Ultrahigh density modulation of aligned single-walled carbon nanotube arrays

Controlling the densities of aligned single-walled carbon nanotube arrays (SWNTs) on ST-cut quartz is a critical step in various applications of these materials. However the growth mechanism for tuning SWNT density using the chemical vapor deposition (CVD) method is still not well understood, preventing the development of efficient ways to obtain the desired results. Here we report a general “periodic” approach that achieves ultrahigh density modulation of SWNT arrays on ST-cut quartz substrates—with densities increased by up to ∼60 times compared with conventional methods using the same catalyst densities—by varying the CH₄ gas “off” time. This approach is applicable to a wide range of initial catalyst densities, substrates, catalyst types and growth conditions. We propose a general mechanism for the catalyst size-dependent nucleation of SWNTs associated with different free carbon concentrations, which explains all the observations. Moreover, the validity of the model is supported by systematic experiments involving the variation of key parameters in the “periodic” CVD approach.      

Odako growth of dense arrays of single-walled carbon nanotubes attached to carbon surfaces

A novel process is demonstrated whereby dense arrays of single-walled carbon nanotubes (SWNT) are grown directly at the interface of a carbon material or carbon fiber. This growth process combines the concepts of SWNT tip growth and alumina-supported SWNT base growth to yield what we refer to as “odako” growth. In odako growth, an alumina flake detaches from the carbon surface and supports catalytic growth of dense SWNT arrays at the tip, leaving a direct interface between the carbon surface and the dense SWNT arrays. In addition to being a new and novel form of SWNT array growth, this technique provides a route toward future development of many important applications for dense aligned SWNT arrays. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. This article is published with open access at Springerlink.com     

Copper catalyzing growth of single-walled carbon nanotubes on substrates

Metallic copper, which is normally considered as a contaminant in the growth of single-walled carbon nanotubes (SWNTs), was found to be an efficient catalyst to grow SWNTs under suitable conditions. It showed very high catalytic activity for the growth of both random SWNT networks and horizontally aligned SWNT arrays. Especially, high-quality SWNT arrays were obtained when monodispersed copper nanoparticles were used. The catalytic behavior of copper for the growth of SWNTs was discussed. The weaker interaction between the copper and silica surfaces plays an important role in the growth of high-quality horizontally aligned SWNT arrays. This new synthesis process of SWNTs with a non-ferromagnetic catalyst brings more convenience to the study of magnetic properties of SWNTs and gives more insight in structure-controlled synthesis of SWNTs.     

Influence of surface chemistry on inkjet printed carbon nanotube films

Carbon nanotube ink chemistry and the proper formulation are crucial for direct-write printing of nanotubes. Moreover, the correct surface chemistry of the self-assembled monolayers that assist the direct deposition of carbon nanotubes onto the substrate is equally important to preserve orientation of the printed carbon nanotubes. We report that the successful formulation of two single walled carbon nanotube (SWNT) inks yields a consistent, homogenous printing pattern possessing the requisite viscosities needed for flow through the microcapillary nozzles of the inkjet printer with fairly modest drying times. The addition of an aqueous sodium silicate allows for a reliable method for forming a uniform carbon nanotube network deposited directly onto unfunctionalized surfaces such as glass or quartz via inkjet deposition. Furthermore, this sodium silicate ingredient helps preserve applied orientation to the printed SWNT solution. Sheet resistivity of this carbon nanotube ink formula printed on quartz decreases as a function of passes and is independent of the substrate. SWNTs were successfully patterned on Au. This amine-based surface chemistry dramatically helps improve the isolation stabilization of the printed SWNTs as seen in the atomic force microscopy (AFM) image. Lastly, using our optimized SWNT ink formula and waveform parameters in the Fuji materials printer, we are able to directly write/print SWNTs into 2D patterns. Dried ink pattern expose and help orient roped carbon nanotubes that are suspended in ordered arrays across the cracks.     

Ultralow feeding gas flow guiding growth of large-scale horizontally aligned single-walled carbon nanotube arrays

On the basis of the rational analysis about the fluidic property of the system, an ultralow gas flow chemical vapor deposition (CVD) strategy was designed to prepare large-scale horizontally aligned ultralong single-walled carbon nanotube (SWNT) arrays. SWNT arrays could be well obtained under extremely low feeding flow of 1.5 sccm in a 1 in. quartz tube reactor. It was confirmed that the tubes grew floatingly and could cross microtrenches or climb over micro-obstacles in ultraslow gas flow. SWNTs arrays also could be formed no matter the substrate was placed vertically or upside down. The growth mechanism was discussed. Both the buoyancy effect induced by gas temperature/density difference and gas flow stability played dominant roles. More attractively, simultaneous batch-scale preparation of SWNT arrays was realized by the ultralow gas flow strategy. This new strategy turns to be more abstemious, efficient, promising, and flexible compared with the high gas flow rate fast-heating CVD processes.     

Catalyst-free growth of oriented single-walled carbon nanotubes on mica by ethanol chemical vapor deposition

In this letter, it is reported for the first time that single-walled carbon nanotubes (SWNTs) can grow on mica substrate without additional catalyst by chemical vapor deposition (CVD) using ethanol as carbon source. The single-wall structure was characterized by Raman spectra and AFM (Atomic Force Microscopy) measurements. The growth of carbon nanotubes on mica surface contributes to the small amount of iron oxide in bare mica. The uniform dispersion and nanosized Fe particles formed from the reduction of iron oxide favor for the growth of SWNTs. Horizontally aligned superlong SWNTs arrays can be successfully generated on the mica surface, which is proved to be guided by the gas flow and under “kite growth mechanism”. The mica is a machinable material which can be easily cut and made a narrow slit on, thus the nanotubes can traverse the slit which can be in millimeter scale and long suspended SWNTs can be generated. This will provide an opportunity to manipulate individual SWNT for various purposes.     

Nanobarrier-terminated growth of single-walled carbon nanotubes on quartz surfaces

Using carbon nanotubes as nanobarriers, the growth of single-walled carbon nanotubes (SWNTs) on a quartz surface can be terminated. First, carbon nanotube nanobarriers were grown on a quartz surface by the gas flow-directed growth mode. Then, the SWNTs were grown on the quartz surface via the lattice-oriented growth mode, in which growth of SWNTs can be terminated by hitting the nanotube nanobarriers. Moreover, using the carbon nanotube nanobarrier as a marker, the mechanism of the growth of SWNTs on the quartz surface can be studied; a base-growth mechanism is indicated. Based on this termination process and the base-growth mechanism, SWNT arrays with controlled lengths can be grown on a quartz surface by fixing the sites of both catalysts and nanobarriers.      

Growth of single-walled carbon nanotube arrays from samarium on substrates

In this letter, it is reported for the first time that samarium is an effective catalyst for single-walled carbon nanotubes(SWNTs) growth via a chemical vapor deposition(CVD) process. Horizontally superlong well-oriented SWNT arrays can be generated under suitable conditions by using ethanol as carbon source. The single-wall structure was characterized by scanning electron microscopy, Raman spectroscopy and atomic force microscopy. The results show that the SWNTs from samarium have better conductivity and better structural uniformity with less defects. This rare earth metal element provides not only an alternative catalyst for SWNTs growth but also a possible way to generate high percentage of superlong semiconducting SWNT arrays for various applications of nanoelectronic device.     

Wafer scale synthesis of dense aligned arrays of single-walled carbon nanotubes

Here we present an easy one-step approach to pattern uniform catalyst lines for the growth of dense, aligned parallel arrays of single-walled carbon nanotubes (SWNTs) on quartz wafers by using photolithography or polydimethylsiloxane (PDMS) stamp microcontact printing (μCP). By directly doping an FeCl₃/methanol solution into Shipley 1827 photoresist or polyvinylpyrrolidone (PVP), various catalyst lines can be well-patterned on a wafer scale. In addition, during the chemical vapor deposition (CVD) growth of SWNTs the polymer layers play a very important role in the formation of mono-dispersed nanoparticles. This universal and efficient method for the patterning growth of SWNTs arrays on a surface is compatible with the microelectronics industry, thus enabling of the fabrication highly integrated circuits of SWNTs.     

Continued growth of single-walled carbon nanotubes

We demonstrate the continued growth of single-walled carbon nanotubes (SWNTs) from ordered arrays of open-ended SWNTs in a way analogous to epitaxy. Nanometer-sized metal catalysts were docked to the SWNT open ends and subsequently activated to restart growth. SWNTs thus grown inherit the diameters and chirality from the seeded SWNTs, as indicated by the closely matched frequencies of Raman radial breathing modes before and after the growth.     

Controlled growth of single-walled carbon nanotubes for unique nanodevices

The controlled growth of bent and horizontally aligned single-walled carbon nanotubes (SWNTs) is demonstrated in this study. The bent SWNTs growth is attributed to the interaction between van der Waals force with substrate and aerodynamic force from gas flow. The curvature of bent SWNTs can be tailored by adjusting the angle between gas flow and step-edge direction. Electrical characterization shows that the one-dimensional resistivity of bent SWNTs is correlated with the curvature, which is due to strain induced energy bandgap variation. Additionally, a downshift of 10 cm(-1) in G-band is found at curved part by Raman analysis, which may be resulted from the bending induced carbon-carbon bond variation. In addition, horizontally aligned SWNTs and crossbar SWNTs were demonstrated. To prove the possibility of integrating the SWNTs having controllable morphology in carbon nanotube based electronics, an inverter with a gain of 2 was built on an individual horizontally aligned carbon nanotube.     

In situ atomic force microscopy tip-induced deformations and Raman spectroscopy characterization of single-wall carbon nanotubes

In this work, an atomic force microscope (AFM) is combined with a confocal Raman spectroscopy setup to follow in situ the evolution of the G-band feature of isolated single-wall carbon nanotubes (SWNTs) under transverse deformation. The SWNTs are pressed by a gold AFM tip against the substrate where they are sitting. From eight deformed SWNTs, five exhibit an overall decrease in the Raman signal intensity, while three exhibit vibrational changes related to the circumferential symmetry breaking. Our results reveal chirality dependent effects, which are averaged out in SWNT bundle measurements, including a previously elusive mode symmetry breaking that is here explored using molecular dynamics calculations.     

Towards a ‘catalyst activity map’ regarding the nucleation and growth of single walled carbon nanotubes

Quantification using scanning electron microscopy (SEM) of single walled carbon nanotubes (SWNTs) grown per unit area using a Co-Fe (50:50) catalyst system, prepared by the incorporation of the appropriate metal salts into a Spin-On Glass substrate, at 900°C. The effects of substrate, as well as catalyst precursor concentration, were investigated. SWNT growth density is maximised with a catalyst precursor concentration of ≥2.5 mM, associated with the formation of catalyst nanoparticles of a critical size for SWNT nucleation. Samples were subjected to secondary growth, using a range of H₂:CH₄ ratios to determine the optimum precursor composition. It was found that nucleation and growth stages are optimal under different conditions. Optimum conditions for nucleation resulted in >10× increase in SWNT density. Optimisation is dependent on temperature and the partial pressure of reagent gas species.     

Cadmium-catalyzed surface growth of single-walled carbon nanotubes with high efficiency

We demonstrate that cadmium (Cd) can catalyze the growth of single-walled carbon nanotubes (SWNTs) with high efficiency. The Cd nanocatalysts, prepared using a diblock copolymer templating method, were uniformly spaced over a large deposition area with an average diameter of 1.9 nm and narrow size distribution. By using the normal-heating and fast-heating method, random and horizontally aligned arrays of SWNTs can be generated. The density of the SWNTs can be altered by the chemical vapor deposition conditions. The morphology and microstructure of the SWNTs characterized by scanning electron microscopy, Raman spectroscopy, atomic force microscopy, and high-resolution transmission electron microscopy revealed that the grown nanotubes do not have carbonaceous particles and have good crystallinity. In addition, after careful check with superlong nanotubes 735 out of 790 nanotubes were found to be deposited with Ag (93%) and only 7% SWNTs without Ag deposition. While for superlong SWNT arrays from Fe, 32% long SWNTs without Ag deposition was found, the high percentage of SWNTs with Ag deposition from Cd indicates that the SWNTs have better conductivity and better structural uniformity with less defects.     

Co-synthesis of single-walled carbon nanotubes and carbon fibers

A new vertical floating catalytic technique is developed and used to prepare both single-walled carbon nanotubes (SWNTs) and carbon fibers (CFs). Scanning electron microscopy (SEM) observation shows a clear separation of these two materials. Thin films of SWNTs can be peeled easily from the CF substrate which just acts as a catalyst support for the SWNT growth. The production process is also semicontinuous, resulting in a yield of ∼1.0 g h⁻¹ of SWNTs film with high purity. Structure and vibrational properties of these materials are investigated by electron microscopy and Raman spectroscopy, respectively.     

Guided growth of large-scale, horizontally aligned arrays of single-walled carbon nanotubes and their use in thin-film transistors

A convenient process for generating large-scale, horizontally aligned arrays of pristine, single-walled carbon nanotubes (SWNTs) is described. The approach uses guided growth, by chemical vapor deposition (CVD), of SWNTs on miscut single-crystal quartz substrates. Studies of the growth reveal important relationships between the density and alignment of the tubes, the CVD conditions, and the morphology of the quartz. Electrodes and dielectrics patterned on top of these arrays yield thin-film transistors that use the SWNTs as effective thin-film semiconductors. The ability to build high-performance devices of this type suggests significant promise for large-scale aligned arrays of SWNTs in electronics, sensors, and other applications.     

Horizontally aligned single-walled carbon nanotube on quartz from a large variety of metal catalysts

Horizontally aligned single-walled carbon nanotubes (SWNTs) are highly desired for SWNT device applications. A large variety of metals including Fe, Co, Ni, Cu, Pt, Pd, Mn, Mo, Cr, Sn, Au, Mg, and Al successfully catalyzed the growth of such tubes on stable temperature (ST)-cut quartz by lattice guidance. In addition, Mg and Al were presented to produce random and aligned SWNTs for the first time. A hypothesis is proposed in which the precipitated carbon shell on the outer surface of the metal catalysts guides the alignment along the crystal lattice but not the catalysts themselves. By elucidating the role of the catalysts, an understanding of the aligned growth mechanism on quartz is further improved. Moreover, a simple "scratch" method by a razor blade such as the carbon steel and tungsten carbide (with 9% cobalt) is presented to pattern the "catalysts" without any complex processing steps such as lithography for the aligned SWNT growth.     

Wafer‐Scale Fabrication of Suspended Single‐Walled Carbon Nanotube Arrays by Silver Liquid Dynamics

Suspended single‐walled carbon nanotubes (SWNTs) have advantages in mechanical resonators and highly sensitive sensors. Large‐scale fabrication of suspended SWNTs array devices and uniformity among SWNTs devices remain a great challenge. This study demonstrates an effective, fast, and wafer‐scale technique to fabricate suspended SWNT arrays, which is based on a dynamic motion of silver liquid to suspend and align the SWNTs between the prefabricated palladium electrodes in high temperature annealing treatment. Suspended, strained, and aligned SWNTs are synthesized on a 2 × 2 cm² substrate with an average density of 10 tubes per micrometer. Under the optimal conditions, almost all SWNTs become suspended. A promising formation model of suspended SWNTs is established. The Kelvin four‐terminal resistance measurement shows that these SWNT array devices have extreme low contact resistance. Meanwhile, the suspended SWNT array field effect transistors are fabricated by selective etching of metallic SWNTs using electrical breakdown. This method of large‐scale fabrication of suspended architectures pushes the study of nanoscale materials into a new stage related to the electrical physics and industrial applications.     

Unexpected hole transfer leads to high efficiency single-walled carbon nanotube hybrid photovoltaic

We report surprisingly efficient photocurrent generation at individual single-walled carbon nanotube (SWNT) /poly(3-hexylthiophene-2,5-diyl) (P3HT) junctions. Contrary to previous prediction, both semiconducting SWNTs (s-SWNTs) and metallic SWNTs (m-SWNTs) function as efficient hole acceptors. By active tuning of SWNTs' Fermi level, we confirm that P3HT p-dopes both s-SWNT and m-SWNT, and the work function difference between the nanotube and P3HT leads to a built-in voltage driving the efficient exciton dissociation and hole transfer. We further demonstrate square millimeter scale SWNT/P3HT bilayer photovoltaics using horizontally aligned SWNT arrays. Importantly, the devices exhibit greater than 90% effective external quantum efficiency. These key findings will not only enhance our knowledge of photocurrent generation at nanoscale interfaces, but also make selective omission of m-SWNT redundant, promising carbon nanomaterial-based, low-cost, high-efficiency hybrid photovoltaics.     

Chemical vapour deposition of single walled carbon nanotubes freely suspended over nanotube supports

Single walled carbon nanotubes (SWNTs) suspended above the substrate can be fabricated simply and rapidly by chemical vapour deposition growth over pre-grown multi-walled carbon nanotubes (MWNTs). SWNTs are suspended either on a randomly organized carbon nanotube network on an unpatterned substrate, or between organized pillars made from vertically aligned nanotube forests on a patterned substrate. All nanotubes are produced during a single growth run using a two step growth technique. This approach enables the fabrication of laterally suspended SWNT networks which are well suited for optical applications.