Influence of carbon structure of the anode on the synthesis of single-walled carbon nanotubes in a carbon arc plasma

Arc plasma evaporation of carbon electrodes doped with various catalysts is one of the most effective methods of single-walled carbon nanotube fabrication. It was found that the reaction yield is strongly influenced not only by the appropriate choice of the catalyst(s), but also by the type of carbon material used for electrode fabrication. Several different carbon powders i.e. graphite powders, glassy carbon and coke, have been tested in order to establish which parameters (primary particle size, granulation, density or conductivity of the electrode) affected the outcome of the reaction the most. The highest yield of single-walled nanotubes was found for anodes fabricated from graphite powders, whilst the electrodes made from glassy carbon or coke yielded significantly smaller amounts of nanotubes. The reaction zone where carbon radicals nucleate (close to the arc gap) was probed by optical absorption spectroscopy. The estimated temperature distributions and contents of C₂ radicals did not depend on the anode characteristics.     

An efficient strategy for the purification of cloth-like single walled carbon nanotube soot produced by arc discharge

High purity single walled carbon nanotubes (SWCNTs) were prepared from arc discharge produced cloth-like soot by a new purification strategy, in which liquid oxidation and steam oxidation were combined with a freeze-drying process to remove the metallic and carbonaceous impurities. The process gives a product of >98% purity, which is acquired from a gram-scale dirty raw soot with an overall yield of ∼75% of the SWCNTs. The purity of the samples was characterized by thermogravimetric analysis, scanning and transmission electron microscopy, Raman and Vis-NIR spectroscopy, and magnetometry. A highly pure SWCNT sample with relative purity of 170.4% and I_G/I_D value of 78.92 is achieved. Experiments showed that HNO₃/HCl refluxing combined with freeze-drying is the key process that renders the crude SWCNTs hydrophilic with a large surface area, and thus remarkably increases the efficiency of the steam treatment to remove most of the carbonaceous impurities.     

Temperature and catalyst effects on the production of amorphous carbon nanotubes by a modified arc discharge

Large amounts of amorphous carbon nanotubes (ACNTs) were prepared with Co-Ni alloy powders as catalyst in hydrogen gas atmosphere by a modified arc discharging furnace which can control temperature during the electric arcing process. The experimental results indicate that the cooperative function of temperature and catalyst plays an important role in the soot production rate and the relative ACNT purity. When temperature increases from 25 °C to 700 °C, the soot production rate increases from around 1 g/h to 8 g/h, the best relative ACNT purity at 600 °C can reach up to 99% compared to the room temperature sample. Without catalyst, only plate graphite is formed at 25 °C and very few carbon nanotubes are found when temperature increases to 600 °C. TEM, SEM, HRTEM and XRD analysis showed that the as-prepared carbon nanotubes are almost amorphous. The soot production rate is 8 g/h and diameter range of amorphous carbon nanotubes is about 7-20 nm, respectively.     

Hole injection enhancement of a single-walled carbon nanotube anode using an organic charge-generation layer

We demonstrate significant hole injection enhancement of single-walled carbon nanotube (SWCNT) anodes in flexible organic light-emitting devices (OLEDs) by the insertion of a strong electron-accepting organic charge-generation layer (CGL), hexaazatriphenylene hexacarbonitrile (HAT–CN). To clarify the origin of hole injection improvement, we investigated interfacial electronic structures using in situ ultraviolet photoelectron spectroscopy, inverse photoelectron spectroscopy, theoretical calculations, and electrical measurements. The HAT–CN layer significantly increased the work function of SWCNT anodes and acted as an efficient CGL due to its deep-lying lowest unoccupied molecular orbital level, which arises from the strong electron-accepting characteristics of the carbonitrile endgroups. We compared the energy level alignment at the interface of the N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) hole transport layer/HAT–CN/SWCNTs with that of NPB/SWCNTs, and found that the highest occupied molecular orbital level of the NPB changed from 1.20 to 0.40 eV with insertion of the HAT–CN layer. As a result, flexible OLEDs with the HAT–CN layer showed an order of magnitude larger current density and luminance than those without the HAT–CN layer.     

Continuous production of single-walled carbon nanotubes using a supported floating catalyst

Using catalytic decomposition, a technique for the production of singe-walled carbon nanotubes (SWCNTs) is reported with a production rate up to 6 g h⁻¹ after purification, and scaling capability up to 220 g h⁻¹. This is achieved by injection of pre-prepared alumina supported catalyst powder into a modified vertical floating reactor. The product is collected in several cyclones connected in series. Wide range Raman studies (laser excitations from λ = 1064 to 488 nm) and temperature programmed oxidation measurements of the samples collected from the different cyclones show that SWCNTs were separated in situ by tube diameter. This is attributed to the different residual times of the catalyst in the reaction zone depending on particle diameter. A series of computational fluid dynamics calculations of the flow and heat transfer in the reactor, as well as modeling of catalyst particle transport reveals the parametrical dependence of the process.     

Synthesis of vertically-aligned carbon nanotubes without a catalyst by hydrogen arc discharge

Vertically-aligned carbon nanotubes (CNTs) were prepared by hydrogen arc discharge, using pure graphite powder as carbon source without catalysts added. Scanning and transmission electron microscopy characterizations show that the aligned CNTs have a bamboo-like structure, and their lengths and diameters are about 30 μm and 40–60 nm, respectively. No metallic impurities can be detected in the samples by careful X-ray photoelectron spectroscopy detection. The activation of hydrogen radicals, the heating effect of the arc, and the electric field surrounding the arc column area are considered to play important roles for the non-catalyst growth of the CNTs.     

Synthesis of single-wall carbon nanotubes and long nanotube ribbons with Ho/Ni as catalyst by arc discharge

The effect of a new bimetallic catalyst Ho/Ni for synthesis of single-walled carbon nanotubes (SWNTs) by arc discharge has been studied. Long ribbons consisting of roughly-aligned SWNT bundles were obtained by a modified arc discharge apparatus. Ribbon lengths can reach as much as 20 cm. Both elements Ho and Ni play important roles in the synthesis of SWNTs with high yield and purity. Changes in the Ho and Ni concentration in the catalyst hardly affect the diameter distribution of SWNTs, but the yield and purity of SWNTs are very sensitive to the concentration. An optimal range of Ho/Ni compositions for synthesis of SWNTs with relatively high purity and yield is given.     

Improving the synthesis of single-walled carbon nanotubes by pulsed arc discharge in air by preheating the catalysts

Single-walled carbon nanotubes (SWCNTs) were synthesized in reduced pressure air using pulsed arc discharge after preheating the catalyst. Our experimental results revealed that preheating the catalysts can assist the synthesis of SWCNTs in air under a pressure of 5-10 kPa. The SWCNTs have a diameter of 1.5-2 nm and length can reach several micrometers. The consumption rate of the anode and the production rate of CNTs and SWCNTs in air are lower than in helium atmosphere at the same pressure, respectively. Further experiment demonstrates that 600 °C is optimum temperature for preheating the catalysts to synthesize SWCNTs in air.     

The effect of electric current on the synthesis of single-walled carbon nanotubes by temperature controlled arc discharge

The effect of discharge current on the synthesis of single-walled carbon nanotubes (SWCNTs) was studied under controlled atmosphere at 500 °C by electric arc discharge. It was shown that the production rate of collected soot was increased but the purity of SWCNTs decreased with increasing discharge current. With a current of 100 A, the SWCNT was very uniform in diameter and a high purity rate of 55% was achieved, as shown by TEM and Raman spectra. Then the influence of electric force, discharge current and catalyst distribution on the formation of SWCNTs was also discussed.     

Influence of magnetic field parallel to the arc on the formation of carbon nano-materials by arc discharge in water

A magnetic field parallel to the carbon arc in water was used to increase the directionality of moving carbon particles and generate carbon nano-materials. The products were analyzed and compared with those obtained without a magnetic field. The study shows that the purity and quality of multi-walled carbon nanotubes in the cathode deposition formed by an arc in water with a magnetic field were both improved, and cylinder-like carbon structures were also found in the deposition. The influence of the magnetic field on the formation of the products was analyzed.     

Two possible emission mechanisms involved in the arc discharge method of carbon nanotube preparation

By investigating the morphologies and microstructures of the cathode deposits prepared by self-sustained arc discharge between graphite rods, we consider that there are two electron emission mechanisms occurring on the cathode: field emission and thermionic emission. The former occurs mainly on the edge of the growing surface, by which we can explain the formation of the outer hard shell of the cathode deposit; while the latter occurs mainly on the growing surface except for the edge area and it is the main cause for the growth of carbon nanotubes.     

Fabrication of single-walled carbon nanotube three-dimensional networks inside the pores of a porous silicon structure

Single-walled carbon nanotube (SWCNT) three-dimensional (3-D) networks were first fabricated in the pores of a porous silicon substrate using thermal decomposition of C₂H₂ at 800 °C. Catalyst nanoparticles were uniformly distributed on the inner wall surfaces of the pores using a dipping method combined with ultrasonication. SWCNTs were synthesized along the inner wall surface of the pores, and spanned it. The suspended SWCNTs inside the pores formed 3-D networks in the results of the chaotic overgrowth of SWCNTs in a confined space under thermal vibration, and van der Waals interactions between SWCNTs.     

A model for the structure and growth of carbon nanofibers synthesized by the CVD method using nickel as a catalyst

Carbon nanofibers were synthesized at 450-800 °C by the catalytic CVD method using alumina plate-supported nickel as catalyst and acetylene as carbon source. It was found that Ni/alumina catalyst exhibited a large catalytic effect on the growth of carbon nanofibers at the temperatures between 550 and 700 °C. TEM observation revealed that most of the carbon nanofibers synthesized at 550 °C had a coil-like shape, and many thick platelet nanofibers were found in the product at 700 °C. A growth model was proposed to explain the structural diversity of the carbon nanofibers. Although the carbon nanofibers showed low crystallinity, they can be easily graphitized at 2500 °C.     

Interplay of interfacial compounds,catalyst thickness and carbon precursor supply in the selectivity of single-walled carbon nanotube growth

This study is devoted to elucidate the interplay of catalyst thickness and growth conditions in the activation and selectivity of single-walled carbon nanotube growth using cobalt deposited on Si/SiO₂ as a model system. In situ Raman studies reveal that thin catalyst layers require a higher pressure of carbon precursor to initiate nanotube growth. However, if the catalysts are pre-reduced, all catalyst thicknesses display the same low threshold pressure and a higher yield of single-walled carbon nanotubes. To explain these results, catalysts formed from a gradient of cobalt thickness are studied. Surface analyses show that during the catalyst preparation, catalyst atoms at the interface with silica form small and hard-to-reduce silicate nanoparticles while the catalyst in excess leads to the formation of large oxide particles. Weakly-reducing conditions of pretreatment or synthesis are sufficient to reduce the large oxide particles and to lead to the growth of large-diameter multi-walled carbon nanostructures. However, highly-reducing conditions are required to reduce the small silicate domains into small cobalt particles able to grow single-walled carbon nanotubes. These results show that reaction of the catalyst with the support to form more refractory compounds greatly impact the nucleation yield and the growth selectivity of single-walled carbon nanotubes.     

The efficient synthesis of carbon nano-onions using chemical vapor deposition on an unsupported Ni–Fe alloy catalyst

Well graphitized carbon nano-onions (CNOs) with large yield have been synthesized by the catalytic decomposition of methane over an unsupported Ni–Fe catalyst at 850 °C. The unsupported Ni–Fe catalyst was prepared by a reduction-substitution method. In the Ni–Fe alloy particle, α-Fe(Ni) phase (kamacite) transforms to γ-Fe–Ni phase at the high temperature for hydrogen reduction and chemical vapor deposition. The synthesized CNOs contain either a Fe_0.64Ni_0.36 particle or a hollow core with thick graphitic layers and a polyhedral shape. Based on the characterization, we believe that the catalyst involved in the synthesis of carbon products is Fe–Ni–C austenite rather than the γ-Fe–Ni phase (Fe_0.64Ni_0.36). A growth mechanism for the CNOs is proposed.     

Influence of transverse magnetic field on the formation of carbon nano-materials by arc discharge in liquid

To change the structures and yields of carbon nano-products, transverse magnetic field (TMF) was introduced to arc discharge in liquid (de-ionized water, liquid nitrogen). Direct current was used to sustain the arc discharge between two graphite electrodes and cobalt powder was filled in drilled anodes as catalyst sometimes. Scanning electron microscopy and high-resolution transmission electron microscopy were used to investigate the nano-products. Some novel carbon nano-structures were obtained with the effect of TMF. For arc discharge in water, curled multi-walled carbon nanotubes and nano-structures with few layers were found in cathode depositions and floating products, respectively. For arc discharge in liquid nitrogen, twists of single-walled carbon nanotubes appeared in cathode depositions and the yields of spherical nano-particles in floating products increased.     

The growth of single-walled carbon nanotubes on a silica substrate without using a metal catalyst

Single-walled carbon nanotubes (SWCNTs) have been directly grown on a SiO₂ substrate using the chemical vapor deposition (CVD) of ethanol without a catalyst. Care was taken to exclude the possibility that the SWCNT growth was induced by conventional metal catalysts such as Fe, Co and Ni resulting from the contamination. Pretreatment of the SiO₂ at 950 °C or a higher temperature in H₂ before CVD was critical for the synthesis of SWCNTs. After CVD process, nano-scale carbon particles were produced besides SWCNTs. Based on these results, we propose that the annealing of SiO₂ substrates in H₂ at high temperature generates defects on their surfaces, and these defects provide nucleation sites for the formation of carbon nanoparticles and assist the formation of carbon nanocaps, thus leading to the SWCNT growth.     

Energy dependence of the carbon plasma beam on the arc voltage and the anode–cathode distance in the pulsed arc discharge method

The energies of the carbon plasma beams produced by the pulsed arc discharge method have been measured as a function of the arc voltage (1500–4000 V) and anode–cathode distance. The energies were determined by using the electro-optical time-of-flight method. The energy of the plasma rises steeply when the anode–cathode distance and voltage are increased. The anode–cathode distance varied from 0.6 to 4.6 cm and the plasma ion energies from 20 to 730 eV, respectively. The discharge voltage of 4000 V and distance of 4.6 cm were necessary for the plasma ion energy of 730 eV. The practical significance of highly energetic carbon plasma for the preparation of the adhesion layer of high-quality amorphous diamond-like carbon (DLC) protective coatings is presented.     

High-efficient synthesis of double-walled carbon nanotubes by arc discharge method using chloride as a promoter

With trace halide as a promoter in an iron sulfide catalyst, relatively perfect structural integrity double-walled carbon nanotubes (DWNTs) have been synthesized in large quantity and high yield by arc discharge method. Scanning electron microscope (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and Raman spectroscopy were used for structural characterization and yield determination. The results revealed that halide was a crucial factor for selectively synthesizing high yield DWNTs. The detailed experimental parameters were systematically investigated. The possible role of halide in growth of DWNTs was discussed as well.     

High yield production of semiconducting p-type single-walled carbon nanotube thin-film transistors on a flexible polyimide substrate by tuning the density of ferritin catalysts

We report on a simple method for fabricating pure p-type single-walled carbon nanotube (SWCNT) thin-film transistors (TFTs) on flexible polyimide substrates without selective removal of metallic SWCNTs from the as-grown CNT films. The density of the SWCNTs was controlled by tuning the concentration of ferritin catalyst, resulting in the control of the metallic percolation pathways in the SWCNT TFTs. For a ferritin solution diluted by 1/2000, approximately 60% of the pristine SWCNT TFTs showed p-type behavior with larger on/off current ratios, (I_on/I_off > 10⁴) and a high photosensitivity to the exposure of UV/visible light.