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.     

Nanoscopically flat open-ended single-walled carbon nanotube substrates for continued growth

Continued growth is a way of growing nanotubes targeted to produce continuous and chirality-controlled single-walled carbon nanotube (SWNT) materials. This growth method strongly depends on efficient preparation of open-ended SWNT substrates. Nanoscopically flat open-ended SWNT substrates have been prepared by cutting the SWNT spun fiber with a focused ion beam cutting technique and followed by etching schemes for cleaning amorphous carbon and opening the ends of the SWNTs. The open ends were effectively characterized through selective etch back of open SWNT ends by carbon dioxide gas at 950 degrees C. High density continued growth was demonstrated from these nanoscopically flat open-ended substrates.     

Negative temperature coefficient of single-walled carbon nanotube-gold nanoparticle hybrid structures

Single-walled carbon nanotubes (SWNTs) were grown on gold nanoparticle (GNP) coated quartz substrates by alcohol catalytic chemical vapor deposition. The GNP coated substrates were coated with Co catalyst by a dip-coat method. The growth was then carried out at 800 degrees C under a pressure of 10 Torr in an atmosphere of ethanol vapor for 30 min. Characterizations have shown larger SWNT diameters with higher negative temperature coefficients for GNP coated substrates as compared to those of quartz substrates without GNPs. It is attributed that SWNT-GNP hybrid structures have a higher fraction of semiconductor-type pathways.     

Identifying and counting point defects in carbon nanotubes

The prevailing conception of carbon nanotubes and particularly single-walled carbon nanotubes (SWNTs) continues to be one of perfectly crystalline wires. Here, we demonstrate a selective electrochemical method that labels point defects and makes them easily visible for quantitative analysis. High-quality SWNTs are confirmed to contain one defect per 4 microm on average, with a distribution weighted towards areas of SWNT curvature. Although this defect density compares favourably to high-quality, silicon single-crystals, the presence of a single defect can have tremendous electronic effects in one-dimensional conductors such as SWNTs. We demonstrate a one-to-one correspondence between chemically active point defects and sites of local electronic sensitivity in SWNT circuits, confirming the expectation that individual defects may be critical to understanding and controlling variability, noise and chemical sensitivity in SWNT electronic devices. By varying the SWNT synthesis technique, we further show that the defect spacing can be varied over orders of magnitude. The ability to detect and analyse point defects, especially at very low concentrations, indicates the promise of this technique for quantitative process analysis, especially in nanoelectronics development.     

Low temperature synthesis of single-walled carbon nanotubes in an inductively coupled plasma chemical vapor deposition system

In this work, we present a parametric study on the low temperature synthesis of single-walled carbon nanotubes (SWNTs) in an inductively coupled plasma (ICP) CVD system using dry bi-layered catalytic thin-films (Fe/Al and Ni/Al, deposited by electron-beam evaporation method) as the catalysts. With a low substrate temperature of 550 degrees C and above, SWNTs were successfully synthesized on both catalysts, as revealed from the characteristic peaks of SWNTs in the micro-Raman spectra. By the reduction of plasma power and the shortening of the process times, the lowest synthesis temperature of SWNTs achieved in our system was approached to 500 degrees C on Ni/Al catalysts; on the other hands, the lowest temperature for Fe/Al catalysts was 550 degrees C. Our results suggest that as compared with Fe/Al, Ni/Al is more favorable for plasma-enhanced CVD (PECVD) synthesis of SWNTs at low temperatures. This work can be used for further improvements and better understanding on the production processes of SWNTs by PECVD methods.     

Mo-Co catalyst nanoparticles: Comparative study between TiN and Si surfaces for single-walled carbon nanotube growth

Highly pure single-walled carbon nanotubes (SWNT) were synthesized by alcohol catalytic chemical vapor deposition on silicon substrates partially covered by a thin layer of TiN. The TiN coating selectively prevented the growth of carbon nanotubes. Field emission scanning electron microscopy and Raman spectroscopy revealed the formation of high purity vertically aligned SWNT in the Si region. X-ray Photoelectron Spectroscopy and Atomic Force Microscopy indicated that Co nanoparticles are present on the Si regions, and not on the TiN regions. This clearly explains the obtained experimental results: the SWNT only grow where the Co is presented as nanoparticles, i.e. on the Si regions.     

Facile fabrication of all-SWNT field-effect transistors

Field-effect transistors (FETs) have been fabricated using as-grown single-walled carbon nanotubes (SWNTs) for the channel as well as both source and drain electrodes. The underlying Si substrate was employed as the back-gate electrode. Fabrication consisted of patterned catalyst deposition by surface modification followed by dip-coating and synthesis of SWNTs by alcohol chemical vapor deposition (CVD). The electrodes and channel were grown simultaneously in one CVD process. The resulting FETs exhibited excellent performance, with an I _ON/I _OFF ratio of 10⁶ and a maximum ON-state current (I _ON) exceeding 13 μA. The large I _ON is attributed to SWNT bundles connecting the SWNT channel with the SWNT electrodes. Bundling creates a large contact area, which results in a small contact resistance despite the presence of Schottky barriers at metallic-semiconducting interfaces. The approach described here demonstrates a significant step toward the realization of metal-free electronics.      

Synthesis-condition dependence of carbon nanotube growth by alcohol catalytic chemical vapor deposition method

We report the dependence of growth yield of single-walled carbon nanotubes (SWNTs) on heat-treatment time and catalyst film thickness by the alcohol catalytic chemical vapor deposition method. Three types of heat-treatment, synthesis of 30 min, synthesis of 30 min after annealing of 30 min, and synthesis of 60 min, were investigated. Thickness of Co catalyst film was varied from 1 to 10 nm. In the case of thinner Co film less than 3 nm, long synthesis time of 60 min is favorable for the effective SWNT growth, because of the small amount of Co catalyst. In the case of thicker Co film more than 3 nm, an amount of grown SWNTs by 30 min synthesis after 30 min annealing and by 60 min synthesis was much higher than that by 30 min synthesis without annealing, showing that total heat-treatment time of 60 min is important for the SWNT growth. Results suggest that the conversion from the thicker film of Co to nano-particle which acts as catalyst takes place during the first 30 min.     

Detection of a nerve agent simulant using single-walled carbon nanotube networks: dimethyl-methyl-phosphonate

Single-walled carbon nanotube (SWNT) networks were used to detect hazardous dimethyl-methyl-phosphonate (DMMP) gas in real time, employing two different metals as electrodes. Random networks of SWNTs were simply obtained by drop-casting a SWNT-containing solution onto a surface-oxidized Si substrate. Although the electrical responses to DMMP at room temperature were reversible for both metals, the Pd-contacting SWNT network sensors exhibited a higher response and a shorter response time than those of the Au-contacting SWNT network sensors at the same DMMP concentration, due to the stronger interactions between the SWNTs and Pd surface atoms. In Pd-contacting SWNT network sensors, the response increased linearly with increasing DMMP concentration and reproducible response curves were obtained for DMMP levels as low as 1 ppm. These results indicate that SWNT networks in contact with Pd electrodes can function as good DMMP sensors at room temperature with scalable and fast response and excellent recovery.     

Charge Transfer from Carbon Nanotubes to Silicon in Flexible Carbon Nanotube/Silicon Solar Cells

Mechanical fragility and insufficient light absorption are two major challenges for thin flexible crystalline Si‐based solar cells. Flexible hybrid single‐walled carbon nanotube (SWNT)/Si solar cells are demonstrated by applying scalable room‐temperature processes for the fabrication of solar‐cell components (e.g., preparation of SWNT thin films and SWNT/Si p–n junctions). The flexible SWNT/Si solar cells present an intrinsic efficiency ≈7.5% without any additional light‐trapping structures. By using these solar cells as model systems, the charge transport mechanisms at the SWNT/Si interface are investigated using femtosecond transient absorption. Although primary photon absorption occurs in Si, transient absorption measurements show that SWNTs also generate and inject excited charge carriers to Si. Such effects can be tuned by controlling the thickness of the SWNTs. Findings from this study could open a new pathway for designing and improving the efficiency of photocarrier generation and absorption for high‐performance ultrathin hybrid SWNT/Si solar cells.     

Hierarchical Three-Dimensional Layer-by-Layer Assembly of Carbon Nanotube Wafers for Integrated Nanoelectronic Devices

We report a general approach to overcome the enormous obstacle of the integration of CNTs into devices by bonding single-walled carbon nanotubes (SWNTs) films to arbitrary substrates and transferring them into densified and lithographically processable "CNT wafers". Our approach allows hierarchical layer-by-layer assembly of SWNTs into organized three-dimensional structures, for example, bidirectional islands, crossbar arrays with and without contacts on Si, and flexible substrates. These organized SWNT structures can be integrated with low-power resistive random-access memory.     

Diameter controlled chemical vapor deposition synthesis of single-walled carbon nanotubes

In this study, we systematically investigated the influence of catalyst preparation procedures on the mean diameter of single-walled carbon nanotubes (SWNTs) synthesized by the alcohol catalytic chemical vapor deposition (ACCVD) process. It was found that the SWNT diameter is dependent upon both reduction temperature and time, with lower reduction temperature and/or shorter reduction time resulting in smaller diameter SWNTs. The morphology of the SWNTs also changed from vertically aligned to randomly oriented when the reduction temperature was below 500 degrees C. We also found that introducing a small amount of water during the catalyst reduction stage significantly decreased the mean diameter of the SWNTs. Lastly, we report on the use of a new binary catalyst system in which rhodium was combined with cobalt. This new Co/Rh combination produced SWNTs of smaller diameter than the conventional Co/Mo catalyst.     

Direct observation of the strong interaction between carbon nanotubes and quartz substrate

We present a chemical vapor deposition (CVD) method for the growth of uniform single-walled carbon nanotube (SWNT) arrays on a stable temperature (ST)-cut single crystal quartz substrate using a mixture of methanol and ethanol as carbon source. It is found that introducing methanol during the growth can improve the density and the length of the well-aligned SWNTs in the arrays as well as increase the SWNT/quartz interaction. Obvious “up-shifts” of G-band frequencies in the Raman spectra have been found for the aligned SWNTs. A welldesigned control experiment shows that the G-band “up-shifts” originate from the strong interaction between SWNTs and the quartz substrate. It is believed that exploring this interaction will help to elucidate the growth mechanism; ultimately, this will help realize the promise of controlling the chirality of SWNTs.     

Employing Raman spectroscopy to qualitatively evaluate the purity of carbon single-wall nanotube materials

Carbon single-wall nanotubes (SWNTs) have highly unique electronic, mechanical and adsorption properties, making them interesting for a variety of applications. Raman spectroscopy has been demonstrated to be one of the most important methods for characterizing SWNTs. For example, Raman spectroscopy may be employed to differentiate between metallic and semi-conducting nanotubes, and may also be employed to determine SWNT diameters and even the nanotube chirality. Single-wall carbon nanotubes are generated in a variety of ways, including arc-discharge, laser vaporization and various chemical vapor deposition (CVD) techniques. In all of these methods, a metal catalyst must be employed to observe SWNT formation. Also, all of the current synthesis techniques generate various non-nanotube carbon impurities, including amorphous carbon, fullerenes, multi-wall nanotubes (MWNTs) and nano-crystalline graphite, as well as larger micro-sized particles of graphite. For any of the potential nanotube applications to be realized, it is, therefore, necessary that purification techniques resulting in the recovery of predominantly SWNTs at high-yields be developed. It is, of course, equally important that a method for determining nanotube wt.% purity levels be developed and standardized. Moreover, a rapid method for qualitatively measuring nanotube purity could facilitate many laboratory research efforts. This review article discusses the application of Raman spectroscopy to rapidly determine if large quantities of carbon impurities are present in nanotube materials. Raman spectra of crude SWNT materials reveal tangential bands between 1500-1600 cm(-1), as well as a broad band at approximately 1350 cm(-1), attributed to a convolution of the disorder-induced band (D-band) of carbon impurities and the D-band of the SWNTs themselves. Since the full-width-at-half-maximum (FWHM) intensity of the various carbon impurity D-bands is generally much broader than that of the nanotube D-band, an indication of the SWNT purity level may be obtained by simply examining the line-width of the D-band. We also briefly discuss the effect of nanotube bundling on SWNT Raman spectra. Finally, sections on employing Raman spectroscopy, and Raman spectroscopy coupled with additional techniques, to identify the separation and possible isolation of a specific nanotube within purified SWNT materials is provided. Every SWNT can be considered to be a unique molecule, with different physical properties, depending on its (n, m) indices. The production of phase-pure (n, m) SWNTs may be essential for some nanotube applications.     

Biocompatibility of native and functionalized single-walled carbon nanotubes for neuronal interface

Single-walled carbon nanotubes (SWNTs) have unique mechanical, electrical, and optical properties and can be easily chemically modified; features that make them excellent candidate materials for applications as sensors and stimulators in neuronal tissue engineering. The purpose of this study was to demonstrate that SWNTs can support neuronal attachment and growth, that simple chemical modifications can be employed to control cell growth, that SWNTs do not interfere with ongoing neuronal function, and that neurons can be electrically coupled to SWNTs. Growth and attachment of the neuroblastoma*glioma NG108, a model neuronal cell, was assessed on unmodified SWNT substrates or substrates from SWNTs modified with 4-benzoic acid or 4-tert-butylphenyl functional groups using a simple functionalization method. SWNT films support cell growth, but at a reduced level compared to tissue culture-treated polystyrene. The order of viability and cell attachment was tissue culture treated polystyrene > SWNTs > 4-tert-butylphenyl-functionalized SWNTs > 4-benzoic acid-functionalized SWNTs. Decreased cell growth after culture on untreated (non adherent) polystyrene suggested that cell attachment was a critical determinant of proliferation and cell growth on SWNTs. Fluorescence and scanning electron microscopy revealed decreased neurite outgrowth in NG108 grown on SWNT substrates. We are also among the first groups to demonstrate electrical coupling of SWNTs and neurons by demonstrating that NG108 and rat primary peripheral neurons showed robust voltage-activated currents when electrically stimulated through transparent, conductive SWNT films. Our data suggest that SWNTs are flexible resource materials for tissue engineering application involving electrically excitable tissues such as muscles and nerves.     

Synthesis-condition dependence of carbon nanotube growth by alcohol catalytic chemical vapor deposition method

We report the dependence of growth yield of single-walled carbon nanotubes (SWNTs) on heat-treatment time and catalyst film thickness by the alcohol catalytic chemical vapor deposition method. Three types of heat-treatment, synthesis of 30 min, synthesis of 30 min after annealing of 30 min, and synthesis of 60 min, were investigated. Thickness of Co catalyst film was varied from 1 to 10 nm. In the case of thinner Co film less than 3 nm, long synthesis time of 60 min is favorable for the effective SWNT growth, because of the small amount of Co catalyst. In the case of thicker Co film more than 3 nm, an amount of grown SWNTs by 30 min synthesis after 30 min annealing and by 60 min synthesis was much higher than that by 30 min synthesis without annealing, showing that total heat-treatment time of 60 min is important for the SWNT growth. Results suggest that the conversion from the thicker film of Co to nano-particle which acts as catalyst takes place during the first 30 min.     

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.     

Diode-like properties of as-grown chemical vapor deposited single-walled carbon nanotubes

Current rectification property of as-grown single-walled carbon nanotubes (SWNTs) is investigated. The SWNTs are grown by chemical vapor deposition (CVD) process. The process allowed to grow long strands of SWNT bundles, which are then used to fabricate multiple arrays of switching devices with the channel length of 3, 5, 7 and 10 microm on a 15 mm x 15 mm SiO2 on Si substrate. Regardless of the channel length, a majority of the fabricated devices show current rectification characteristics, with high throughput of current (I) in the forward bias (V) giving the forward and reverse current ratio (Ifor/Irev) of approximately 10(6). Atomic force microscopic (AFM) analysis of the device structure and surface topology of SWNT suggest the observed rectification of current to possibly result from (a) cross-tube junctions, (b) a mixture of metallic and semiconducting tubes in the SWNT bundles, and/or (c) chirality change along a single tube. The exact mechanism underlying the observed rectification could not be conclusively established. However, the analyses of the experimental results strongly suggest the observed rectification to result from Schottky-type diode properties of SWNTs with mixed chirality along the tube.     

Charge Transfer at Junctions of a Single Layer of Graphene and a Metallic Single Walled Carbon Nanotube

Junctions between a single walled carbon nanotube (SWNT) and a monolayer of graphene are fabricated and studied for the first time. A single layer graphene (SLG) sheet grown by chemical vapor deposition (CVD) is transferred onto a SiO₂/Si wafer with aligned CVD‐grown SWNTs. Raman spectroscopy is used to identify metallic‐SWNT/SLG junctions, and a method for spectroscopic deconvolution of the overlapping G peaks of the SWNT and the SLG is reported, making use of the polarization dependence of the SWNT. A comparison of the Raman peak positions and intensities of the individual SWNT and graphene to those of the SWNT‐graphene junction indicates an electron transfer of 1.12 × 10¹³ cm^?2 from the SWNT to the graphene. This direction of charge transfer is in agreement with the work functions of the SWNT and graphene. The compression of the SWNT by the graphene increases the broadening of the radial breathing mode (RBM) peak from 3.6 ± 0.3 to 4.6 ± 0.5 cm^?1 and of the G peak from 13 ± 1 to 18 ± 1 cm^?1, in reasonable agreement with molecular dynamics simulations. However, the RBM and G peak position shifts are primarily due to charge transfer with minimal contributions from strain. With this method, the ability to dope graphene with nanometer resolution is demonstrated.     

Synthesis and characterization of new polyaniline/nanotube composites

New polyaniline/nanotube (PANI/NT) composites have been synthesized by “in situ” polymerization processes using both multi-wall carbon nanotubes (MWNTs) and single-wall carbon nanotubes (SWNTs) in concentrations ranging from 2 to 50 wt.%. Although no structural changes are observed using MWNTs above a concentration of 20 wt.%, the in situ synthesis results in electronic interactions between nanotubes and the quinoid ring of PANI leading to enhanced electronic properties and thus to the formation of a genuine PANI/MWNT composite material. On the other hand, using SWNTs favors the formation of inhomogeneous mixtures rather than of a homogeneous composite materials, independent of the SWNT concentration. X-ray diffraction, Raman and transport measurements show the different behavior of both classes of nanotubes in PANI/NT materials. The difficulties in the formation of a true PANI/SWNT composite are related to the far more complex structure of the SWNT material itself, i.e. to the presence of entangled bundles of SWNTs, amorphous carbon and even catalytic metal particles.