Growth of Single‐Walled Carbon Nanotubes with Controlled Structure: Floating Carbide Solid Catalysts

Single‐walled carbon nanotube (SWNT) horizontal arrays with specific chirality can be enriched using solid carbide catalysts on substrates. However, scale‐up production by continuous loading of the solid catalysts onto the substrates is challenging. Described here is the preparation of a floating carbide solid catalyst (FSC) for the controlled growth of SWNTs. The FSC, titanium carbide (TiC) nanoparticle, was directly obtained in the carrier gas phase by decomposition and carbonization of the titanocene dichloride precursor at high temperature. By using the TiC nanoparticle FSC, both SWNT horizontal arrays and randomly distributed networks can be obtained. The chirality of the as‐grown SWNTs were thermodynamically controlled to have fourfold symmetry. Further optimization of growth condition resulted in an abundance of (16,8) tubes with about a 74 % content. This FSC chemical vapor deposition (FSCCVD) method has potential for realizing mass growth of SWNTs with controlled structures.     

Selective synthesis combined with chemical separation of single-walled carbon nanotubes for chirality selection

Single-walled carbon nanotubes (SWNTs) are potential materials for future nanoelectronics. Since the electronic and optical properties of SWNTs strongly depend on tube diameter and chirality, obtaining SWNTs with narrow (n,m) chirality distribution by selective growth or chemical separation has been an active area of research. Here, we demonstrate that a new, bimetallic FeRu catalyst affords SWNT growth with narrow diameter and chirality distribution in methane CVD. At 600 degrees C, methane CVD on FeRu catalyst produced predominantly (6,5) SWNTs according to UV-vis-NIR absorption and photoluminescence excitation/emission (PLE) spectroscopic characterization. At 850 degrees C, the dominant semiconducting species produced are (8,4), (7,6), and (7,5) SWNTs, with much narrower distributions in diameter and chirality than materials grown by other catalysts. Further, we show that narrow diameter/chirality growth combined with chemical separation by ion exchange chromatography (IEC) greatly facilitates achieving single (m,n) SWNT samples, as demonstrated by obtaining highly enriched (8,4) SWNTs with near elimination of metallic SWNTs existing in the as-grown material.     

SWNT Nucleation from Carbon-Coated SiO(2) Nanoparticles via a Vapor-Solid-Solid Mechanism

Since the discovery of single-walled carbon nanotubes (SWNTs) in the early 1990s, the most commonly accepted model of SWNT growth on traditional catalysts (i.e., transition metals including Fe, Co, Ni, etc.) is the vapor-liquid-solid (VLS) mechanism. In more recent years, the synthesis of SWNTs on nontraditional catalysts, such as SiO(2), has also been reported. The precise atomistic mechanism explaining SWNT growth on nontraditional catalysts, however, remains unknown. In this work, CH(4) chemical vapor deposition (CVD) and single-walled carbon nanotube (SWNT) nucleation on SiO(2) nanoparticles have been investigated using quantum-chemical molecular dynamics (QM/MD) methods. Upon supply of CH(x) species to the surface of a model SiO(2) nanoparticle, CO was produced as the main chemical product of the CH(4) CVD process, in agreement with a recent experimental investigation [Bachmatiuk et al., ACS Nano 2009, 3, 4098]. The production of CO occurred simultaneously with the carbothermal reduction of the SiO(2) nanoparticle. However, this reduction, and the formation of amorphous SiC, was restricted to the nanoparticle surface, with the core of the SiO(2) nanoparticle remaining oxygen-rich. In cases of high carbon concentration, SWNT nucleation then followed, and was driven by the formation of isolated sp(2)-carbon networks via the gradual coalescence of adjacent polyyne chains. These simulations indicate that the carbon saturation of the SiO(2) surface was a necessary prerequisite for SWNT nucleation. These simulations also indicate that a vapor-solid-solid mechanism, rather than a VLS mechanism, is responsible for SWNT nucleation on SiO(2). Fundamental differences between SWNT nucleation on nontraditional and traditional catalysts are therefore observed.     

Chemical vapor depositions of single-walled carbon nanotubes catalyzed by uniform fe(2)o(3) nanoclusters synthesized using diblock copolymer micelles

Inversed micelles formed by polystyrene-block-poly(2-vinyl-pyridine) in toluene loaded with FeCl3 were used to synthesize and deliver discrete Fe2O3 nanoclusters with uniform diameters to flat substrates. Single-walled carbon nanotubes (SWNTs) were grown by chemical vapor deposition using these nanoclusters as the catalysts. Atomic force microscope characterizations revealed that high density SWNT mats were grown on the surface and the diameter of nanotubes was controlled by the diameter of nanoclusters. Electrical measurement revealed that the dense SWNT mats contained both semiconducting and metallic SWNTs and could be used to build thin film transistors.     

Growth of millimeter-long and horizontally aligned single-walled carbon nanotubes on flat substrates

Millimeter-long and well-aligned single-walled carbon nanotubes (SWNTs) have been produced on silica/silicon surfaces using the carbon monoxide chemical vapor deposition (CO-CVD) method. The orientation of the nanotube arrays can be well-controlled by the gas flow during the growth. The majority of the orientated SWNTs are straight and individual. The length of the nanotubes can be >2 mm for a 10 min growth. Furthermore, multidimensional crossed-networks of SWNT can be easily generated by multistep processes. These results present a great opportunity in the controllable production of organized SWNT arrays for large-scale carbon nanotube-based nanodevice fabrication.     

Supramolecular hybrid of metal nanoparticles and semiconducting single-walled carbon nanotubes wrapped by a fluorene-carbazole copolymer

The first approach for the preparation of metal nanoparticle/semiconducting single-walled carbon nanotube (SWNT) hybrids with specified chirality is described. For this purpose, a copolymer of a fluorene derivative with two long-chain alkyl substituents and a carbazole derivative carrying a thiol group was used. The copolymer was found to selectively dissolve (7,6)- and (8,7)SWNTs, as determined by UV/Vis/NIR absorption and Raman spectroscopy and 2D photoluminescence mapping. Gold and silver nanoparticles with diameters of about 3.8 and about 3.2 nm, respectively, were readily attached along the SWNTs by means of coordination bonds between the nanoparticles and the thiol moieties on the copolymer, as revealed by atomic force and electron microscopy studies. The study provides a novel way to design and fabricate metal nanoparticle/semiconducting SWNT hybrids with specific nanotube chirality.     

Crystal plane dependent growth of aligned single-walled carbon nanotubes on sapphire

On single-crystal substrates, such as sapphire (alpha-Al 2O 3) and quartz (SiO 2), single-walled carbon nanotubes (SWNTs) align along specific crystallographic axes of the crystal, indicating that the SWNT growth is influenced by the crystal surface. Here, we show that not only the orientation, but also the diameter and chirality of SWNTs are affected by the crystal plane of the sapphire substrate. The aligned SWNTs grown on the A- and R-planes of sapphire have narrower diameter distributions than randomly oriented tubes produced on the C-plane sapphire and amorphous SiO 2. Photoluminescence measurements reveal a striking difference between the aligned SWNTs: near-zigzag tubes are observed on the A-plane and near-armchair tubes on the R-plane. This study shows the route for the diameter and chirality control of SWNTs by surface atomic arrangements of a single-crystal substrate.     

Selective matching of catalyst element and carbon source in single-walled carbon nanotube synthesis on silicon substrates

We have studied the compatibility of various catalysts for ethylene and ethanol chemical vapor deposition (CVD) syntheses of single-walled carbon nanotubes (SWNTs) on Si substrates. A strong selectivity between the catalyst elemental species and carbon source was found; SWNT yield for Fe (Co) catalysts was much higher for ethylene (ethanol) CVD than for ethanol (ethylene) CVD. This strong and completely opposite selectivity implies significantly different SWNT growth mechanisms for ethanol and ethylene CVD on Si substrates.     

Spatially selective guided growth of high-coverage arrays and random networks of single-walled carbon nanotubes and their integration into electronic devices

The chemical vapor deposition growth of unusual arrangements of single-walled carbon nanotubes (SWNTs) by the combined of use patterned catalysts and quartz substrates is reported. Nearly perfectly aligned, high-coverage arrays of SWNTs can be generated in this manner. High-coverage random networks of SWNTs can also be created in the same growth step, with good spatial alignment and electrical interfaces to the aligned arrays. Tubes with these geometries are ideally suited to applications in thin-film electronic devices. We demonstrate this possibility through the construction of thin-film-type transistors in which the random networks form the source and drain electrodes and the aligned arrays form the channel.     

Identification of the structures of superlong oriented single-walled carbon nanotube arrays by electrodeposition of metal and Raman spectroscopy

In this Communication, we have demonstrated a facile and effective approach to identify the structure of the superlong well-aligned single-walled carbon nanotubes (SWNTs) by the combination of electrodeposition of metal (Ag) with Raman spectroscopy. The suitable density and the visibility of the Ag-deposited long oriented nanotubes make it possible to acquire Raman spectra from isolated individual nanotubes very easily. The results reveal that the well-oriented SWNT arrays on SiO2/Si wafer fabricated by EtOH chemical vapor deposition using Fe/Mo nanoparticles as catalyst exhibit a low percentage of metallic SWNTs (5%). Among other SWNTs about 62.3% are semiconducting SWNTs, and a small amount of nanotubes are quasimetallic. About 32% are a so-called quasi-insulator, which is caused inevitably by the defects during growth. Furthermore, the structural uniformity of the long SWNTs can be also evaluated by the deposition of Ag along the length and Raman spectroscopy. This method also provides an approach to deposit other metals on long SWNTs, which could have various potential applications such as for use as sensors, etc. More importantly, this facile method can be applied to long SWNT arrays fabricated from other different catalytic systems so that the relationship between the growth conditions and the structures of SWNTs are expected to be ruled out.     

Rational concept to recognize/extract single-walled carbon nanotubes with a specific chirality

Single-walled carbon nanotubes (SWNTs) have remarkable and unique electronic, mechanical, and thermal properties, which are closely related to their chiralities; thus, the chirality-selective recognition/extraction of the SWNTs is one of the central issues in nanotube science. However, any rational materials design enabling one to efficiently extract/solubilize pure SWNT with a desired chirality has yet not been demonstrated. Herein we report that certain chiral polyfluorene copolymers can well-recognize SWNTs with a certain chirality preferentially, leading to solubilization of specific chiral SWNTs. The chiral copolymers were prepared by the Ni(0)-catalyzed Yamamoto coupling reaction of 2,7-dibromo-9,9-di-n-decylfluorene and 2,7-dibromo-9,9-bis[(S)-(+)-2-methylbutyl]fluorene comonomers. The selectivity of the SWNT chirality was mainly determined by the relative fraction of the achiral and chiral side groups. By a molecular mechanics simulation, the cooperative interaction between the fluorene moiety, alkyl side chain, and graphene wall were responsible for the recognition/dissolution ability of SWNT chirality. This is a first example describing the rational design and synthesis of novel fluorene-based copolymers toward the recognition/extraction of targeted (n,?m) chirality of the SWNTs.     

Preparation of horizontally aligned single-walled carbon nanotubes with floating catalyst

A strategy to prepare horizontally aligned single-walled carbon nanotubes(SWNTs) at moderate temperatures(≤600 ℃) were developed.Using ferocene as the catalyst precursor,Fe nanoparticles are formed in the gaseous phase and catalyze the nucleation and growth of SWNTs in situ.Then the resultant SWNTs are deposited onto the substrates downstream and aligned by the surface lattice of the ST-cut single crystal quartz.The preparation of SWNT arrays at moderate temperatures is important for combining the tube growth with device fabrication.     

Electrochemical templating of metal nanoparticles and nanowires on single-walled carbon nanotube networks

The use of single-walled carbon nanotube (SWNT) networks as templates for the electrodeposition of metal (Ag and Pt) nanostructures is described. Pristine SWNTs, grown on insulating SiO2 surfaces using catalyzed chemical vapor deposition, served as the working electrode. In the simplest case, electrical contact was made by depositing a gold strip on the SWNT substrate (device 1). Deposition of Ag and Pt over extensive periods (30 s) resulted in a high density of particles on the SWNTs, with almost contiguous nanowire formation from the Au/SWNT boundary moving to isolated nanoparticles at further distances from the contact. For direct electrochemical studies of Ag and Pt nucleation, the assembly was coated in a resist layer and a small window opened up to expose only the electrically connected SWNTs to solution (device 2). In this case, the electrochemical signature in voltammetric and amperometric studies of metal deposition was due solely to processes at the SWNTs. Coupled with high-resolution microscopy measurements (atomic force microscopy and field emission scanning electron microscopy), this approach provided detail on the nucleation and growth mechanisms of Ag and Pt on SWNTs under electrochemical control. In particular, Ag growth was found to be rapid and progressive with an increasing nanoparticle density with time, whereas Pt deposition was characterized by lower nucleation densities and slower growth rates with a tendency for larger particles to be produced over long times.     

Effect of Backbone Chemical Structure of Polymers on Selective (n,m)Single‐Walled Carbon Nanotube Recognition/Extraction Behavior

The development of a simple and facile method to extract single‐walled carbon nanotubes (SWNTs) with a specific chirality index is one of the most‐crucial issues in the fundamental study and applications of the SWNTs. We have compared the selective recognition/extraction of the SWNT chirality of poly(9,10‐dioctyl‐9,10‐dihydrophenanthrene‐2,7‐diyl) (2C8‐PPhO) to that of poly(9,9‐dioctyfluoreny1‐2,7‐diyl) (2C8‐PFO) that are able to extract specific semiconducting SWNTs free of any metallic SWNTs. Vis/NIR absorption, 2D photoluminescence, and Raman spectroscopy as well as molecular mechanical simulations were used to analyze and understand the obtained chiral selective solubilization behavior. We found that 2C8‐PPhO selectively extracts and enriches the (8,6), (8,7), and (9,7)SWNTs, whose behaviors are different from that of 2C8‐PFO, which preferentially extracts the (7,5), (7,6), (8,6), and (8,7)SWNTs. Our results indicate that 2C8‐PPhO preferably recognizes larger‐diameter SWNTs with higher chiral angles compared to those recognized by 2C8‐PFO. These findings demonstrate that the difference in the non‐aromatic ring numbers on the polymers results in different SWNT chirality recognition/extraction behaviors.     

Recent progress in chemical detection with single-walled carbon nanotube networks

Single-walled carbon nanotubes (SWNTs) have had significant impact on the development of gas sensors in the last decade. However, useful applications of SWNTs are limited by the lack of manufacturable routes to device formation. This Highlight article chronicles recent progress in this area and demonstrates the great promise of a new room temperature deposition method for SWNT networks in gas sensing applications. This liquid deposition technique allows the deposition of pre-treated, highly aligned SWNT networks on a wide variety of substrates. A significant advantage of SWNT-network sensors is that fluctuations in the electrical response of individual SWNTs become less important as the size of the network increases. Therefore, device properties can be controlled by the overall density of the network rather than the physical properties of any individual SWNT. At densities where semiconducting pathways dominate, highly sensitive thin-film chemoresistive sensors can be fabricated. Such devices also have higher signal-to-noise ratios and are easier to fabricate than devices based on a single SWNT.     

Changing chirality during single-walled carbon nanotube growth: a reactive molecular dynamics/Monte Carlo study

The growth mechanism and chirality formation of a single-walled carbon nanotube (SWNT) on a surface-bound nickel nanocluster are investigated by hybrid reactive molecular dynamics/force-biased Monte Carlo simulations. The validity of the interatomic potential used, the so-called ReaxFF potential, for simulating catalytic SWNT growth is demonstrated. The SWNT growth process was found to be in agreement with previous studies and observed to proceed through a number of distinct steps, viz., the dissolution of carbon in the metallic particle, the surface segregation of carbon with the formation of aggregated carbon clusters on the surface, the formation of graphitic islands that grow into SWNT caps, and finally continued growth of the SWNT. Moreover, it is clearly illustrated in the present study that during the growth process, the carbon network is continuously restructured by a metal-mediated process, thereby healing many topological defects. It is also found that a cap can nucleate and disappear again, which was not observed in previous simulations. Encapsulation of the nanoparticle is observed to be prevented by the carbon network migrating as a whole over the cluster surface. Finally, for the first time, the chirality of the growing SWNT cap is observed to change from (11,0) over (9,3) to (7,7). It is demonstrated that this change in chirality is due to the metal-mediated restructuring process.     

Dendrimer-templated Fe nanoparticles for the growth of single-wall carbon nanotubes by plasma-enhanced CVD

A fourth-generation (G4) poly(amidoamine) (PAMAM) dendrimer (G4-NH2) has been used as a template to deliver nearly monodispersed catalyst nanoparticles to SiO2/Si, Ti/Si, sapphire, and porous anodic alumina (PAA) substrates. Fe2O3 nanoparticles obtained after calcination of the immobilized Fe3+/G4-NH2 composite served as catalytic "seeds" for the growth of single-wall carbon nanotubes (SWNTs) by microwave plasma-enhanced CVD (PECVD). To surmount the difficulty associated with SWNT growth via PECVD, reaction conditions that promote the stabilization of Fe nanoparticles, resulting in enhanced SWNT selectivity and quality, have been identified. In particular, in situ annealing of Fe catalyst in an N2 atmosphere was found to improve SWNT selectivity and quality. H2 prereduction at 900 degrees C for 5 min was also found to enhance SWNT selectivity and quality for SiO2/Si supported catalyst, albeit of lower quality for sapphire supported catalyst. The application of positive dc bias voltage (+200 V) during SWNT growth was shown to be very effective in removing amorphous carbon impurities while enhancing graphitization, SWNT selectivity, and vertical alignment. The results of this study should promote the use of exposed Fe nanoparticles supported on different substrates for the growth of high-quality SWNTs by PECVD.     

General rules for selective growth of enriched semiconducting single walled carbon nanotubes with water vapor as in situ etchant

The presence of metallic nanotubes in as-grown single walled carbon nanotubes (SWNTs) is the major bottleneck for their applications in field-effect transistors. Herein, we present a method to synthesize enriched, semiconducting nanotube arrays on quartz substrate. It was discovered that introducing appropriate amounts of water could effectively remove the metallic nanotubes and significantly enhance the density of SWNT arrays. More importantly, we proposed and confirmed that the high growth selectivity originates from the etching effect of water and the difference in the chemical reactivities of metallic and semiconducting nanotubes. Three important rules were summarized for achieving a high selectivity in growing semiconducting nanotubes by systematically investigating the relationship among water concentration, carbon feeding rate, and the percentage of semiconducting nanotubes in the produced SWNT arrays. Furthermore, these three rules can be applied to the growth of random SWNT networks on silicon wafers.     

Single wall carbon nanotube amplification: en route to a type-specific growth mechanism

With the desire to mass produce any specific n,m type of single wall carbon nanotube (SWNT) from a small sample of the same material, we disclose here the preliminary work directed toward that goal. The ultimate protocol would involve taking a single n,m-type nanotube sample, cutting the nanotubes in that sample into many short nanotubes, using each of those short nanotubes as a template for growing much longer nanotubes of the same type, and then repeating the process. The result would be an amplification of the original tube type: a parent SWNT serving as the prolific progenitor of future identical SWNT types. As a proof-of-concept, we use here a short SWNT seed as a template for vapor liquid solid (VLS) amplification growth of an individual long SWNT. The original short SWNT seed was a polymer-wrapped SWNT, end-carboxylated, and further tethered with Fe salts at its ends. The Fe salts were to act as the growth catalysts upon subsequent reductive activation. Deposition of the short SWNT-Fe tipped species upon an oxide surface was followed by heating in air to consume the polymer wrappers, then reducing the Fe salts to Fe(0) under a H2-rich atmosphere. During this heating, the Fe(0) can etch back into the short SWNT so that the short SWNT acts as a template for new growth to a long SWNT that occurs upon introduction of C2H4 as a carbon source. Analysis indicated that the templated VLS-grown long SWNT had the same diameter and surface orientation as the original short SWNT seed, although amplifying the original n,m type remains to be proven. This study could pave the way for an amplified growth process of SWNTs en route to any n,m tube type synthesis from a starting sample of pure nanotubes.     

QM/MD simulation of SWNT nucleation on transition-metal carbide nanoparticles

The mechanism and kinetics of single-walled carbon nanotube (SWNT) nucleation from Fe- and Ni-carbide nanoparticle precursors have been investigated using quantum chemical molecular dynamics (QM/MD) methods. The dependence of the nucleation mechanism and its kinetics on environmental factors, including temperature and metal-carbide carbon concentration, has also been elucidated. It was observed that SWNT nucleation occurred via three distinct stages, viz. the precipitation of the carbon from the metal-carbide, the formation of a "surface/subsurface" carbide intermediate species, and finally the formation of a nascent sp(2)-hybidrized carbon structure supported by the metal catalyst. The SWNT cap nucleation mechanism itself was unaffected by carbon concentration and/or temperature. However, the kinetics of SWNT nucleation exhibited distinct dependences on these same factors. In particular, SWNT nucleation from Ni(x)C(y) nanoparticles proceeded more favorably compared to nucleation from Fe(x)C(y) nanoparticles. Although SWNT nucleation from Fe(x)C(y) and Ni(x)C(y) nanoparticle precursors occurred via an identical route, the ultimate outcomes of these processes also differed substantially. Explicitly, the Ni(x)-supported sp(2)-hybridized carbon structures tended to encapsulate the catalyst particle itself, whereas the Fe(x)-supported structures tended to form isolated SWNT cap structures on the catalyst surface. These differences in SWNT nucleation kinetics were attributed directly to the relative strengths of the metal-carbon interaction, which also dictates the precipitation of carbon from the nanoparticle bulk and the longevity of the resultant surface/subsurface carbide species. The stability of the surface/subsurface carbide was also influenced by the phase of the nanoparticle itself. The observations agree well with experimentally available data for SWNT growth on iron and nickel catalyst particles.