Preferential Growth of Semiconducting Single-Walled Carbon Nanotubes on Substrate by Europium Oxide

In this paper, we have demonstrated that europium oxide (Eu₂O₃) is a new type of active catalyst for single-walled carbon nanotubes (SWNTs) growth under suitable conditions. Both random SWNT networks and horizontally aligned SWNT arrays are efficiently grown on silicon wafers. The density of the SWNT arrays can be altered by the CVD conditions. This result further provides the experimental evidence that the efficient catalyst for SWNT growth is more size dependent than the catalysts themselves. Furthermore, the SWNTs from europium sesquioxides have compatibly higher quality than that from Fe/Mo catalyst. More importantly, over 80% of the nanotubes from Eu₂O₃ are semiconducting SWNTs (s-SWNTs), indicating the preferential growth of s-SWNTs from Eu₂O₃. This new finding could open a way for selective growth of s-SWNTs, which can be used as high-current nanoFETs and sensors. Moreover, the successful growth of SWNTs by Eu₂O₃ catalyst provides new experimental information for understanding the preferential growth of s-SWNTs from Eu₂O₃, which may be helpful for their controllable synthesis.     

Lateral growth of single-walled carbon nanotubes across electrodes and the electrical property characterization

To realize the commercialization of single-walled carbon nanotube (SWNT)-based nanoelectronic and optoelectronic devices, the development of a fabrication process of catalytic chemical vapour deposition (CCVD) growth of SWNTs across electrodes is required. In this work, we report on the process of the lateral growth of SWNTs across catalytic pads. Using the conventional photolithography technique followed by thin film evaporation and lift off, the catalytic pads were prepared, consisting of nickel (Ni) and silicon dioxide (SiO₂) double layers, on the thermal silicon oxide substrate. The SWNTs were laterally grown across the catalytic pads in a thermal pyrolysis CVD system at 800–900 °C fed with a mixed gas flow of methane (CH₄) and hydrogen (H₂). The SiO₂, as the upper layer on Ni pads, not only plays a role as a barrier to prevent vertical growth but also serves as a porous medium that helps in forming smaller nano-sized Ni particles, so that the use of ultrathin Ni film would not be necessary for growth of SWNTs. Lateral growth across pads of various inter-spacing up to tens of microns was conducted for devices of different applications. The characterization by micro-Raman spectroscopy, atomic force microscopy and electron microscopy revealed the structure and diameters of the SWNTs and most importantly the SWNT density controlled by changing growth temperature. Following SWNTs growth, post-definition of metallic electrodes was conducted and the electrical properties were also measured.     

Surface modification of single‐walled carbon nanotubes with polyethylene via in situ Ziegler–Natta polymerization

Single‐walled carbon nanotubes (SWNTs) were modified with polyethylene (PE) prepared by in situ Ziegler–Natta polymerization. Because of the catalyst pretreated on the surface of the SWNTs, the ethylene was expected to polymerize there. Scanning electron microscopy images and solubility measurements showed that the surface of the SWNTs was covered with a PE layer, and a crosslink may have formed between the SWNTs and PE. When the SWNTs covered with a PE layer were mixed with commercialized PE by melt blending, the resulting composite had better mechanical properties than the composite from the SWNTs without a PE layer. The yield strength, the tensile strength and modulus, the strain at break, and the fracture energy of the modified‐SWNT/PE composites were improved by 25, 15.2, 25.4, 21, and 38% in comparison with those of the raw‐SWNT/PE composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3697–3700, 2004     

Synthesis and properties of poly(methyl methacrylate)/carbon nanotube composites covalently integrated through in situ radical polymerization

Poly(methyl methacrylate) (PMMA)/single‐walled carbon nanotube (SWNT) composites were synthesized by the grafting of PMMA onto the sidewalls of SWNTs via in situ radical polymerization. The free‐radical initiators were covalently attached to the SWNTs by a well‐known esterification method and confirmed by means of thermogravimetric analysis and Fourier transform infrared spectroscopy. Scanning electron microscopy and transmission electron microscopy were used to image the PMMA–SWNT composites; these images showed the presence of polymer layers on the surfaces of debundled, individual nanotubes. The PMMA–SWNT composites exhibited better solubility in chloroform than the solution‐blended composite materials. On the other hand, compared to the neat PMMA, the PMMA–SWNT nanocomposites displayed a glass‐transition temperature up to 6.0°C higher and a maximum thermal decomposition temperature up to 56.6°C higher. The unique properties of the nanocomposites resulted from the strong interactions between the SWNTs and the PMMA chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Complete elimination of metal catalysts from single wall carbon nanotubes

The complete removal of entrapped metallic impurities (i.e. Ni and Co) incorporated within single wall carbon nanotubes (SWNTs) has been a long-standing issue. A sonication-mediated treatment of as-obtained SWNT soot in a 1:1 mixture of aqueous hydrofluoric and nitric acids resulted in the complete elimination of these impurities as shown by energy dispersive X-ray analysis (EDAX). Contact angle measurements indicated that the wetting of SWNTs is enhanced in the presence of HF. The presence of HNO₃ and surfactant was found essential in removing the catalyst due to SWNT etching of end-caps/defects and providing better dispersion, respectively. Moreover, Raman spectroscopy indicated that the structural purity of the SWNTs is not compromised by the HF/HNO₃ purification treatment.     

An effective surfactant-free isolation procedure for single-wall carbon nanotubes

An optimised isolation procedure of single-wall carbon nanotubes (SWNTs) from a SWNT soot without using any surfactant is reported. Amorphous carbon and small graphitic particles were washed away with N-methyl-2-pyrrolidone (NMP) and acetone. A large amount of graphite-coated metal particles were removed with the oxidation of the SWNT material with HNO₃ (6.5 and 4 M) and by washing the oxidised SWNT material with a mixture of methanol (MeOH) and deionised water. The isolated material was investigated with transmission electron microscopy (TEM) and Raman scattering (647.1 and 532 nm). An elemental analysis of the content of Co and Ni in the SWNT samples isolated at different steps of the isolation procedure was performed. On the basis of the TEM images and elemental analysis it was estimated that the purified material contains more than 75 wt.% of SWNTs.     

Fabrication of surfactant‐removed polymer composites with single‐walled carbon nanotube networks

Polystyrene (PS) composites with a network of single‐walled carbon nanotubes (SWNTs) were fabricated by using monodispersed PS micospheres. First, PS spheres and surfactant‐dispersed SWNTs were mixed in water, then a hybrid cake was obtained by filtration via a microporous membrane and the SWNTs were filled within the spaces of packed polymer spheres. At this stage, the surfactants for dispersing SWNTs were totally removed from the composites by a thorough washing. Then the composite films with SWNT networks were obtained by compression molding at 160°C. Structure of the composites had been characterized by transmission electron microscopy and scanning electron microscopy. The present SWNT composites showed a low percolation threshold of electrical conductivities. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of single-walled carbon nanotubes on morphology and mechanical properties of NBR/PVC blends

Dynamically vulcanized thermoplastic elastomer based on Nitrile butadiene-rubber (NBR)/PVC with functionalized single-walled carbon nanotubes (f-SWNTs) and non-functionalized single-walled carbon nanotubes (SWNTs) were prepared using a brabender internal mixer. Effects of two types of SWNTs (functionalized and non-functionalized) on morphology and mechanical properties of NBR/PVC blends were studied. Results showed that the mechanical properties of NBR/PVC/SWNTs nanocomposites improved with the increasing of SWNTs content and in particular with the increase of f-SWNTs content. Moreover, the enhancement of mechanical properties of NBR/PVC blends reinforced with functionalized SWNT was higher than that of NBR/PVC blends with non-functionalized SWNT. Dispersion of SWNTs and morphology of NBR/PVC/SWNT nanocomposites were determined by scanning electron microscopy and transmission electron microscopy (TEM) techniques. TEM images illustrated that f-SWNTs were dispersed uniformly in NBR/PVC matrix while non-functionalized SWNTs showed much aggregation. Dynamic mechanical thermal analysis of NBR/PVC/SWNTs nanocomposites was also studied. The outcomes indicated that in the case of f-SWNTs, the intensity of tan ?? peak was lower than that in the case of non-functionalized SWNTs. Meanwhile, the intensity of tan ?? peak reduced when the content of f-SWNTs was increased.     

Effects of buffer layer materials and process conditions on growth mechanisms of forming networks of SWNTs by microwave plasma chemical vapor deposition

This study investigates the growth mechanism of IC compatible processes and to the feasibility of synthesizing networks of single-walled carbon nanotubes (SWNTs) at lower temperatures (610 °C) on Si wafer using microwave plasma chemical vapor deposition (MPCVD) with CH₄ and H₂ as source gases. The effects of the buffer layer materials (ZnS–SiO₂, Al₂O₃, AlON, and AlN ) and process conditions on growth of carbon nanostructures with Co as catalyst were also examined, where the buffer layers and Co catalyst were deposited in sequence by physical vapor deposition (PVD), followed by H-plasma pretreatment before deposition of carbon nanostructures. Additionally, the morphologies and bonding structures of carbon nanostructures were characterized by field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), and Raman Spectroscopy. Analytical results demonstrate that networks of SWNTs are more favorable to be synthesized by selecting proper buffer layer material (e.g., AlON), and under higher temperatures, thinner catalyst thickness (e.g., 5 nm) and lower CH₄ / H₂ ratio (e.g., 5 / 100 sccm/sccm). The networks of SWNTs can be fabricated at temperatures as low as 610 °C by manipulating these parameters. In conclusion, the growth mechanism determines the conditions for the formation of nano-sized extrusions on catalyst particles surface.     

Hierarchical morphology of carbon single-walled nanotubes during sonication in an aliphatic diamine

Dispersion of single-walled carbon nanotubes (SWNTs) by sonication into diamine curing agents is studied as a means to improve the dispersion of SWNTs in cured epoxy. Cured and uncured specimens are analyzed by light microscopy, electron microscopy, light scattering (LS), ultra small-angle X-ray scattering (USAXS), electrical conductivity and Raman spectroscopy. A flexible diamine (D2000) forms a stable SWNT suspension leading to good homogeneity in both the diamine and the cured epoxy. High resolution transmission electron microscopy (TEM) shows that small ropes of SWNTs (mostly under 15 nm) are present despite the sample's visual homogeneity. Further morphological investigation of cured and uncured D2000 resins using light and small-angle X-ray scattering indicates that the SWNTs are networked into fractal clusters that electrically percolate at low SWNTs loadings (0.05 wt%).     

Hybrid gas sensor based on platinum nanoparticles/poly(methyl methacrylate)-coated single-walled carbon nanotubes for dichloromethane detection with a high response magnitude

A dichloromethane (DCM) sensor with a high response magnitude was successfully fabricated using the integration of single-walled carbon nanotubes (SWNTs), poly(methyl methacrylate) (PMMA) and platinum nanoparticles (Pt NPs). A pristine SWNT network was first formed by drop-casting onto printed circuit board (PCB) substrates. Next, PMMA was coated onto the pre-dropped SWNT network by spin coating using a PMMA-toluene solution, followed by the deposition of Pt NPs by electron-beam evaporation (hereafter referred to as Pt/PMMA/SWNT). The Pt/PMMA/SWNT enabled an approximately 69-fold improvement in DCM detection compared to pristine SWNT. The high response magnitude of the Pt/PMMA/SWNT was successfully achieved because of the incorporation of PMMA and Pt functions. Swelling of the PMMA matrix as a result of DCM adsorption leads to PMMA volume expansion, thereby increasing the SWNT-SWNT distance, which results in an increase in the resistance. Pt NPs promote the dissociation of DCM to CO, and consequently the CO oxidation on the Pt NPs catalyst and electron donation from Pt NPs to SWNTs, resulting in an increase in the resistance. Moreover, a linear relationship was obtained between the sensor response of the Pt/PMMA/SWNT and the concentration of DCM. These results suggest that the integration of SWNTs with PMMA and Pt NPs is a promising approach for improving DCM detection at room temperature.     

Well-dispersed single-walled carbon nanotube/polyaniline composite films

Single-walled carbon nanotube (SWNT)/polyaniline (PANI) composite films with good uniformity and dispersion were prepared by electrochemical polymerization of aniline containing well-dissolved SWNTs. The results of atomic force microscopy (AFM) and UV-Vis adsorption spectroscopy show that aniline can be used to solubilize SWNTs via formation of donor-acceptor complexes. The electrochemical deposition of SWNT-aniline solutions have been investigated by cyclic voltammetry. The results show that SWNT-based aniline solutions exhibit a drastic increase in peak current within the potential scanning region. The doping effect of SWNTs on PANI films was investigated by electrochemistry and FTIR spectroscopy. The results indicate that the enhanced electroactivity and conductivity of the SWNT/PANI composite films may be due to the strong interaction between SWNTs and PANI, which facilitates the effective degree of electron delocalization.     

Preparation and characterization of transparent and conductive thin films of single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs), synthesized using the arc-discharge method and the direct-injection-pyrolytic synthesis (DIPS) method, were dispersed in a tetrahydrofuran solution containing propylamine and used to prepare transparent and conductive thin films on PET films using an airbrush technique. The SWNTs were analyzed using vis-near infrared absorption spectroscopy, Raman spectroscopy, scanning electron microscopy, and atomic force microscopy. The surface resistivity of the SWNT films on the substrates was measured using a four-point probe conductivity measurement. The results revealed that the purity, length, and proportion of the metallic SWNTs are important factors in decreasing the sheet resistance.     

Characterization of single-wall carbon nanotubes by N2 adsorption

N₂ adsorption isotherms at 77 K of single-wall carbon nanotubes (SWNTs), multi-wall carbon nanotubes (MWNTs), and mixtures of these carbon nanotubes (CNTs) were analyzed for differences in their pore size distributions (PSDs). The PSDs, calculated in the microporous region by the Horvath–Kawazoe method and in the mesoporous region by the BJH method, are in agreement with the structures of both types of CNTs deduced from high-resolution transmission electron microscopy. A characteristic peak in the microporous region in the PSD of SWNTs is not present in the PSDs of MWNTs and impurities such as amorphous carbon, metal residues of catalysts, etc. The evaluation of this peak is proposed as a convenient tool for the quantitative characterization of SWNT purity in carbon nanotube-containing samples.     

Investigation of ionomers as dispersants for single wall carbon nanotubes

A novel conjugated ionomer was prepared from a diamine and a bis(pyrylium salt). Single-walled carbon nanotubes (SWNT) were dispersed in solutions of the ionomer in N,N-dimethylacetamide resulting in homogenous suspensions or quasi-solutions. These suspensions were used to cast unoriented thin films. In addition, the ionomer/SWNT solutions were used to aid in the dispersal of SWNTs in a soluble, low color polyimide. The use of the ionomer as a dispersant enabled the nanotubes to be dispersed at loading levels up to 1 wt% in a polyimide solution without visual agglomeration. SWNTs were well dispersed in the thin films as evidenced by visual inspection, optical microscopy, and high resolution scanning electron microscopy. The films were further characterized for their electrical and mechanical properties.     

Magnetic separation of Fe catalyst from single-walled carbon nanotubes in an aqueous surfactant solution

We report an efficient technique to separate ferromagnetic catalyst particles from an aqueous surfactant solution of single-walled carbon nanotubes (SWNTs) by the use of a 1.3 T permanent magnet. High resolution transmission electron microscopy (HRTEM) demonstrates that SWNTs are coated with a surfactant layer that stabilises the aqueous dispersions of SWNTs. The residual quantities of Fe catalyst (∼3%) can be effectively removed from a colloid solution of SWNTs in a magnetic field while absorbance spectra of the initial and purified solutions show that the nanotube diameter distribution remains unchanged.     

Synthesis and Raman characterization of boron-doped single-walled carbon nanotubes

A systematic study was carried out to dope single-walled carbon nanotube (SWNT) bundles with varying amounts of boron using the pulsed laser vaporization technique. Targets containing boron concentrations ranging from 0.5 to 10 at.% boron were prepared by mixing elemental boron with carbon paste and the Co/Ni catalysts. The laser-generated products that were obtained from these targets were characterized by high resolution transmission electron microscopy, electron energy loss spectroscopy (EELS), thermoelectric power (TEP) measurements, and Raman scattering experiments. Electron microscopy and Raman studies revealed that the presence of various levels of boron concentration in the target strongly affected the products that were prepared. SWNTs were found in the products prepared from targets containing up through 3 at.% boron, and high resolution EELS estimated that less than 0.05-0.1 at.% boron is present in the SWNT lattice. The absence of SWNT bundles in the products derived from targets containing more than 3 at.% boron implies that the presence of excess boron in the carbon plume severely inhibits the carbon nanotube growth. The overall effect of the boron incorporation primarily leads to: (i) a systematic increase in intensity of the disorder-induced band (D-band) upon boron doping, with increasing D-band intensity observed for higher doping levels, (ii) a systematic downshift in the G′-band frequency due the relatively weaker C-B bond, and (iii) a non-linear variation in the RBM and G′-band intensities which is attributed to shifts in resonance conditions in the doped tubes. Resonant Raman spectroscopy thus provides large changes in the intensity of prominent features even when the dopant concentration is below the detectable limit of EELS (0.05-0.1 at.%). Thermoelectric power data also provide complementary evidence for the presence of a small boron concentration in the SWNT lattice which transforms the SWNTs into a permanently p-type material.     

Comparison of flocculated and dispersed single‐wall carbon nanotube‐based coatings using nonionic surfactants

Single‐wall carbon nanotubes (SWNTs) are promising filler materials for advanced polymer composites, but the impressive properties that have been predicted theoretically have not been realized experimentally. This gap is generally attributed to aggregation and nonideal dispersion of the SWNTs. Here, nonionic surfactants based on poly(ethylene oxide) are used to disperse SWNTs in either water or ethanol using sonication. The dispersed aqueous SWNTs are stable, while the analogous ethanol system yields loosely flocculated SWNTs. After drying these dispersions, the electrical conductivity of the flocculated system is at least an order of magnitude greater than the dispersed system at the same SWNT loading with conductivity greater than 20 S/cm obtained for the flocculated systems containing unsorted, commercial SWNTs. These flocculated systems can be readily sprayed to create conductive coatings. Despite their high electrical conductivity, these coatings provide only modest electromagnetic interference shielding (<20 dB) when testing large areas (30.5 × 30.5 cm²), which suggests significant heterogeneity or defects in these coatings that are not readily visible by eye or scanning electron microscopy. This defect mechanism is consistent with a decrease in shield efficacy at high SWNT loadings, despite no statistical change in the electrical conductivity of the coating. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Synthesis and characterization of pH-responsive single-walled carbon nanotubes with a large number of carboxy groups

A new type of pH-responsive single-walled carbon nanotubes (SWNTs) with a large number of carboxy groups was prepared by in situ grafting polymerization. Through exfoliating the SWNT bundles with sodium dodecylbenzene sulfonate (SDBS), individual SWNTs have been obtained. Due to the existence of SDBS, the individual SWNTs could be readily dispersed in water, then forming stable dispersions. Grafting polymerization of acrylonitrile was performed in micelles of SWNTs to produce polyacrylonitrile funtionalized SWNTs (PAN-SWNTs). Experimental results showed that adsorbing acrylonitrile on the SWNT surfaces plays a key role in the grafting process. After hydrolyzing PAN, polyacrylic acid functionalized SWNTs (PAA-SWNTs) were obtained. The amount of PAA grafted could be controlled by changing the feed ratio of initiator to monomer, and the maximum grafting amount could reach 40 wt%. The solubility of PAA-SWNTs in water could be adjusted by pH, with better solubility at higher pH. The large number of carboxy groups on the SWNT surfaces lends the systems convenient for further modification via amidation or esterfication.     

Solid-liquid-solid growth mechanism of single-wall carbon nanotubes

Reasons are presented which suggest that the liquefaction of the catalytic particles is a decisive condition for formation of single wall carbon nanotubes (SWNTs) by physical synthesis techniques. It is argued that the SWNT growth mechanism is a kind of solid-liquid-solid graphitization of amorphous carbon or other imperfect carbon forms catalyzed by molten supersaturated carbon-metal nanoparticles. The assumption of low temperature melting of these nanoparticles in contact with amorphous carbon followed by its precipitation in the form of SWNTs allows to explain qualitatively the experimentally observed SWNT growth rates and temperature dependence of the SWNT yield. Guidelines for increasing SWNT yield are proposed.