Carbon 43 (2005) 2571–2578 www.elsevier.

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Continuous deposition of carbon nanotubes on a moving substrate by open-air laser-induced chemical vapor deposition
Kinghong Kwok, Wilson K.S. Chiu
Received 21 January 2005; accepted 11 May 2005 Available online 5 July 2005

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Department of Mechanical Engineering, University of Connecticut, 191 Auditorium Road, Storrs, CT 06269-3139, USA

Abstract Continuous deposition of carbon nanotubes under open-air conditions on a moving fused quartz substrate is achieved by pyrolytic laser-induced chemical vapor deposition. A CO2 laser is used to heat a traversing fused quartz rod covered with bimetallic nanoparticles. Pyrolysis of hydrocarbon precursor gas occurs and subsequently gives rise to rapid growth of a multi-wall carbon nanotube forest on the substrate surface. A ‘‘mushroom-like’’ nanotube pillar is observed, where a random orientation of carbon nanotubes is located at the top of the pillars while the growth is more aligned near the base. The typical carbon nanotube deposition rate achieved in this study is approximately 50 lm/s. At high power laser irradiation, various carbon microstructures are formed as a result of excessive formation of amorphous carbon on the substrate. High-resolution transmission and scanning electron microscopy, and X-ray energy-dispersive spectrometry are used to investigate the deposition rate, microstructure, and chemical composition of the deposited carbon nanotubes. Ó 2005 Elsevier Ltd. All rights reserved.
Keywords: Carbon nanotubes; Chemical vapor deposition; Electron microscopy; X-ray energy-dispersive spectrometry; Reaction kinetics

1. Introduction A vast amount of research effort has been devoted to the development of synthesis techniques that would have the capability of growing high quality, by-product free carbon nanotubes. Arc-discharge, laser ablation, and high-pressure carbon monoxide (HiPco) techniques have been widely used for the growth of single- and multi-wall carbon nanotubes [1–4]. However, low production rate and high deposition temperature or pressure (typically between 3000 and 4000 °C) required by these techniques resulted in a scale-up production of carbon nanotubes that is prohibitively expensive. Thermal CVD and various forms of plasma CVD techniques [5–7] have been successful in growing a relatively
Corresponding author. Tel.: +1 860 486 3647; fax: +1 860 486 5088. E-mail address: wchiu@engr.uconn.edu (W.K.S. Chiu). 0008-6223/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2005.05.016
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large quantity (kilogram and even ton level) of carbon nanotubes. However, relatively low deposition temperature in CVD (550–1200 °C) results in carbon nanotubes with high defect densities and a low degree of graphitization [4], thereby restricting their usage for advanced applications. Recently, Kwok and Chiu [8] have successfully demonstrated the feasibility of using pyrolytic LCVD to deposit carbon nanotubes on stationary fused quartz substrates in open-air. It was found that different regions of carbon growth occur as a result of non-uniform temperature distribution and the reactant gas jetÕs crossflow configuration. However, this technique is not suitable for mass production of nanotubes because a significant amount of pyrolytic carbon by-products are deposited as a result of elevated substrate temperature induced by direct laser irradiation. Furthermore, our previous investigation focused primarily on the fundamental aspect of open-air LCVD synthesis, so that the

1. which is connect to a high-torque electric motor that can move the substrate at a constant velocity across the laser targeted spot. Then the electrical motor is initialized and begins driving the linear stage along with the substrate through the reactor at a constant velocity. The main scientific justification for the study of carbon nanotube growth on a moving substrate is the potential in discovering new fundamental physics regarding the growth mechanism of carbon nanotubes. which is favorable for mass production of carbon nanotubes. Extensive search in the open literature reveals no documented experimental study on the growth of carbon nanotubes on a moving substrate using an open-air CVD technique. Chiu / Carbon 43 (2005) 2571–2578 effect of experimental parameters on carbon nanotube growth kinetics. The catalytic substrate is attached to a supporting arm as shown in Fig.S. A scanning laser-induced CVD technique is proposed and investigated in order to reduce the amount of undesirable by-products and increase the yield of carbon nanotubes. microstructure. the influence of laser power intensity and substrate movement on nanotube growth is studied. In addition. In this study.2572 K. W. . Kwok. A plano/convex zinc selenide (ZnSe) lense is used in order to focus the laser beam to a desired diameter on the substrate without altering the beam profile. During an experimental run. 1. Furthermore. the laser power is varied systematically in order to study its effect on the growth kinetics and Fig. the coaxial nozzle and the exhaust hood are turned on and set to the appropriate laser power and flow rates. This finding is expected because the existing CVD techniques involve (i) large-area deposition that requires no moving components and (ii) enclosed deposition chamber restricts the movement of the heat source and the substrate. A 30-W CO2 laser with a wavelength of 10. Fused quartz (SiO2) rods of 3-mm diameter are used as the substrate.K. the laser heated spot moves with respect to the substrate at a prescribed velocity and direction. Experimental apparatus The laser-induced CVD system used for the continuous growth of carbon nanotubes on a moving substrate is shown in Fig. the substrate is first mounted onto the traverse mechanism. The CO2 laser. The overall experimental setup is similar to that used for laser deposition on a stationary substrate [8]. An integrated computer data acquisition and control system is used to control the laser power output. Deposition occurs when the substrate intercepts the laser beam and the reactant gas jet. The objective of this work is to study the feasibility of using open-air pyrolytic LCVD to deposit carbon nanotubes on a moving substrate with direct application to scale-up continuous production of nanotubes. 2. The mechanism is designed to slide on linear ball bearings to minimize the effect of both static and dynamical friction. 1.6 lm and a Gaussian beam profile is used to heat the substrate. and only a brief description is given here. a moving laser beam will irradiate a larger substrate surface area in a continuous manner. and chemical composition has not been examined. The formation rate of pyrolytic carbon film decreases as a result of reduced temperature. The substrate supporting apparatus sits on a linear traverse mechanism. Open-air laser-induced chemical vapor deposition (LCVD) system with a substrate moving mechanism. thereby reducing the amount of temperature rise on the substrate surface and the laser residence time [9]. In this technique. which is positioned away from the laser heating spot. which will enhance the carbon nanotube growth by allowing the catalyst particles to remain active for a longer period of time. and the procedure for preparing catalyst particles on the substrate was outlined in [8].

respectively. As the laser beam enters the section covered with catalyst. and chemical composition of the carbon materials deposited in this study. reaction kinetics. W. The scanning laser beam can be described as a moving heat source that induces a large temperature gradient on the glass surface. (b) Laser-induced growth of bulk carbon nanotube material on the moving substrate with the same velocity as in (a). 3a and b shows two ESEM images of the bulk carbon material shown in Fig. which provides an estimation of its height. . 2b.25 MW/m2) and the substrate velocity is 0.14 mm/s and 350 nm. Continuous synthesis of carbon nanotube forest by open-air LCVD In the pyrolytic LCVD technique. growth of bulk carbon nanotube material could be immediately observed by a magnifying camera as shown in Fig. and an environmental scanning electron microscope (Philips 2020 ESEM) are used to examine the microstructure. The flow rates of propane. the effect of moving the substrate in one dimension perpendicular to the focused CO2 laser beam is the same as scanning the laser beam along the substrate. (a) Laser heating of an uncoated section on the fused quartz substrate moving at 0. 2c.14 mm/s. 2c. The height of the carbon nanotube pillars Fig. Investigation of the deposited material by an optical microscope reveals no detailed microstructural information except for the fact that they appear to be grayish and chunky. The ‘‘mushroom-like’’ geometry could be due to random orientation of the carbon nanotubes locate at the top of the pillars while the growth is more aligned near the base. The accumulation of carbon nanotubes occur very rapidly at the trailing edge of the laser heating zone and also within the laser heating spot. The hydrocarbon precursor gas used is propane (C3H8) with 99. Fig. the laser power used for heating is 13. Results and discussion 3. respectively. Chiu / Carbon 43 (2005) 2571–2578 2573 microstructure of the deposited carbon nanotubes while the substrate moving velocity and the catalyst particle size are fixed at 0. Rapid temperature raise becomes obvious by observing the bright spot on the substrate surface. hydrogen and nitrogen are 0.1. 1.K. A transmission electron microscope (JEOL 2010 FasTEM) equipped with an X-ray energy-dispersion spectrometry (EDS) system.95% purity and is mixed with ultra-high purity grade hydrogen gas.2.K. ESEM investigation reveals pillars of ‘‘mushroom-like’’ carbon trees that form a carbon nanotube forest. 2a shows laser heating at the beginning section of the fused quartz substrate where no catalyst is presented. which subsequently leads to thermal decomposition of gas-phase precursors and results in the deposition of a continuous stripe of desired material. The side view of the bulk nanotube material. This observation suggests that both sufficient temperature and residence time is required for the nucleation and subsequent growth of carbon nanotubes since no observable nanotube growth occurs near the front of the moving laser beam. Higher magnification ESEM studies reveal individual pillars consisting of carbon nanotubes in tangled form with the primary growth direction perpendicular to the substrate surface.5 W (5.0 and 10 SLPM.S. Fig. The direct observation of the nanotube growing process within the laser-heating zone has demonstrated the rapidness of this laser driven technique. In this case. 3. 2. Kwok. is shown in Fig. and (c) a side view of the resulting bulk nanotube material.14 mm/s.

The absence of catalyst particles observed by TEM and EDS suggests that base-growth is the primary nanotube growth mode in this study. 3. Chiu / Carbon 43 (2005) 2571–2578 Fig. A small amount amorphous carbon is observed among the nanotube bundle. which indicates that amorphous carbon is also deposited during the nanotube growing process. (c) TEM image of carbon nanotubes in tangled form with diameter ranging from 5 to 20 nm. catalyst particles remain attached to the substrate surface as the carbon nanotubes lengthen.5 mm. 4 shows the EDS spectrum taken directly from the carbon nanotube bundle shown in Fig. A stripe of carbon nanotube forest that is approximately 3 cm long and 0.3 cm wide is dispersed in an ethanol solution by an ultrasonic process. the hollow core and the graphitic walls can also be directly seen in the image. (a) ESEM image of the pillars of ‘‘mushroom-like’’ carbon trees deposited by scanning LCVD.2574 K.5 to 2. the diameter of the nanotube and its core are approximately 3 and 10 nm. In this case. X-ray energy dispersive spectrometry was performed on a LCVD-grown carbon nanotube sample in order to determine its chemical composition. which implies the absence of nanotube contamination by catalyst particle intrusion. deposited in this study ranges from 0. 3c shows a TEM image of carbon nanotubes in tangled form with diameter ranging from 5 to 20 nm with the majority of the nanotubes having a diameter of 15 nm. However. In base-growth mode. Fig. It clearly reveals the tubular graphite lattice structure of carbon nanotubes observed by Iijima [10]. the shaded area represents the characteristic X-ray signal generated from the nanotube sample. but the length of individual nanotubes within the pillars is very difficult to measure because of the tangling of nanotubes and resolution limit of the ESEM. High-resolution TEM (HRTEM) study was performed in order to examine the detailed microstructural features of LCVD-grown carbon nanotubes. 3c. and oxides forming on the nanotube surface after laser deposition process gives rise to the oxygen peak observed in the EDS spectrum. Kwok. The distance between graphitic walls is 0. Carbon nanotube bundles within the sample gives rise to the carbon peak. which matches the separation distance in bulk graphite.S. The length measurement terminates at a point where further tracing becomes impossible.K. Small fragments of the carbon nanotube bundle are transferred onto a TEM grid. it is found that their lengths exceed 50 lm. 3d shows a HRTEM image of a pair of carbon nanotubes overlapping each other. (d) HRTEM image of a pair of carbon nanotubes overlapping each other. Fig. (b) ESEM image of carbon nanotube bundles. W. by following several relatively straight carbon nanotubes among the bundles. In addition. respectively. Fig. while the area under the line represents those from the TEM grid which is composed of amorphous carbon and copper.34 nm. In the spectrum. as opposed to tipgrowth mode where catalyst particles are lifted off from . No palladium or gold signal is detected.

Carbon nanotube bundles are not found in this region as a result of excessive amorphous carbon deposition. which is relatively high compared to rates reported by thermal and plasmaenhanced chemical vapor deposition [11–14]. 4. 5a and b. which is equal to the diameter of the laser beam.8 mm as the laser beam diameter and 0. Fig. The average height of the pillars deposited with a laser power of 13. . Fig.15]. Since less hydrocarbon molecules would undergo thermal decomposition at a lower substrate temperature. Since this study used 1. The ESEM and the TEM results have clearly demonstrated the feasibility of using scanning pyrolytic laserinduced chemical vapor deposition to grow a continuous stripe of carbon nanotube forest on a moving glass surface. 5c. The nanotube growth time is defined as the duration of a given substrate section residing within the laser beam.65 mm. and therefore the surface temperature is lower compared to Region A. In this case. thereby terminating carbon nanotube growth. Region B forms at the perimeter of Region A. which covered up potential nanotube precipitation sites on the catalyst surface. ESEM investigation of Region D shown in Fig.K. which may cause further reduction in growth rate of carbon nanotubes observed in the region.5 s. Carbon nanotubes with diameter ranging from 30 to 50 nm and length ranging from 5 to 50 lm are observed in Region B. and look similar under SEM. In addition. 5e. 5e and f. EDS spectrum taken directly from the LCVD-grown multiwall carbon nanotubes.K. while the area under the line represents those from the TEM grid. Chiu / Carbon 43 (2005) 2571–2578 2575 Fig. Beside carbon fibers. W. Effect of laser power on carbon nanotube forest morphology A second set of experiments were performed in order to study the effect of intense laser irradiation on the microstructure and the growth kinetics of carbon nanotubes by pyrolytic LCVD. 5a shows a schematic of a continuous stripe of nanotube forest with two distinctive regions of growth. 5f reveals columns of fiber-like carbon structures sprouting perpendicular to the substrate surface with an average diameter of 10 lm and height ranging from 30 to 100 lm. and consists of loosely packed multi-wall carbon nanotubes growing in random orientation as shown in Fig.S. carbon nanotube bundles are occasionally observed branching out from near the tip of the carbon fibers as shown in Fig.14 mm/s as the substrate velocity.5 W (8. and the remaining area within the path of the laser beam is labeled as Region D. The appearance of this bulk carbon material resembles the nanotube forest observed in the previous sample except that they are discontinuous islands rather than a continuous stripe. it is expected that less carbon nanotubes will form in Region B. divide by the substrate moving velocity. the growth time is calculated to be 12. the rapid formation of nanotube pillars in Region A interferes with the transport of reactants to Region B. Kwok. In addition. the substrate and carried along by the nanotube as it grows in length so that nanoparticle traces will be found within the bundle. A third set of experiments are performed with the laser power increased to 21. deposition of individual bulk carbon chunks was observed by visual inspection of the resulting sample as shown in Fig. The same experimental parameters are used in this case but with the laser power increased to 15. a significant amount of amorphous carbon is deposited on the surface. ESEM investigation also reveals two distinctive regions of carbon growth. The ‘‘mushroom-like’’ carbon nanotube pillars are found in Region A as shown Fig. the bulk carbon islands are labeled as Region C. 5e shows that Region C consists of densely packed carbon fibers grown in random orientation with length reaching several hundred microns. The resulting deposition rate is determined to be 50 lm/s. 3. 5d. carbon nanotubes have a much smaller diameter than the fiber and have well-graphitized walls [4. No amorphous carbon layer is observed to deposit on the substrate surface when a lower laser power of 13. and the morphology of the carbon deposit within each region is shown in Fig. However. The shaded area in the EDS spectrum represents the characteristic X-ray signal derived from the nanotube sample.35 MW/m2). The formation of a carbon layer on the substrate surface covers the catalyst particles. This region is located at the edge of the Gaussian laser beam.75 MW/m2). However. In this case.2.5 W was used. The deposition rate of multi-wall carbon nanotubes achieved in this study is determined based on the height of the pillars since each pillar consists of densely packed carbon nanotubes.5 W (5. a layer of amorphous carbon film forms beneath the pillars as a result of increased laser power.5 W is measured by ESEM to be 0. It is important to point out that carbon fibers and multi-wall carbon nanotubes have a similar structure.

(c) Loosely packed multi-wall carbon nanotubes grew in random orientation found in Region B. (e) Densely packed carbon fibers grown in random orientation and (f) columns of fiber-like carbon structures sprouting perpendicular to the substrate surface with a significant amount of amorphous carbon. (d) Bulk carbon chunks deposited at high laser power irradiation with two distinctive regions of growth.S. 6 shows a series of HRTEM images of carbon nanotubes and carbon fibers found in Region C. Detailed examination under TEM reveals that a multi-wall carbon nanotube is embedded into each carbon fiber core as indicated in Fig. Kwok. Initially. 5e. 5. have similar diameter and microstructure compared to those deposited in the previous set of experiments where a lower laser power is used. W. (a) A schematic of a continuous stripe of nanotube forest showing two distinct regions of growth. Chiu / Carbon 43 (2005) 2571–2578 Fig. shown in Fig. Fig. This observation clearly indicates that the formation of carbon fibers begin with the growth of carbon nanotubes since it is unlikely for car- bon nanotubes to grow inside the solid carbon fiber.K.2576 K. 6b. . carbon atoms precipitate from the carbon-saturated metal particle surface and form a carbon nanotube. (b) ‘‘Mushroom-like’’ carbon nanotube pillars were found in Region A. The thickness of the amorphous carbon layer increases as the nanotube lengthens and eventually becomes the carbon fiber observed in Fig. The multi-wall carbon nanotubes observed in Region C. The formation of carbon fiber could be explained by the following proposed mechanism. rapid pyrolysis of hydrocarbon molecules due to the intense laser irradiation results in excessive amorphous carbon deposited onto the carbon nanotube. However. 6a.

W.K. 6c and d) obtained from the fibers confirm the formation of a polycrystalline carbon layer [15.) HRTEM investigation of carbon fibers with diameter ranging from 75 to 250 nm reveals a polycrystalline structure as shown in Fig. The selected area electron diffraction patterns (inserted in Fig. (Inserts are selected area electron diffraction patterns.K. which is not observed in the previous case where a lower laser power was used. Similar nanotube branching phenomenon have been reported in microwave plasma-enhanced CVD of multi-wall carbon nanotubes by Tsai et al. (a) HRTEM image of carbon nanotubes found in Region C. which allows the subsequent growth of carbon nanotubes to lift the unbounded metal particles from the surface and carry them along on the nanotube as it lengthens. (c. 6. Chiu / Carbon 43 (2005) 2571–2578 2577 Fig. Conclusions In this study. 6b–d shows that metal particles are scattered along the carbon fiber. the feasibility of using open-air laser-induced chemical vapor deposition to grow carbon nanotubes on a moving substrate is successfully . 4. (b) Multi-wall carbon nanotube coated with a thick layer of amorphous carbon with metal particles scattered along the nanotube. The lifted metal particle acts as the catalyst for the growth of carbon nanotube bundles that branch out from the tip of the carbon fibers as shown in Fig.S. 6c and d. 6c. [18]. Kwok. The adhesion force between metal particles and the substrate surface reduces dramatically [17] when the metal particles start to melt. but occasionally a carbon nanotube core can be seen on the fiber as shown in Fig. d) are TEM images of large diameter carbon fibers revealing polycrystalline structure. Fig. Notice that it is difficult to see the carbon nanotube within the large diameter carbon fiber because the thick layer of carbon prevents the penetration of the electron beam used in TEM imaging.16] on the fiber surface. This three-layer carbon fiber structure is very interesting because it combines three distinctive forms of solid carbon with sp2 bonding state into a single structure. 5e. This result indicates that high power laser irradiation can induce a sufficiently high surface temperature to melt the catalyst particles during the initial nanotube growth stage. The build-up of a polycrystalline carbon layer forms yet another layer on the fiber. Notice that only a portion of the original metal particle seed is being lifted since the size of metal particles found along the nanotube is approximately 1/7 of the original particle.

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