is incorporated into a nanotube wall. Neither of these models is applicable to the transformation of carbon nanotubes from carbon black. Although carbon vapor is present in the plasma during the nanotube formation on the carbon black surface in the anode, we believe that the growth process to be a solidstate transformation. If growth was from the vapor phase, then nanotubes should have grown across the entire anode surface not just on the carbon black. Currently, no
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theory for nanotube growth is sufficient to explain the observed transformation of carbon black to MWNT. We propose the following explanation for our observations. When the plasma forms, a current is drawn between the cathode electrode and the anode cup, and the temperature of the anode rapidly increases to about 3000 C. Some of the carbon black in the anode cup evaporates while the remainder begins to sinter and shrinks into uniformly distributed islands or hills [Fig. 8(b)]. The island formation is localized near the carbon black surface due to the steep temperature gradient in the carbon black slug. As these islands are formed, the carbon black at the center of the islands is exposed to a higher electric field because it is closer to the cathode. The carbon black in these regions begins to deform and transform into MWNTs by solidstate diffusion14 with the assistance of the strong electric field in the plasma sheath between the top of the islands and the plasma. The electric-field intensity on top of the islands will also grow as the MWNTs form sharp tips. This electric field assisted instability causes the rapid growth of MWNTs on top of the islands. The MWNTs grow preferentially oriented normal to the carbon black surface due to the electric field created in the plasma sheath region of the interface. As the top of the islands are covered with nanotubes, the surface conductivity on top will be higher than at the island boundaries. As the diameters of the islands increase, the surface charges also spreads. The process causes the increase of the electric field at the boundaries, where there is still exposed carbon black, causing nanotube growth at the island boundaries. As the growth of MWNTs continues, the MWNT island layers will merge together, forming a continuous layer across the top of the carbon black surface. Once a continuous layer was complete, after 1 min, we found that the amount of nanotubes formed quickly saturates by the end of three minutes. This saturation indicates that temperature is not the sole driving force for carbon black conversion. In experiments where carbon black was heated to high temperatures but not exposed to the electric field at the sheath of the plasma, we observed little nanotube growth, similar to the findings of our earlier work.14 To understand the nucleation and growth of these nanotubes, we examined nanotubes formed in runs under 10 s using SEM to determine the location where nanotube nucleation occurred. Nanotubes are frequently observed to terminate at carbon black particles. Figure 11 shows the root of a nanotube joined to a carbon black particle. The carbon black particle is acting as a seed for the formation of the nanotube. In situ nanoscopic measurements are needed to give complete explanation of how the carbon black transforms into MWNTs. However, recent work by Wang et al. using in situ TEM measurements have shown that carbon nanotube tips are deformed under high electric fields.41 We believe that such a deformation process is occurring in the carbon
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FIG. 11. SEM micrograph showing a nanotube attached to a carbon black particle by its root.

black in the anode. In conditions similar to our experiment, it has been estimated that the electric field in the growth region can be as high as 108 V/cm.42 Since the carbon black particles are composed of tangled graphene sheets that contain pentagon and heptagon defects, when they are exposed to the high temperature and electric field of the plasma, they begin to deform their shape. The high electric field causes deformation and elongation of the carbon black particles, while the high temperature allows for diffusion of the defects within the graphene sheets. As the particles sharpen, the electric field at the tip intensifies allowing for additional elongation, transforming them into nanotubes. As the nanotubes form, the high temperature allows the nanotubes to form with few defects, unlike CVD nanotubes grown at temperatures below 1000 C.
V. CONCLUSIONS

In conclusion, we demonstrated a novel process by which carbon nanotubes can be produced using a solidstate transformation. We have shown that these nanotubes have few defects and are very long. In addition, these nanotubes can be cleaned by exposing the nanotubes to a microwave-generated hydrogen plasma. These nanotubes appear structurally similar to typical arcgrown nanotubes and their field-emission properties are in the same range as those arc-grown nanotubes used for field-emission displays. Further study of this system is necessary to better understand the growth and nucleation mechanisms. This process has the potential for expansion to large-scale production.
ACKNOWLEDGMENTS

This project was supported by the National Science Foundation (NSF), Grant No. DMR-0071737. The use of the facilities of the Materials Research Science and

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S.P. Doherty et al.: Solid-state synthesis of multiwalled carbon nanotubes

Engineering Center (MRSEC) at Northwestern University supported by the NSF Grant No. DMR-9632472 is acknowledged.
REFERENCES
1. S. Iijima, Nature 354, 56 (1991). 2. M.M.J. Treacy, T.W. Ebbesen, and J.M. Gibson, Nature 381, 678 (1996). 3. S.J. Tans, M.H. Devoret, H.J. Dai, A. Thess, R.E. Smalley, L.J. Geerligs, and C. Dekker, Nature 386, 474 (1997). 4. Q.H. Wang, A.A. Setlur, J.M. Lauerhaas, J.Y. Dai, E.W. Seelig, and R.P.H. Chang, Appl. Phys. Lett. 72, 2912 (1998). 5. H.J. Dai, J.H. Hafner, A.G. Rinzler, D.T. Colbert, and R.E. Smalley, Nature 384, 147 (1996). 6. A.C. Dillon, K.M. Jones, T.A. Bekkedahl, C.H. Kiang, D.S. Bethune, and M.J. Heben, Nature 386, 377 (1997). 7. Z. Yao, H.W.C. Postma, L. Balents, and C. Dekker, Nature 402, 273 (1999). 8. R. Martel, T. Schmidt, H.R. Shea, T. Hertel, and P. Avouris, Appl. Phys. Lett. 73, 2447 (1998). 9. M.F. Yu, O. Lourie, M.J. Dyer, K. Moloni, T.F. Kelly, and R.S. Ruoff, Science 287, 637 (2000). 10. T.W. Ebbesen and P.M. Ajayan, Nature 358, 220 (1992). 11. T. Guo, P. Nikolaev, A. Thess, D.T. Colbert, and R.E. Smalley, Chem. Phys. Lett. 243, 49 (1995). 12. J. Kong, A.M. Cassell, and H.J. Dai, Chem. Phys. Lett. 292, 567 (1998). 13. L. Thien-Nga, J.M. Bonard, R. Gaal, L. Forro, and K. Hernadi, Appl. Phys. Lett. 80, 850 (2002). 14. A.A. Setlur, S.P. Doherty, J.Y. Dai, and R.P.H. Chang, Appl. Phys. Lett. 76, 3008 (2000). 15. J.M. Calderon-Moreno and M. Yoshimura, Mater. Trans. 42, 1681 (2001). 16. J.M.C. Moreno, S.S. Swamy, T. Fujino, and M. Yoshimura, Chem. Phys. Lett. 329, 317 (2000). 17. R. Sen, S. Suzuki, H. Kataura, and Y. Achiba, Chem. Phys. Lett. 349, 383 (2001). 18. D.B. Geohegan, H. Schittenhelm, X. Fan, S.J. Pennycook, A.A. Puretzky, M.A. Guillorn, D.A. Blom, and D.C. Joy, Appl. Phys. Lett. 78, 3307 (2001). 19. T.S. Wong, C.T. Wang, K.H. Chen, L.C. Chen, and K.J. Ma, Diamond Relat. Mater. 10, 1810 (2001). 20. L.P. Biro, R. Ehlich, R. Tellgmann, A. Gromov, N. Krawez, M. Tschaplyguine, M.M. Pohl, E. Zsoldos, Z. Vertesy, Z.E. Horvath, and E.E.B. Campbell, Chem. Phys. Lett. 306, 155 (1999).

21. N. Grobert, M. Terrones, A.J. Osborne, H. Terrones, W.K. Hsu, S. Trasobares, Y.Q. Zhu, J.P. Hare, H.W. Kroto, and D.R.M. Walton, Appl. Phys. A, Mater. Sci. Proc. 67, 595 (1998). 22. Y. Chen, L.T. Chadderton, J.S. Williams, and J.F. Gerald, in Metastable, Mechanically Alloyed and Nanocrystalline Materials, Parts 1 and 2 (Trans Tech Publications Inc., Vetikon-Zurich, Switzerland, 2000), Vol. 343-3, p. 63. 23. L.T. Chadderton and Y. Chen, Phys. Lett. A 263, 401 (1999). 24. B. Adhikari, A.K. Ghosh, and S. Maiti, J. Polym. Mater. 17, 101 (2000). 25. L. Karasek and M. Sumita, J. Mater. Sci. 31, 281 (1996). 26. J.B. Donnet, Carbon 20, 266 (1982). 27. Q.L. Zhang, S.C. Obrien, J.R. Heath, Y. Liu, R.F. Curl, H.W. Kroto, and R.E. Smalley, J. Phys. Chem. 90, 525 (1986). 28. V.I. Berezkin, Phys. Solid State 42, 580 (2000). 29. V.I. Berezkin, Phys. Status Solidi B, Basic Res. 226, 271 (2001). 30. H.W. Kroto, J.R. Heath, S.C. Obrien, R.F. Curl, and R.E. Smalley, Nature 318, 162 (1985). 31. X.K. Wang, X.W. Lin, M. Mesleh, M.F. Jarrold, V.P. Dravid, J.B. Ketterson, and R.P.H. Chang, J. Mater. Res. 10, 1977 (1995). 32. J.M. Lauerhaas, J.Y. Dai, A.A. Setlur, and R.P.H. Chang, J. Mater. Res. 12, 1536 (1997). 33. S. Iijima and T. Ichihashi, Nature 363, 603 (1993). 34. D.S. Bethune, C.H. Kiang, M.S. Devries, G. Gorman, R. Savoy, J. Vazquez, and R. Beyers, Nature 363, 605 (1993). 35. C. Journet, W.K. Maser, P. Bernier, A. Loiseau, M.L. dela Chapelle, S. Lefrant, P. Deniard, R. Lee, and J.E. Fischer, Nature 388, 756 (1997). 36. E.G. Gamaly and T.W. Ebbesen, Phys. Rev. B, Condens. Matter 52, 2083 (1995). 37. T. Guo, P. Nikolaev, A.G. Rinzler, D. Tomanek, D.T. Colbert, and R.E. Smalley, J. Phys. Chem. 99, 10694 (1995). 38. J.C. Charlier, A. DeVita, X. Blase, and R. Car, Science 275, 646 (1997). 39. J.Y. Dai, J.M. Lauerhaas, A.A. Setlur, and R.P.H. Chang, Chem. Phys. Lett. 258, 547 (1996). 40. A.A. Setlur, J.M. Lauerhaas, J.Y. Dai, and R.P.H. Chang, Appl. Phys. Lett. 69, 345 (1996). 41. Z.L. Wang, R.P. Gao, W.A. de Heer, and P. Poncharal, Appl. Phys. Lett. 80, 856 (2002). 42. R.E. Smalley, Mater. Sci. Eng. B, Solid State Mater. Adv. Technol. 19, 1 (1993).

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