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On-substrate growth of single-walled carbon nanotube networks by an all-laser processing route

B. Assa a, D. Therriault b, M.A. El Khakani
a

a,*

Institut National de la Recherche Scientique, INRS-Energie, Materiaux et Telecommunications, 1650 Boulevard Lionel Boulet, C.P. 1020, Varennes, Quebec, Canada J3X 1S2 b Mechanical Engineering Department, Ecole Polytechnique de Montreal, P.O. Box 6079, Montreal, Canada H3C 3A7

A R T I C L E I N F O

A B S T R A C T

Article history: Received 20 November 2010 Accepted 3 March 2011 Available online 6 March 2011

We report on the process latitude of an all-laser approach for the controlled growth of single-walled-carbon-nanotube (SWCNT) mats at predened locations on silicon substrates. Unlike the conventional laser ablation methods where the SWCNTs are produced in the soot form, from the concomitant ablation of a graphite target loaded with metal catalyst, the all-laser process proceeds in two consecutive and independent steps. Indeed, the same KrF pulsed laser is rst used to deposit at room temperature, the Co/Ni catalyst nanoparticles (NPs) onto the substrates of which size and surface density can be controlled by adjusting the number of laser ablation pulses and subsequently to grow SWCNTs onto the Co/Ni NPs sites, from the laser ablation of a pure graphite target. The grown SWCNT networks are shown to be fairly controllable by choosing the appropriate ratio of graphite to Co/Ni-NPs laser ablation pulses. The Co/Ni NPs and the grown SWCNTs were systematically characterized by atomic force microscopy, scanning/tunnelling electron microscopy, Raman spectroscopy and thermogravimetry analysis, and their potential as an active material in thin lm transistor was evaluated. Obtained characterization data have led to identify key growth parameters of this novel approach, and to propose growth mechanism models that best describe our observations. 2011 Elsevier Ltd. All rights reserved.

1.

Introduction

Carbon nanotubes (CNTs) continue to attract considerable interest for both fundamental and applications viewpoints because of their unpaired electrical, optical, thermal and mechanical intrinsic properties [1]. The incorporation of such one-dimensional systems into a variety of devices has proven their potential to impact many elds [2]. Central to the development of the CNT related applications is the ability to grow of high quality materials. Several synthesis methods using either evaporation of solid targets or hydrocarbon gas dissociation have been used to grow CNT materials. The most common methods are arc discharge [3], chemical vapor deposition

(CVD) [4] and laser ablation methods [5]. Other techniques, such as plasma-enhanced CVD [6], laser induced CVD [7] and detonation chemistry [8] have also been investigated and published. Laser ablation is considered as one of the best methods to grow single walled carbon nanotube (SWCNT) material of high quality and purity [9]. In the conventional scheme, the laser ablation based methods produce CNTs from the ablation of graphite targets loaded with transition metal catalysts, in a controlled atmosphere at high temperatures (typically P1100 C). CNTs are thus produced in carbonaceous soot, where impurities such as amorphous carbon (a-C), graphitic carbon, and residual transition metal catalysts are also present as by-products. Although these

* Corresponding author: Fax: +1 450 929 8102. E-mail address: elkhakani@emt.inrs.ca (M.A. El Khakani). 0008-6223/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2011.03.006

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catalysts promote the growth of nanotubes, they also require complex purifying treatments, which often damage and dope the nal product. The properties of catalyst nanoparticles (NPs) are known to inuence those of produced SWCNTs. Therefore, controlling the size and location of the catalytic NPs is necessary to produce homogeneous SWCNTs with specic physical properties [10]. Various synthesis techniques have been applied to produce catalyst NPs. The most widely used ones are wet chemical routes such as the precipitation of metal salts on nanoporous supports followed by drying and/or calcination [1012]. Even though these methods produce discrete metal or metal oxide NPs, the catalyst nanoparticles need to be supported by high surface-area materials such as SiO2 and Al2O3 to catalyze SWCNTs by CVD [1316]. Other physical vapor deposition (PVD) techniques, such as sputtering and evaporation methods have been also used for the catalyst NPs production [1718]. The pulsed laser deposition (PLD) technique has been also recently shown to be a powerful and highly versatile plasma-deposition technique that enables the direct deposition of well dispersed metal NPs at room temperature [19]. Moreover, PLD is a highly exible technique that allows a fair control of the NPs size by appropriately monitoring deposition parameters, such as background pressure, laser energy density, and laser ablation time [19,20]. On the other hand, the ability to achieve the controlled growth of CNT mats directly on a substrate is highly desirable for nanoelectronic, sensing or eld emission device applications. When combined with standard microfabrication processing, the localized growth of CNTs by the all-laser process has been shown to be very effective in the direct integration of SWCNTs into eld effect transistors with very high switching ratios [21]. In this work, we present a detailed investigation of the onsubstrate growth of SWCNT networks by the all-laser process, in order to better understand the interplay limits of the Co/Ni NPs and ablated carbon feedstock for the most effective conversion of graphite into SWCNTs and the possible growth mechanism involved. The effect of growth parameters (such as Co/Ni NPs/ablated graphite amounts ratio, furnace temperature, and post-annealing purication) have been investigated, and the most signicant results are reported. The developed all-laser approach can be viewed as a CVD-like process, which separately uses metal catalyst NPs and decomposed carbon feedstock for the CNT growth, with the specicity that all ingredients (i.e., catalyst NPs and dissociated carbon species) are laser-processed. Indeed, the all-laser synthesis of SWCNTs directly on silicon substrates was carried out by using the same UV KrF excimer laser, to rst deposit the Co/Ni NPs, and to subsequently grow SWCNTs from the laser ablation of a pure graphite target. Finally, focus is also put on the successful use of the all-laser growth process for the direct integration of SWCNT networks as an active channel into eld effect transistor (FET) -like devices, where the random networks of SWCNT exhibit a p-type FET behavior.

rate = 10 Hz, incident angle of 45) onto SiO2/Si substrates, located 50 mm away from the target. The PLD deposition of Co/ Ni NPs was achieved by ablating a polycrystalline Co/Ni target (99.95%) with an on-target laser intensity of $4 108 W/cm2 under a He pressure of $300 mTorr at room temperature. Prior to lling the chamber with He, it was rst turbo-pumped down to 106 Torr. The target was animated by a dual rotational and translational motion to ensure a uniform erosion of its surface. The size of Co/Ni NPs and their surface density (number of NPs per unit area) were varied by increasing the number of laser ablation pulses. These NPs were used as seeds (or nucleation sites) for the direct growth of SWCNTs, which was accomplished by placing the Co/Ni-decorated substrates in the center of another reactor (which can be heated by a surrounding electric furnace up to 1150 C), and exposing them to the carbon vapor produced by the KrF-laser ablation of a pure graphite target, under an argon atmosphere (at a constant pressure of $5 Torr). The laser beam is swept over the graphite target surface at right angle (90), with an on-target laser intensity of $3 108 W/cm2. The SWCNT growth was investigated at various furnace temperatures ranging from 700 to 1100 C. The as-deposited Co/Ni NPs were systematically characterized by atomic force microscopy (AFM) (NanoScope III, Digital Instrument) operated at room temperature in ambient air. The grown SWCNT were characterized by scanning electron microscopy (SEM) using a Jeol JSM-6300F microscope, and by the bright-eld transmission electron microscopy (TEM) using a JEOL JEM-2100 F FEG-TEM (200 kV) microscope.The Raman measurements on SWCNT deposits were performed with the 514.5 nm (2.41 eV) laser radiation of an Ar+ laser focused onto the sample with a spot of 1 lm (microRaman spectroscopy, Renishaw Imaging Microscope WireTM). The Raman spectra were taken with a backscattering geometry at room temperature in the 1002000 cm1 region. Thermogravimetric (TGA) analyses were performed using the Q-500 TGA system (TA instruments). In order to purify the SWCNT mats by means of thermal oxidation, samples of the as-grown SWCNTs were scratched-out from their original silicon substrates and were subjected to heating treatments in air with temperatures of up to 900 C (with a linear heating ramp of 10 C/min). Finally, transport measurements were performed to elucidate the electrical properties of the grown SWCNT mats. The synthesized nanotube -networks were directly integrated as an active channel, into the FET like-devices, by using Ti/Pt electrodes as source and drain (deposited by PLD), and heavily doped Si substrate (resistivity $0.01 ohms cm) as a back gate (as illustrated in Fig. 9(a)). These devices were characterized at room temperature in air using a HewlettPackard 4140B semiconductor parameter analyzer.

3.

Results and discussion

2.

Experimental

Catalyst Co/Ni NPs were rst deposited by PLD using a KrF excimer laser (k = 248 nm; pulse duration = 15 ns; repetition

Fig. 1(a)(d) show typical AFM images of the Co/Ni NPs, asdeposited onto SiO2/Si substrates, from 20, 50, 500 and 1000 laser ablation pulses. The AFM images of the same Co/Ni samples after their subjection to an annealing treatment of 1100 C under argon atmosphere (in order to simulate the

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Fig. 1 Typical AFM images and size distribution histograms of as-deposited (a)(d) and annealed (e)(h) Co/Ni NPs grown by PLD onto SiO2/Si substrates, as a function of the number of laser pulses used. The NPs were annealed under argon at 1100 C. The distribution curves were obtained by tting a Gaussian-model to the data.

CNT growth conditions) are shown in Fig. 1(e)(h). The mean particle size of the Co/Ni NPs was determined from the topographic heights in the AFM images and their associated distribution histograms (tted with a Gaussian distribution) are shown next to the gures (right-hand panels) for each number of laser pulses (N). The AFM images show that the Co/Ni NPs are uniformly distributed onto the substrate surface. Their mean size and surface density are seen to increase with the number of laser pulses. Indeed, the Co/Ni NPs grown with 20 laser pulses have a mean size of 1.7 0.5 nm (Fig. 1(a)), while those deposited with N = 50, 500 and 1000 laser pulses

grow in size with particle size distributions centered around 1.8 0.3, 2.5 0.5 and 2.6 0.5 nm, respectively (Fig. 1(b)(d)). The Co/Ni-NPs size is found to saturate (around $2.6 nm) for N P 500. This concentration corresponds to a threshold at which the Co/Ni NPs tend to form a continuous lm. Fig. 2(a) shows the variation of the Co/Ni NPs mean size (d) with respect to the number of laser pulses. The mean size (d) of the as-deposited NPs was found to increase exponentially with (N). A similar laser-pulse-number dependence is also observed for (d) when the Co/Ni NPs were subjected to annealing, with a clear increase in the size of the NPs (up-shift of

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Fig. 2 (a) Variation of the mean size (d) of the as-deposited and annealed Co/Ni NPs with the number of laser ablation pulses. (b) Plot in a loglog form of the data displayed in (a).

the variation curve). Indeed, (d) is seen to increase from $3.0 0.5 up to 6.8 0.5 nm as N are increased from 20 to 1000, respectively. This annealing temperature induced NPs coarsening is highly likely the result of a higher surface mobility which is expected to lead to larger NPs through the merging and/or coalescence of smaller NPs. Such increase in size of the NPs is accompanied with a reduction in their surface density. Some of the Co/Ni NPs could also sublimate, as the melting temperature of NPs is known to be lowered signicantly, than that of their bulk state, as the NPs diameter is diminished [22]. On the other hand, evolution for each (d) displayed in Fig. 2(a) was plotted in a loglog form in Fig. 2(b). Interestingly, for both conditions (i.e., as-deposited and annealed NPs), all of the (d) values were found to follow a sort of universal percolated behavior with a threshold equivalent to 100 laser pulses of ablated Co/Ni. This highlights most probably two distinct growth regimes, corresponding to two populations of NPs. Indeed, for smallest NPs, (i.e., for N < 100 laser pulses), (d) remains almost constant with the number of laser pulses employed, and could be ascribed to a nucleation phase of NPs onto SiO2/Si substrates; for the second growth regime

(N P 100 laser pulses), Co/Ni NPs are found to grow considerably in size with N. More importantly, a linear relation between log (d) and log (N) was obtained (Fig. 2(b)), and by tting the experimental data, we nd an evolution relationship of the type of d / t1/Z, with a dynamic growth exponent Z = 4.05 1.2%. Similar comportment was observed in our precedent work for the pulsed laser deposition of platinum NPs on HOPG substrate [19]. These results demonstrate that, by properly adjusting the PLD parameters, and even after annealing at high temperature, Co/Ni NPs with nanometer size are still present and well dispersed on the SiO2/Si substrates. In our all-laser growth process, these NPs will serve as a nucleation sites for CNTs growth. Growth mechanisms involving catalysts are diverse, complex and rather difcult to ascertain. Nevertheless, since the products of the plasma methods (laser, arc discharge. . .) and the CVD techniques can be viewed as almost identical, in the sense that the laser ablated products, for example, consist of supersaturated vapor of carbon, it is therefore reasonable to interpret our CNTs growth results in the light of the socalled VaporLiquidSolid (VLS) model, which was rst introduced in 1960s to explain the growth of silicon whiskers and was adopted by Saito [23] to explain the formation of SWCNTs in the arc method. Thus, the interaction of the laser vaporized carbon with the quasi-molten Co/Ni NPs (i.e., the liquid phase) at high growth temperatures, is expected to lead to the formation of CNTs (i.e., the solid phase). This growth is expected to continue as long as carbon species can continue to diffuse through the liquid Co/Ni NPs at a given growth temperature. Thus, the temperature of the catalyst NPs is denitely an important parameter for the nucleation of CNTs, since the solubility of carbon in a catalyst metal particle is temperature dependent. (It is worth noting that different metal catalysts would have their optimum catalytic activity at different temperatures [12]). In this context, we have studied the effect of furnace temperature on the Co/Ni-NPs catalyzed growth of CNTs. This study was conducted by the furnace temperatures from 700 to 1100 C in steps of 50 C, for a xed growth condition (namely, 100 laser ablation pulses of carbon onto SiO2/Si substrates pre-decorated with 50 laser pulses of Co/Ni NPs). Fig. 3 shows typical SEM micrographs of the obtained growths as a function of furnace temperature. For samples prepared at temperatures below of 900 C, no tubular structures were observed, and only a nodular surface with rounded particles (see inset of Fig. 3(a)) can be seen. These particles are highly likely Co/Ni metal catalyst NPs wrapped with a-C resulting from the laser ablation of the graphite target. At 900 C, these carbon covered NPs seem to grow in size and some nanolament germination starts to take place at the surface of the Co/Ni NPs, as can be observed in the inset of Fig. 3(b) (white arrows). At a furnace temperature of 950 C, clear nanotubular structures were formed on the substrate (see arrows in Fig. 3(c)). As the temperature is increased at 1000 C and above, SEM images reveal clearly the formation of a dense and entangled network of carbon nanotubular structures, which are seen to cover the entire surface of the substrate ($4 cm2). Finally, at 1100 C, denser networks of thinner and straighter CNTs were obtained. Moreover, these CNTs were found to feature a very high aspect ratio ($102103), with lengths easily reaching up

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to several micrometers. The CNTs are found to generally self assemble into bundles having diameters in the $520 nm range. The Raman spectra of the all-laser synthesized CNTs as a function of their growth temperatures (in the 7001100 C range) are shown in Fig. 4(a). No Radial Breathing Mode (RBM) peaks (the typical signature of SWCNTs) were detected for samples grown below 900 C. On the other hand, clear RBM bands appear for temperatures of 950 C and above, conrming thereby the presence of SWCNTs in the deposits. These Raman results corroborates well with the direct SEM observations discussed above. From the RBM position, the nanotube diameter can be determined by using the relation of Bandow et al. [24]. Thus, the mean diameter of the all-laser synthesized SWCNTs is found to vary slightly from $1.1 to $0.9 nm when their growth temperature is raised from 950 to 1100 C. It is well worth noting that the diameter distributions of the

Fig. 3 Typical SEM micrographs of the all-laser deposits at increasing furnace temperatures ranging from 700 (a) to 1100 C (e). Insets show high magnication SEM images.

Fig. 4 (a) Raman spectra of all-laser grown SWCNTs onto SiO2/Si substrates under various furnace temperatures. (b) The variation of the G/D intensity ratio with the growth temperature.

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Fig. 5 SEM micrographs panels of the SWCNTs deposits grown by the all-laser process with various amount of ablated graphite onto SiO2/Si substrates decorated with 50 laser pulses of Co/Ni NPs (a)(g). The (h)(n) images are from deposits with increasing Co/Ni NPs (from 1 to 200 laser pulses) and a xed amount of vaporized carbon obtained from the laser ablation of graphite with 100 laser pulses) and a xed amount of vaporized carbon obtained from the laser ablation of graphite with 100 laser pulses.

all-laser grown SWCNTs is quite narrow, as reected from their corresponding RBM peaks. Nevertheless, one has to recall that the observed RBM bands do not reect all of the diameters distributions in the measured SWCNT samples, but only those excited when the laser energy of 2.41 eV (514 nm) is equivalent to the electronic energy gap between the Van Hove singularities of the nanotubes themselves [25 27]. In order to have a qualitative evaluation of the quality of the grown SWCNTs, the G to D (peaking at 1600 cm1 and 1350 cm1, respectively) intensity ratio (IG/ID) is generally used as a quality indicator [2829]. The D band is mainly due to a-C and/or to other disordered sp2 carbon structures [2526,30]. Fig. 4(b) shows the variation of the IG/ID ratio of the all-laser grown SWCNTs as a function of their growth temperature. This ratio is clearly seen to increase linearly with the growth temperature (Fig. 4(b)), indicating that the relative amount of amorphous or disordered carbon diminishes to the prot of high quality CNTs as the temperature is raised from 700 to 1100 C (the corresponding IG/ID ratio increases from 0.6 to 1.5). In sum, the SEM observations are quite consistent with Raman results pointing out a temperature threshold of $950 C for the start of the all-laser growth of SWCNTs and the improvement of their structural quality as the temperature is raised towards 1100 C. These results can be discussed in the light of the VLS growth model where the growth temperature would inuence not only the formation of the liquid Co/Ni NPs but also their subsequent interaction with the laser-vaporized carbonaceous species. The rst step of the process is the formation of the liquid nanocatalyst of metal, supersaturated with carbon resulting from the absorption of carbon on the surface of the nanocatalyst [31]. During the synthesis, the liquid Co/ Ni NPs are able to incorporate a large amount of carbon. Upon cooling, the solubility limit of carbon decreases and therefore carbon atoms start to segregate toward the surface (segregation increases when temperature decreases and reach its level close the solidication point). At this stage, there is a competition between formation of graphitic sheets and nucleation of nanotubular structures. Once the nanotubes nuclei are formed, growth is expected to proceed through further incorporation of carbon at the Co/Ni NP base, and the growth process continues until the temperature becomes too low leading thereby to the solidication of the catalyst NPs (i.e., catalyst poisoning). Although all of our growth experiments were carried out at temperatures below the melting temperature of catalyst and the catalyst-carbon eutectic temperature (1326 C for NiC, and 1320 for CoC phase), the nanosize of the catalyst NPs ensures them to reach the liquid state at much lower temperatures. As an example, $5 nm-diameter Ni NPs can melt at a temperature of 900 C [12], which is close to our starting growth temperature. The solubility and diffusion of carbon in such metal NPs can also be signicantly enhanced. Indeed, while the solubility of carbon in bulk Ni is of $10.7 at.%, it increases to $20 at.% for 5 nm-diameter particles [12]. As the solubility of carbon in the catalysts decreases at lower temperature, no tubular nanostructures formation was observed at temperatures below 900 C.

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Fig. 6 SEM micrographs of the all-laser grown SWCNTs after their annealing under owing oxygen at increasing temperatures of up to 550 C (a)(d), and the corresponding variation of both FWHM of the G-band and the IG/ID intensity ratio of the all-laser SWCNTs deposits (e).

Our results have shown that higher temperatures are needed to increase the diffusion rate of carbon in the Co/Ni catalyst NPs, and the CNTs formation is mainly controlled by this catalytic process. A serious catalyst deactivation process is the catalyst poisoning that can result from an excess of a-C onto their surface, preventing thereby the Co/Ni NPs from their catalytic function. This accumulation of a-C may arise from an unbalanced carbon feed rate in the growth process [32]. As the all-laser process offers the latitude to control independently the ratio of the carbon feed rate to the catalyst concentration, we have investigated the all-laser growth by varying the number of laser pulses for the ablation of the graphite target, at a given Co/Ni NPs concentration. Then, at the ablated carbon amount giving the highest

SWCNTs density, we have varied the concentration of the Co/Ni catalyst NPs. Fig. 5 shows two panels of SEM micrographs of the all-laser deposits, grown under the two following conditions: (i) for a xed amount of Co/Ni NPs (i.e., obtained from 50 laser pulses of Co/Ni target), the amount of carbon feed was varied from 1 to 200 laser ablation pulses (Fig. 5(a)(g)); and (ii) for a xed amount of carbon feed equivalent to 100 laser ablation of pulses of graphite, the amount of Co/Ni NPs on the substrate was varied by adjusting the number of the laser ablation shots of the Co/Ni target from 1 to 200 (Fig. 5(h)(n)). As the amount of ablated carbon increases, the formation of SWCNTs is seen to take place progressively and the entire surface of the substrate is covered with CNTs after 50 laser

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pulses of carbon (Fig. 5(e)). A very dense lm of SWCNTs is obtained for 100 carbon laser pulses (Fig. 5(f)). When the amount of ablated carbon is further increased to 200 laser pulses, no CNTs can be easily observed, instead nodular-carbon coated brous nanostructures were observed on the surface of the substrates (Fig. 5(g)). This is thought to be the consequence of a carbon feed rate high enough to cover rapidly the catalyst NPs and stops the catalyzed growth of CNTs (i.e., catalyst poisoning). On the other hand, for a xed amount of supplied carbon (from 100 ablation pulses), Fig. 5(h)(n) reveal that a minimum amount of pre-deposited Co/Ni NPs (from 20 laser pulses) is needed to obtain an effective growth of CNTs. Our results show that 50 laser pulses of Co/Ni seem to be the optimum amount of catalyst to transform efciently the 100 laser pulses of carbon into a dense network of nanotubes. For higher amounts of Co/Ni (laser pulses P 100), the CNTs growth is still favoured, but an excess of Co/Ni metal NPs seem to not be consumed in the growth process, as they can be easily identied in the deposits (black arrows in Fig. 5(n)). Finally, one can note in Fig. 5(a) that SWCNTs can be grown from an amount of carbon as small as that produced by one single laser ablation shot of the graphite target (estimated to an equivalent continuous layer of $0.04 nm-thick). This shows that our all-laser process is extremely efcient in converting the ablated graphite into CNTs. The on-substrate growth of SWCNTs is accompanied with a-C deposition, which also concomitantly lands on the substrates. In order to investigate the possible removal of amorphous carbon (at least partially), the all-laser grown SWCNTs deposits were subjected to annealing for 1 h, at temperatures ranging from 200 to 550 C, in owing oxygen ($500 sccm). The SWCNTs deposits were then analyzed systematically both by SEM and Raman spectroscopy. Fig. 6(a)(d) show SEM micrographs of the SWCNTs after their annealing at various temperatures. It is clearly seen that when the annealing temperature is increased from 300 to 550 C, the nanotubes become thinner and their surface smoother and cleaner, denoting thereby their effective purication. Consistent with these SEM observations, the corresponding Raman D and G bands of the annealed SWCNTs deposits were also found to be sensitive to this thermal purication process, as illustrated in Fig. 6(e). Indeed, as the annealing temperature is increased up to 550 C, not only the full width at half maximum (FWHM) of the graphitic mode (IG) decreases from $67 to 50 cm1, but there is a clear increase in the G/D intensity ratio from $1 to 1.6 (Fig. 6(e)). These Raman results conrm the progressive burning of a-C and/or other forms of disordered carbon structures. Raman characterizations were also carried out on the alllaser grown SWCNTs scratched from their original substrates and deposited onto a bare Si (100) substrate (the latter also serves for frequency calibration with its characteristic Raman peak sharply peaking at 520 cm1). The rather high G/D intensity ratio ($5) for the as-grown samples indicates the overall good-quality of the SWCNT mats (Fig. 7(a)). This ratio decreases slightly ($4) after subjecting the nanotubes to the purication process (i.e., annealed samples), which suggests that heat oxidization treatment created additional structural defects in the nanotubes. Moreover, the clear

improvement in the G/D ratio (comparatively with SWCNTs when they are on substrate (see Fig. 4(a)) suggests also that some carbon species present on the SiO2/Si support cannot be removed completely even by a dry oxidation process. The carbon nanotubes were also analyzed by means of thermogravimetry. Fig. 7(b) shows TGA curves and their associated differentiated curves (DTA) of both AG and PU SWCNT. For the AG-SWCNT material, TGA data reects two major stepwise weight-loss transitions namely, rst oxidation starting at $450 C (corresponding to $33% of the analyzed mass that can be assigned to amorphous carbon, and curly, entangled and opened tips SWCNT [33]), while main part of the deposit oxidizes in the 650850 C range ($67% of the mass). For the annealed-SWCNT material, the rst oxidation starts at higher temperatures ($550 C) and represents almost 22% of the deposit, and the second oxidation occurs in the 650 850 C (as for the AG-SWCNT). For both the AG and PU materials, the second oxidation occurring in the 650850 C temperature range is believed to be due mainly to non-defective nanotubes and other graphitized carbon nanostructures. This temperature range corresponds to those reported elsewhere for the burning temperature of SWCNT (of which

Fig. 7 (a) Raman spectra of the scratched-out AG and PU SWCNT mats, excited by laser energy of 2.41 eV, and (b) their corresponding mass loss experimental data (TGA) and its derivative mass loss (DTG) with respect to the temperature, with a heating rate of 10 C/min.

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Fig. 8 Representative TEM morphologies of CNTS networks, after their scratching from the substrate and dispersion in alcohol. (a) Bundles of SWCNTs, (b) TEM image of a network of MWCNT. The inset shows close up view of DWCNT. (c) Isolated SWCNTs, and (d) Nanobamboo CNT. ignition occurs $600 C [34]) and the oxidation of highlygraphitized carbon bers ($800 C). Moreover, our all-laser synthesized SWCNT have been shown to exhibit a rather high oxidation resistance as some of them survived annealing temperatures in excess of 800 C [35]. In the other hand, from 800 C, a residue value of 5% of the mass constitutes most probably the Co/Ni catalyst residual oxide. Following the TGA analysis, it can be deduced that the yield of our laser process can be close to $78%. It is worth to note clearly at this level that all the ablated carbon species reaching the substrate do not necessarily contribute to the exclusive growth of SWCNTs, and consequently other carbon by-products (nanohorns, nanocages, amorphous carbon, etc.), together with some multiwall-carbon nanotubes and/or nanobers are also present in the all-laser deposits, as previously observed and here revealed by TEM analysis. Indeed, the laser deposits were characterized by means of transmission electron microscopy to examine their structure at the nanoscale (after their scratching out from their original substrate and dispersed in alcohol). Bundles of only few nanotubes, to rope of several SWCNTs (having a mean diameter of $1.1 nm) were the most observed structures (Fig. 8(a)). TEM analysis also reveals that some carbon deposits exhibit a middle-hollow structure (Fig. 8(b)), and are a MWCNT, with possible three and/or double walled carbon nanotubes (TWCNT and DWCNT, see inset of Fig. 8(b)). The inset image indicates also that the DWCNTs have clear graphite layers

aligned to the tube axis. The interlayer spacing is about 0.34 nm, corresponding to the (0 0 2) plane of graphite [36], and are exceptionally pure since no contaminant (metallic NPs and/or other carbon nanostructures) were found either inside or outside the tubes. On the other hand, some isolated SWCNTs have been also observed occasionally (Fig. 8(c)), with a diameter distribution varying from $1 to 1.5 nm. The length of these isolated nanotubes is of tens to hundreds of nanometer. Finally, Fig. 8(d) shows a good example of nanostructures that are rarely found in the deposits. However, other groups have ever reported similar nanostructures albeit under different atmospheres [37]. This specic structure is a so-called nanobamboo. It is one of the intermediate stages between multiwall nanotubes and nanobers. In sum, even if the grown carbon nanostructures were mainly found to be bundles of SWCNTs, we refer to these deposits as carbon nanotubular structure (CNTS) throughout this section. Also, even if the surface density of the grown CNTS was found almost homogenous over the whole substrate surface, one can note their spatial inhomogeneity -in terms of their structural properties (diameter, length, etc.)with respect to their location on the substrate. This spatially non uniformity seems to be inherent to the growth process itself and to the carbon deposition sequences reaching the substrate. In fact, and contrary to the CVD growth process where the carbon feedstock reaches vertically the substrate surface simultaneously, in our process, the laser beam is swept over

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Fig. 9 Various SEM micrographs showing (a) base-growth, (b) tip-growth and (c) grown nanotubes with closed ends, observed on SiO2/Si substrates. A schematic representation of possible growth mechanism of the all-laser CNTS is also shown (e)(j). the graphite target surface at right angle (90), and the ablated carbon species start the reach the silicon substrate sequentially from one side to the other (i.e., spanning the whole substrate dimension). On the other hand, from our experimental results, it appears that in addition to the most important parameters controlling the all-laser growth of SWCNTs (i.e., the growth temperature and the balanced ratio of catalyst to carbon feedstock rates), the substrate plays also a key role. Indeed, the interaction of the catalyst NPs with the substrate can be characterized by its contact angle at the growth temperature, analogous to hydrophobic (i.e., weak interaction) and hydrophilic (i.e., strong interaction) surfaces. In the present work, nickel on silica (SiO2) is known to have a large contact angle which results in a weak interaction, leading thereby to an easy lift-up of the NPs, which would rather favor the CNTS tip-growth mechanism [3843]. In contrast, cobalt or Fe

NPs are known to interact strongly with SiO2 substrates (hydrophilic behavior) [4447], which will promote more the CNTS base-growth mechanism. Thus, as we are using bimetallic Co/Ni NPs as a catalyst material (which may contain both hydrophobic and hydrophilic parts), we have observe in our deposits the co-existence of both tip- and base- growth mechanism, as illustrated in Fig. 9, and the CNTS were found to generally have closed ends with metal NPs as junction points (Fig. 9(d)). We can speculate that this mixed growth mechanisms and associated NPs junction points between the nanotubes situation may originate from the combination of the two following phenomena: (i) the merging of CNTS sprouting from separated sets of Co-NPs and Ni-NPs, forming then the same structure of CNTS (Fig. 9(f)), and/or (ii) the presence of both Co and Ni NPs within the same nucleation site, which split after receiving the ablated carbon leading to both CNTS grown from Co-NPs (attached to the

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substrate according to the base-growth mechanism) and to CNTS grown from Ni-NPs (which are lifted up according to the tip-growth mechanism), as schematized in Fig. 9(j). Our results show that in the rather complex growth mechanism of CNTS by the all-laser process, the use of bi-metallic Co/ Ni catalyst NPs can lead to a mixture of both base- and tipgrowth of CNTS. These observed growth mechanism models reported here are rather a speculation based on rough observation and do not pretend in any case to be a universal tendency related to the Co/Ni catalyst material, and other hypothesis are completely possible and not excluded, particularly when one considers the variety and complexity of growth mechanism involved in CNT structures. Also, as our related growth mechanism models are intimately correlated to the presence of underlying substrate, we do not feel comfortable to draw any nal conclusion at this point, and more available data are needed to analyze more deeply (/exhaustively) this particular issue. Indeed, fully characterization of the grown nanostructures, as a function of their exact location on the substrate, together with the laser plasma plume characterization through the time-resolved spectroscopy, and the segmented growth that should be correlated to the pulsed supply of carbon via laser ablation and the growth mechanism involved at each step are needed do draw a relevant conclusions. Finally, the laser grown SWCNT networks (subjected to annealing treatment to minimize the a-C) were integrated into FET-like devices as active transistor channel (as illustrated in Fig. 10(a)) and their electrical properties were investigated. Fig. 10(b) shows example of the typical ISDVSD output characteristics, at various VG values, for the SWCNT-based FET devices, having a channel density equivalent to ve carbon laser pulses of SWCNT-network. The ISD current through the channel is seen to increase steadily with the VSD voltage, while very low current ows in the channel when gating with large positive VG voltages. This behavior is similar to conventional p-type depletion-mode eld effect transistor. In fact, because of the thick gate oxide (typically 500 nm), relatively high gate voltages (tens of volts) are needed to gate the CNTs-based active channels. On the other hand, when positive gate voltages were applied, the conductance (ISD) did not reach the ultimate zero value (i.e., the ideal OFF-state). This result indicates that the SWCNT networks are mixtures of semiconducting and metallic nanotubes. Indeed, it is worth noting here that the nanotube diameters identied in the present work (i.e., in the range of $0.971.08 nm), they can be either metallic, such as (4,10), (10,4) and (8,8) tubes, or semiconducting, such as (12,1), (1,12), (9,7) and (7,9) tubes, by considering the possible combinations, according to the well-known diameter-chirality dependence formula [21]. Its important to note here that the presence of some metallic CNT (m-CNT) in a bundle can denitely affect the performance of the CNT-based FET devices. Indeed, the highest is the percentage of m-CNTs in the deposit, the lowest is the number of working FETs devices. However, to fully-short a CNTs-based FET or affect the gate modulation of neighboring semiconducting nanotubes (s-CNTs), the m-CNT has to be the straightest possible and directly bridges both ends of the gap (i.e., a percolating m-CNTs pathway), otherwise it will act just as metal interconnect between adjacent s-CNTs with-

in the bundle or a group of bundles. This additional condition dramatically diminishes the effect of m-CNTs on the shortage of FET devices. Also, regardless to the theoretical domination of semiconducting nature of the as-grown CNT vs. the metallic ones (66 vs. 33%), and even if we assume the presence of

Fig. 10 (a) Schematics of the developed SWCNT-networksbased FET active-channel, and (b) example of the typical ISD VSD output characteristics of the device (for channel density obtained with 5 carbon laser pulses). (c) Associated ON/OFF switching ratios of the various FET devices as a function of the SWCNT-channel densities. Inset is the conductance (ISD) vs. gate voltage (VG) of the SWCNT networks-based device plotted in (b).

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some m-CNT in the devices, an electrical breakdown of the metallic pathways when current ow the network channel can easily occur. Indeed, the current-induced electrical breakdown method has been shown to be effective for the selective removal of metallic SWCNTs [48], and this process can yield to CNT with s-CNT enriched compared to the expected 2/3 population. This scenario lowers additionally and signicantly the chances of simple shortage by metallic tubes in CNTs-based devices. Nonetheless, not all the fabricated CNTs-FET devices were functional, and a certain percentage of them did not show any gate modulation or were simply shorted, probably because of the presence of large amount of m-CNTs or other amorphous C nanostructures. A typical transfer characteristics (ISD as a function of the gate voltage), at VSD = 10 V, were deduced and reported in the inset of Fig. 10(c). The conductance of the SWCNT-based devices is seen to reach its highest values in the negative VG range, determining thereby the ON-state of the transistors. As VG is swept towards positive values, ISD starts to decrease until it reaches its lowest value (corresponding to the OFFstate of the FETs). These transfer characteristics conrm the p-type behavior of these SWCNT-based devices (i.e., switching between the accumulation (hole carriers) and depletion states). These results corroborate well with previous reports where not only isolated single nanotubes [21], but also random networks of SWCNT-bundles [49] were found to behave as p-type FETs in air. In order to point out the effect of the FET channel density (interpreted here by the number of carbon laser pulses used to grow the SWCNT networks) on the corresponding transistor properties, FETs with various SWCNT channel densities (namely, 1, 5, 20, 50 and 100 laser pulses) were fabricated, and their ON to OFF switching ratios recorded from their corresponding ON and OFF-states, respectively, were measured and plotted in Fig. 10(c). Except the channel density equivalent to one laser pulse of carbon for which the formed SWCNTs seem most probably to not fully-percolate the overall network over the whole channel length ($1 mm)- These FETs switching behaviors are shown to be inversely proportional to the channel density (Fig. 10(c)). This behavior is most probably a consequence of the formation of continuous path of touching metallic nanotube (m-SWCNT) through the whole channel network, where indeed, the m-SWCNT could easily come into contact with one another to form a percolated network with respect to the channel density, resulting in an electrically percolated metallic network. In sum, even if our all-laser approach is shown to be a very effective tool for the localized growth of SWCNTs and their direct integration into FET like devices, with minimum post-processing, there is inevitable need to develop strategies to achieve exclusively semiconducting tubes in the bundles for high performances SWCNT-networks-based FET device.

conditions. This novel approach gives more latitude to control separately the two main ingredients for SWCNT growth, namely the catalyst NPs and the vaporized carbon feedstock. Thus, by investigating the PLD deposition of Co/Ni NPs, we were able to show that by properly adjusting the number of laser pulses, the size of Co/Ni catalyst NPs can be monitored in the (1.52.7) nm range. On the other hand, by controlling the growth temperature and the ratio of carbon feed rate to Co/Ni NPs amount, optimal conditions leading to the growth of dense CNTS deposits were identied. Our results demonstrate that the diameters of individual SWCNTs are in the range of $1 nm, independently of the initial size of catalytic nanoparticles, most probably because of the agglomeration of Co/Ni NPs into larger ones during the growth process. The all-laser CNTS were also found to mainly self-assemble into SWCNT bundles having diameters in the (520) nm range. The all-laser process was also shown to lead to a concomitant deposition of a-C on the substrate, which can be removed at least partially by thermal oxidation at temperatures around 550 C. Finally, based on our SEM observations, our results were discussed in the light of the VLS growth model. In particular, we have shown that both base-growth and tip-growth mechanism models occur in our all-laser approach. Finally, in addition to being exible and relatively easy to implement, this novel growth process has opened a new way for the localized growth of CNTS for their direct integrated into functional devices, with minimum post-processing. Our electrical results have not only demonstrated that transport through the SWCNT networks was dominated by positive carriers (holes), but also that SWCNT-networks consist of mixtures of semiconducting and metallic nanotubes. These are needs for improving the quality of CNTs-based nanoelectronic devices by developing strategies to achieve exclusively semiconducting tubes.

Acknowledgments
This work was nancially supported by the FQRNT (Le Fonds Quebecois de la Recherche sur la Nature et les Technologies) and the Natural Science and Engineering Research Council (NSERC) of Canada.

R E F E R E N C E S

4.

Conclusion

We have investigated the on-substrate growth of SWCNTs with the all-laser growth process, which uses the laser ablation approach to rst deposit the Co/Ni catalyst NPs at desired locations on the substrate, and then to grow SWCNTs, by laser ablating a pure graphite target under appropriate

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