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.     

Role of subsurface diffusion and Ostwald ripening in catalyst formation for single-walled carbon nanotube forest growth

Here we show that essentially any Fe compounds spanning Fe salts, nanoparticles, and buckyferrocene could serve as catalysts for single-walled carbon nanotube (SWNT) forest growth when supported on AlO(x) and annealed in hydrogen. This observation was explained by subsurface diffusion of Fe atoms into the AlO(x) support induced by hydrogen annealing where most of the deposited Fe left the surface and the remaining Fe atoms reconfigured into small nanoparticles suitable for SWNT growth. Interestingly, the average diameters of the SWNTs grown from all iron compounds studied were nearly identical (2.8-3.1 nm). We interpret that the offsetting effects of Ostwald ripening and subsurface diffusion resulted in the ability to grow SWNT forests with similar average diameters regardless of the initial Fe catalyst.     

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.     

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.     

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.     

Patterning catalyst via inkjet printing to grow single-walled carbon nanotubes

We demonstrated a method to pattern catalyst via inkjet printing to grow SWNTs, using metal salt solutions as the inks and an ordinary office-use printer. We printed water solutions of cobalt acetate on hydrophilic Si substrates and grew high quality SWNT films.     

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.     

高温煅烧Mo改性的Fe／MgO催化剂用于制备管径分布均一的单壁碳纳米管

研究了在以甲烷化学气相沉积法制备单壁碳纳米管的过程中高温煅烧预处理(900℃煅烧10h)对Mo改性Fe/MgO催化剂的作用.发现这种预处理有利于Fe在催化剂中的稳定和分散,从而制备出管径均一的单壁碳纳米管.采用能谱元素分析、高分辨透射电镜、X射线衍射、比表面积测量、拉曼光谱和热重分析对样品进行了表征.结果表明,在碳纳米管生长的过程中,铁元素在催化剂表面富集,单壁碳纳米管生长于富集铁的纳米颗粒上,并存在碳管直径与铁颗粒尺寸的依赖关系.Mo存在时可煅烧形成FeMoO4复合氧化物,后者比MgFe2O4相更加稳定.Mo/Fe比例对提高单壁碳纳米管的生长密度、纯度与管径均一性等均有明显影响.上述研究对进一步精确控制制备单壁碳纳米管有重要意义.     

Surfactant-resisted assembly of Fe-containing nanoparticles for site-specific growth of SWNTs on Si surface

This paper describes a facile approach to the site-specific growth of single-walled carbon nanotubes (SWNTs) on silicon surfaces by chemical vapor deposition (CVD). The approach is based on the use of a surfactant as a resist to define patterns of silicon oxide nanodomains onto which nanoparticles of iron hydroxide (Fe(OH)3), 1-5 nm diameter, could be deposited. In base growth mode, the SWNTs can grow from the oxide nanodomains. By controlling the location of oxide nanodomains, site-specific growth could be obtained. The iron hydroxide nanoparticles were prepared by hydrolysis of ferric chloride (FeCl3). Patterned hydroxylated silicon oxide nanodomains were created by scanning probe oxidation (SPO) of silicon substrates modified with aminopropyltrimethoxysilane (APTMS, H2N(CH2)3Si(OCH3)3). Due to electrostatic interaction, Fe(OH)3 nanoparticles can be selectively deposited on hydroxyl groups present on silicon oxide nanodomains. To inhibit the assembly of the nanoparticles on a APTMS-coated silicon surface, sodium dodecyl sulfate (SDS) was introduced, which restricted deposition to the hydroxylated nanodomains. A model mechanism for the selective deposition mechanism has been proposed. It was possible to convert the patterned Fe(OH)3 nanoparticles to iron oxide, which served as a catalyst for the site-specific growth of SWNTs. Raman spectroscopy and AFM were used to characterize the nanotubes on the Si substrate. This will offer the possibility for future integration with conventional microelectronics as well as the development of novel devices.     

A rapid synthesis of iron phosphate nanoparticles via surface-mediated spontaneous reaction for the growth of high-yield, single-walled carbon nanotubes

The direct formation of iron phosphate nanoparticles on hydroxyl-terminated SiO(2)/Si substrates with a narrow size distribution (average diameter = 2.2 nm) is achieved by a simple room temperature spontaneous reaction of ferric chloride and phosphoric acid. Single-walled carbon nanotubes (SWNTs) are grown in high yield from the synthesized iron phosphate nanoparticles by the thermal chemical vapor deposition (CVD) method, as confirmed by atomic force microscopy (AFM) and Raman spectroscopy. Furthermore, three-terminal, p-type, nanotube network field effect transistor (FET) devices are successfully fabricated using the synthesized SWNTs via the photolithography technique. The reduced solubility of Fe(III) ions when they form iron phosphate salts in aqueous media is the main driving force for the nanoparticle formation. Systematic control experiments reveal that the surface property, concentration, and pH of the reaction solution play equally important roles in the formation of nanoparticles.     

Gas sensor array based on metal-decorated carbon nanotubes

Here we demonstrate design, fabrication, and testing of electronic sensor array based on single-walled carbon nanotubes (SWNTs). Multiple sensor elements consisting of isolated networks of SWNTs were integrated into Si chips by chemical vapor deposition (CVD) and photolithography processes. For chemical selectivity, SWNTs were decorated with metal nanoparticles. The differences in catalytic activity of 18 catalytic metals for detection of H(2), CH(4), CO, and H(2)S gases were observed. Furthermore, a sensor array was fabricated by site-selective electroplating of Pd, Pt, Rh, and Au metals on isolated SWNT networks located on a single chip. The resulting electronic sensor array, which was comprised of several functional SWNT network sensors, was exposed to a randomized series of toxic/combustible gases. Electronic responses of all sensor elements were recorded and the sensor array data was analyzed using pattern-recognition analysis tools. Applications of these small-size, low-power, electronic sensor arrays are in the detection and identification of toxic/combustible gases for personal safety and air pollution monitoring.     

Substrate-induced Raman frequency variation for single-walled carbon nanotubes

We report on the monotonic Raman frequency shift and intensity variation when a laser spot moves along the same single-walled carbon nanotube (SWNT) for both the radial-breathing mode (RBM) and the G-band. Our substrates are Si wafers coated with thermal oxide, and trenches with widths of 1-80 mum are etched in the SiO2 by photolithography and reactive ion etching. SWNTs are grown by chemical vapor deposition and lie on top of the SiO2 and across the trenches. When the laser spot moves from the middle of the trench to the SiO2 region along the nanotube, we observe a clear upshift in the RBM and G-band frequencies and a decrease of intensity. The effect is more significant with large ( approximately 2 nm) diameter nanotubes and appears to be chirality dependent. These studies provide important information about environmental effects on single-walled carbon nanotube resonant Raman spectroscopy.     

Electronically selective chemical functionalization of carbon nanotubes: correlation between Raman spectral and electrical responses

Single-walled carbon nanotubes (SWNTs) demonstrate remarkable electronic and mechanical properties useful in developing areas such as nanoelectromechanical systems and flexible electronics. However, the highly inhomogeneous electronic distribution arising from different diameters and chirality in any given as-synthesized SWNT samples imposes severe limitations. Recently demonstrated selective chemical functionalization methods may provide a simple scalable means of eliminating metallic tubes from SWNT transistors and electronic devices. Here, we report on combined electron transport and Raman studies on the reaction of 4-bromobenzene diazonium tetrafluoroborate directly with single and networks of SWNT transistors. First, Raman studies are carried out on isolated individual SWNTs grown on SiO2/Si substrates by chemical vapor deposition with and without metal contacts. Metallic tubes are found to have, on average, higher reactivity toward diazonium reagents. However, a considerable degradation of electrical properties of semiconducting tubes occurs if the reaction is carried out to the point where the conductivity of metallic tubes is significantly suppressed. Insights from single-tube studies are then applied to elucidate the electrical and the Raman responses of SWNT random network transistors of different channel lengths to chemical functionalization.     

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.     

Effects of ionic surfactant adsorption on single-walled carbon nanotube thin film devices in aqueous solutions

Field-effect transistors were fabricated using high-density single-walled carbon nanotube (SWNT) thin films directly grown on suitable substrates. Such approach eliminated the variations of device behaviors in individual SWNT devices by utilizing a large number of SWNTs in each device. We have found that the behaviors of such devices are closely related to the surface charge densities around SWNTs in aqueous solutions. Adsorption of ionic surfactants on the surface could significantly modulate the device characteristics, which could be detected by measuring the conductance of the devices. The devices could be tuned to be sensitive to either anionic or cationic surfactants by tailoring the surface properties of SiO(2) substrates around SWNTs. This effect could be potentially used to design chemical and biological sensors.     

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.     

Insights in the plasma-assisted growth of carbon nanotubes through atomic scale simulations: effect of electric field

Carbon nanotubes (CNTs) are nowadays routinely grown in a thermal CVD setup. State-of-the-art plasma-enhanced CVD (PECVD) growth, however, offers advantages over thermal CVD. A lower growth temperature and the growth of aligned freestanding single-walled CNTs (SWNTs) makes the technique very attractive. The atomic scale growth mechanisms of PECVD CNT growth, however, remain currently entirely unexplored. In this contribution, we employed molecular dynamics simulations to focus on the effect of applying an electric field on the SWNT growth process, as one of the effects coming into play in PECVD. Using sufficiently strong fields results in (a) alignment of the growing SWNTs, (b) a better ordering of the carbon network, and (c) a higher growth rate relative to thermal growth rate. We suggest that these effects are due to the small charge transfer occurring in the Ni/C system. These simulations constitute the first study of PECVD growth of SWNTs on the atomic level.     

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.     

Influence of the catalyst type on the growth of carbon nanotubes via methane chemical vapor deposition

The preparation of the catalyst is one of the key parameters which governs the quality of carbon nanotubes (CNTs) grown by catalyzed chemical vapor deposition (CVD). We investigated the influence of three different procedures of catalyst preparation on the type and diameter of CNTs formed under identical growth conditions via methane CVD. In the first one, chemically synthesized colloidal iron oxide or iron molybdenum alloy nanoparticles were used, which were homogeneously deposited on silicon substrates by spin coating to prevent them from coalescence under CVD growth conditions. The obtained multiwall CNTs (MWNTs) exhibited diameters corresponding to the catalyst particle size, whereas no formation of single-wall CNTs (SWNTs) was observed. In the second method, commercial porous alumina nanoparticles were used in association with iron and molybdenum salts and the Fe/Mo catalyst was formed in situ. We determined that the alumina concentration significantly influenced the morphology of the catalyst and that below a critical value of the range of 1 g/L no CNTs were formed. While yielding nearly defect-free SWNTs, their diameter could not be controlled using this procedure, resulting in a large distribution of tube sizes. In a third, new preparation method, associating alumina and iron-based nanoparticles, SWNTs of a different size and narrower diameter distribution as compared to the second method were obtained. Our results are evidence of the essential role of alumina particles in the formation of SWNTs, and the newly developed method opens up a way to the synthesis of diameter-controlled SWNTs via catalyzed CVD.     

Aqueous treatment of single-walled carbon nanotubes for preparation of Pt–Fe core–shell alloy using galvanic exchange reaction: Selective catalytic activity towards oxygen reduction over methanol oxidation

We have demonstrated a new, cost effective synthesis of single-walled carbon nanotube supported Pt–Fe core–shell alloy catalyst (Pt–Fe/SWNT) for the direct methanol fuel cell using galvanic exchange reaction. The Pt–Fe/SWNTs have shown much larger Pt active surface area (150 m²/g-Pt) than the commercial catalyst (54 m²/g-Pt). Furthermore, four-fold enhancement of catalytic activity of the Pt–Fe/SWNTs for oxygen reduction reaction (ORR) has been observed. This catalyst has also demonstrated its tolerance to methanol in ORR.