Root growth of multi-wall carbon nanotubes by MPCVD

This work examines the relationships among the growth and interlayer reactions of carbon nanotubes (CNTs) to develop an effective process for controlling the nanostructure, orientation and characteristics of CNTs. Vertically oriented CNTs were successfully synthesized by microwave plasma chemical vapor deposition (MPCVD) with CH₄/H₂ as source gases. Additionally, the Ti and SiO₂ barrier layers and the Co catalyst were used in an experiment on the growth of CNTs on the Si wafer. Then, the SiO₂ barrier layer was deposited by low-pressure chemical vapor deposition (LPCVD). The Ti barrier layer and Co catalyst films were deposited on the Si wafer by physical vapor deposition (PVD). The deposited nanostructures were characterized by scanning and transmission electron microscopy, the results of which reveal that the deposited MWCNTs were grown under the influence of a catalyst on Si substrates with or without a barrier layer, by MPCVD. Vertically grown, dense MWCNTs attached to a catalytic film demonstrate that various MWCNTs penetrated the root particles. The diameter of the root particles, of approximately in the order of 100 nm, is larger than those of the tube, 10–15 nm. The well-known model of the growth of CNTs includes base- and tip-root growth. The interaction between the catalytic film and the supporting barrier layer is suggested to determine whether the catalytic particles are driven up or pinned down on the substrate during the growth.     

Application of aromatization catalyst in synthesis of carbon nanotubes

In a typical chemical vapour deposition (CVD) process for synthesizing carbon nanotubes (CNTs), it was found that the aromatization catalysts could promote effectively the formation of CNT. The essence of this phenomenon was attributed to the fact that the aromatization catalyst can accelerate the dehydrogenation–cyclization and condensation reaction of carbon source, which belongs to a necessary step in the formation of CNTs. In this work, aromatization catalysts, H-beta zeolite, HZSM-5 zeolite and organically modified montmorillonite (OMMT) were chosen to investigate their effects on the formation of multi-walled carbon nanotubes (MWCNTs) via pyrolysis method when polypropylene and 1-hexene as carbon source and Ni₂O₃ as the charring catalyst. The results demonstrated that the combination of those aromatization catalysts with nickel catalyst can effectively improve the formation of MWCNTs.     

Synthesis and characterization of Ni-Si mixed oxide nanocomposite as a catalyst for carbon nanotubes formation

Ni-Si mixed oxide nanocomposite was prepared by co-precipitation method with Ni(NO₃)₂ · 6H₂O and tetraethylorthosilicate (TEOS) at pH = 10.5 under reflux condition for 6 days. It was then used as a catalyst for the formation of carbon nanotubes (CNTs) by CVD procedure. Characterization of the catalyst and the CNTs was carried out using X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The results showed that Ni-Si mixed oxides nanorods with the average diameter of 3 to 4 nm play a key role in CNTs formation.     

Growth of aligned carbon nanotubes on ALD-Al2O3 coated silicon and quartz substrates

The smooth surface of the amorphous Al₂O₃ film on either silicon or quartz, coated by atomic layer deposition (ALD), was changed to rough surface by annealing in either air or hydrogen at high temperature (745°C) due to the formation of nanosized pinholes and micrometre pimples during the crystallisation of the amorphous Al₂O₃. The rough surface makes the growth of long carbon nanotubes (CNTs) by chemical vapour deposition impossible. Nevertheless, we were able to develop new catalyst recipes for successful growth of vertically aligned CNTs on ALD-Al₂O₃ coated silicon and quartz substrates. The lengths of the CNTs reached 90?µm on silicon substrates and 180?µm on quartz substrates. Furthermore, it is observed that the adhesion of CNTs on silicon substrates is much stronger than that on quartz substrates.     

Effect of Co and Ni nanoparticles formation on carbon nanotubes growth via PECVD

The effect of cobalt (Co) and nickel (Ni) nanoparticle catalysts on the growth of carbon nanotubes (CNTs) were studied, where the CNTs were vertically grown by plasma enhanced chemical vapour deposition (PECVD) method. The growth conditions were fixed at a temperature of 700 °C with a pressure of 1000 mTorr for 40 minutes with various thicknesses of sputtered metal catalysts. Only multi-walled carbon nanotubes are present from the growth as large average diameter of outer tube (～10–30 nm) were measured for both of the catalysts used. Experimental results show that high density of CNTs was observed especially towards thicker catalysts layers where larger and thicker nanotubes were formed. The nucleation of the catalyst with various thicknesses was also studied as the absorption of the carbon feedstock is dependent on the initial size of the catalyst island. The average diameter of particle size increases from 4 to 10 nm for Co and Ni catalysts. A linear relationship is shown between the nanoparticle size and the diameter of tubes with catalyst thicknesses for both catalysts. The average growth rate of Co catalyst is about 1.5 times higher than Ni catalyst, which indicates that Co catalyst has a better role in growing CNTs with thinner catalyst layer. It is found that Co yields higher growth rate, bigger diameter of nanotube and thicker wall as compared to Ni catalyst. However, variation in Co and Ni catalysts thicknesses did not influence the quality of CNTs grown, as only minor variation in I_G/I_D ratio from Raman spectra analysis. The study reveals that the catalysts thickness strongly affects not only nanotube diameter and growth rate but also morphology of the nanoparticles formed during the process without influencing the quality of CNTs.     

Improved electrochemical capacitive characteristics by controlling the carbon nanotube morphology and electrolyte solution concentration

Carbon nanotubes (CNTs) have been used as the electrochemical double layer in capacitor (EDLC) electrodes. CNTs were synthesized using thermal chemical vapor deposition (CVD) at a growth temperature of 750 °C by flowing C₂H₂. The surface morphology of the synthesized CNTs could be controlled with or without Al film deposition between the stainless (SUS) sheet and Fe catalyst film. Electrochemical measurements were performed in a three-electrode arrangement. H₂SO₄ with different concentrations was used as the electrolyte solution. The relation between the specific capacitance and the surface morphology of the CNTs and the electrolyte concentration were investigated. The results showed that the electrode formed using vertically aligned CNTs with higher electrolyte concentration exhibited higher specific capacitance.     

Catalytic-free growth of VACNTs for energy harvesting

Abstract

The present study introduces a process to grow micro-honeycomb (µ-HC) vertically aligned carbon nanotubes (VACNTs) using thermal chemical vapor deposition technique. Methane is used as a source of carbon and hydrogen gas as a reducing agent. Where, the fabricated µ-HC structure reported in literature involves complex synthesis process and requires a catalyst layer, the novelty of the process used here lies in the fact that no catalyst layer is used for the growth of CNT network, rather copper foil is used as a substrate. The in-situ cracking of CNTs due to water treatment leads to the formation of µ-HC CNT network, which is confirmed by Raman spectroscopy. Further scanning electron microscopy analysis shows that the length of developed µ-HC CNT is ～5?µm. Hexagonal µ-HC network shows more than 94% absorption in UV-Vis-NIR wavelength region. The designed process provides high-yield with a low-cost synthesis of vertically aligned CNTs having 3?D microarchitecture. The fabricated CNT network can be used as an electrode for supercapacitor, as an active layer in a photovoltaic cell and most of the energy harvesting devices.     

Synthesis of binary and triple carbon nanotubes over Ni/Cu/Al2O3 catalyst by chemical vapor deposition

Novel binary and triple carbon nanotubes (CNTs) with one common catalytic particle encapsulated have been synthesized using Ni/Cu/Al₂O₃ catalyst, which was produced by a sol-gel method. But when using Ni/Al₂O₃ as catalyst, a mass of common CNTs, that is, one CNT with one catalytic particle encapsulated, was obtained. The results showed that copper-element doping to the Ni/Al₂O₃ catalyst played a key role in the synthesis of CNTs, signifying a novel approach to modify the Ni/Al₂O₃ catalyst. Based on the transmission electron microscopy observations, a simple growth mechanism was developed to describe the growth of the binary or triple CNTs, which could be well explained by a diffusion segregation process.     

Investigation of the effective parameters in the growth of carbon nanotubes by thermal chemical vapour deposition method

Synthesis and growth of carbon nanotubes (CNTs) from C₂H₂ by thermal chemical vapour deposition (TCVD) using a mixture of different gases were investigated. A thin film of nickel was coated as catalyst on silicon substrates by ion beam sputtering technique. Various parameters such as thickness of oxide layer and time, as well as reduction temperature were investigated in view of obtaining the best conditions for CNTs growth. C₂H₂ was very effective as carbon feedstock and NH₃ pretreatments were crucial steps towards obtaining a high density of nucleation sites for CNTs growth by inhibiting amorphous carbon generation in the initial stage of the synthesis. The substrate oxide layer was analysed by secondary ion mass spectrometry. The prepared CNTs were confirmed by Raman spectroscopy and were further characterised using scanning electron microscopy and transmission electron microscopy.     

Multi-barrier layer-mediated growth of carbon nanotubes

Variation in the height of carbon nanotubes (CNTs) grown has been co-related to the type of multi-barrier-layer used. Initially, various types of barrier-layers such as Al, Al₂O₃, Al/SiO₂, Al₂O₃/SiO₂ were prepared onto a n-type Si (100) substrate. The thickness of SiO₂ was ∼ 550 nm, where as, Al₂O₃ and Al were ∼ 15 nm thick. These samples were covered with ∼ 1 nm thick Fe catalyst layer. The coated samples were subjected to the thermal chemical vapor deposition (T-CVD) process. SEM analysis showed that, for Al₂O₃/SiO₂ barrier layers, the average height of the CNTs was ∼ 10 μm, where as, for other types of samples it was less than ∼ 1 μm. To investigate this, multi-barrier layers were characterized by dynamic secondary ion mass spectrometry (D-SIMS). The observed variation in height of CNTs is attributed to the variation in diffusivity of Fe atoms into multi-barriers-layers. The results showed that, diffusion of Fe catalyst atoms could severally affect height of CNTs.     

Simple method for synthesis of carbon nanotubes over Ni-Mo/Al2O3 catalyst via pyrolysis of polyethylene waste using a two-stage process

Synthesis of valuable multi-walled carbon nanotubes (MWCNTs) by thermal pyrolysis of low-density polyethylene (LDPE) waste was investigated via a two-stage process. The first stage was the thermal pyrolysis of LDPE to gaseous hydrocarbons, and the second stage was the catalytic decomposition of the pyrolysis gases over Ni-Mo/Al₂O₃ catalysts. Two catalysts with the compositions of 5.2%Ni-10.96%Mo/Al₂O₃ and 10%Ni-9.5%Mo/Al₂O₃ were tested for carbon nanotubes (CNTs) formation. The catalyst containing 10%Ni showed better activity in terms of CNTs production. Accordingly, the impact of either pyrolysis or decomposition temperatures was investigated using the 10%Ni-9.5%Mo/Al₂O₃ catalyst. TEM, XRD, Raman spectroscopy, TGA, TPR, and BET analysis tools were used to characterize the fresh catalysts as well as the obtained carbon nanomaterials. TEM images proved that MWCNTs with various morphological structures were obtained at all pyrolysis and decomposition temperatures. Moreover, cup-stacked carbon nanotubes (CS-CNTs) were observed at the decomposition temperature of 600°C. MWCNTs with the best quality were produced at decomposition temperature of 750°C. The optimum pyrolysis and decomposition temperatures in terms of CNTs production were at 700 and 650°C, respectively.     

Alumina powder assisted carbon nanotubes reinforced Mg matrix composites

Mg matrix composites reinforced by carbon nanotubes (CNTs)-Al₂O₃ mixture, which was synthesized by in situ growing CNTs over Al₂O₃ particles through chemical vapor deposition (CVD) using Ni catalyst, were fabricated by means of powder metallurgy process, followed by hot-extrusion. By controlling synthesis conditions, the as-grown CNTs over Al₂O₃ particles possessed high degree of graphitization, ideal morphology, higher purity and homogeneous dispersion. Due to the ‘vehicle’ carrying effect of micrometer-level A₂O₃, CNTs were easy to be homogeneously dispersed in Mg matrix under moderate ball milling. Meanwhile, Al₂O₃ particles as catalyst carriers, together with CNTs, play the roles of synergistic reinforcements in Mg matrix. Consequently, the Mg matrix composites reinforced by CNTs-Al₂O₃ mixture exhibited remarkable mechanical properties.     

Growth of carbon nanotubes using a thermal insulator investigated by in-situ mass spectroscopy

The low-temperature synthesis (500-560 °C) of carbon nanotubes (CNTs) on a triple-layered catalyst, Al/Fe/Mo was performed using complex hydrocarbon radicals which were produced from pyrolysis of C₂H₂. These radicals were produced using a high-temperature heater (~ 830 °C), but the substrate where the CNTs were grown was placed on a thermal insulator. This then enabled the substrate to be at a much lower temperature (500-560 °C). A simulated temperature distribution inside the chamber was also used to describe this low-temperature configuration. The synthesis of CNTs relies on the thermal dissociation and dissociative recombination of C₂H₂ for the formation of complex high-order radicals (i.e. C₆H₉, C₅H₉, and C₆H₁₃), and their presence was confirmed by in-situ mass spectroscopy. To explain this, a simple gas-phase radical chain process and a growth model are presented.     

Effect of ferrocene catalyst particle size on structural and morphological characteristics of carbon nanotubes grown by microwave oven

The influence of catalyst particle size on the formation and diameter of carbon nanotubes (CNTs) is investigated. Ferrocene catalyst with an average diameter of 19.7, 21.4, 23.6 and 27.0 µm is used for the growth of CNTs by a cost-effective and facile method using microwave oven. Morphological observations by transmission electron microscopy and field emission scanning electron microscopy reveal consistently that smaller catalyst diameter generates CNTs with smaller diameter. Raman spectroscopy indicates that the full width at half maximum of G-, D- and 2D-bands decreases gradually with increasing CNTs diameter; meanwhile, G-band/D-band intensity ratio is found to be sensitive to crystal defects, showing a drop for CNTs diameter in the range 25–40 nm then followed by a slight increase for higher diameters. This may be associated with CNTs curvature and strain which developed along tube walls. X-ray diffraction analysis demonstrates an increase in d ₍₀₀₂₎ interlayer spacing with decreasing CNTs diameter. Furthermore, CNTs diameter is found to be inversely proportional to (002) linewidth. Finally, the energy band gap estimated from UV–NIR–Vis measurements increases slightly with CNTs diameter, 5.69–5.84 eV.     

Magnetic field enhances the graphitized structure and field emission effect of carbon nanotubes

This study uses a low temperature thermal chemical vapor deposition with an applied external magnetic field to grow carbon nanotubes (CNTs) on Ni/Ag-printed glass substrates. A mixture of C₂H₂ and H₂ gas was used for the growth of the CNTs. A Ni catalyst layer was deposited on the Ag-printed glass substrate by pulse electroplating. Scanning electron micrographs as well as the presence of two sharp peaks at 1320 cm⁻¹ (D band) and 1590 cm⁻¹ (G band) in the Raman spectra indicate that the graphitized structure of CNTs synthesized under a magnetic field has higher quality (i.e., a D-band to G-band intensity ratio of 0.303) than CNTs synthesized without a magnetic field. Transmission electron micrographs show a fine Ni catalyst at the tip of the tube for CNTs synthesized under a magnetic field, exhibiting a CNT “tip-growth” model. The synthesis of CNTs in the presence of a magnetic field also generates better field emission properties and better lighting morphology than without a magnetic field.     

Synthesis and characterization of large area well-aligned carbon nanotubes by ECR-CVD without substrate bias

Large area, well-aligned carbon nanotubes (CNTs) were synthesized on porous silicon by electron cyclotron resonance chemical vapor deposition (ECR-CVD). No bias was applied on the substrate in this experiment. CH₄ and H₂ were used as source gases and Fe₃O₄ nanoparticles as the catalyst. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction spectroscopy (XRD), and Raman spectrum were used to evaluate the structure and composition. The results show that these CNTs have varying outer diameters from 10 to 90 nm and uniform length over 10 μm. They display hollow tubular and chain structures. The possible formation mechanism of aligned CNTs is discussed.     

Studying the growth of carbon nanotubes on carbon fibers surface under different catalysts and electrochemical treatment conditions

A special electrochemical anodic oxidation (EAO) method was applied to modify the surface of carbon fibers (CFs) with fatty alcohol polyoxyethylene ether phosphate (O₃P), triethanolamine (TEA), fatty alcohol polyoxyethylene ether ammonium phosphate (O₃PNH₄), and ammonium bicarbonate (NH₄HCO₃) used as the electrolyte respectively. Then different catalysts, including Ni, Co, and Cu, were used to catalyze the growth of carbon nanotubes (CNTs) on the surface of CFs. The variation regulation of structure and property of CNTs on CFs surface was investigated by different methods. The results showed that the optimal effect of surface modification of CFs was achieved when O₃PNH₄ served as an electrolyte and the optimal electrochemical treatment intensity (ETI) was 100C/g. Also, with temperature variety, there are different microstructure changes for CNTs that adopt different catalysts. Through the experiment, a uniform catalyst coating was obtained on the surface of CFs after reduction process, which laid the foundation for the growth of uniform and regular CNTs.     

Growth of carbon nanotubes on glass substrate by MPECVD

We have grown carbon nanotubes (CNTs) with a microwave plasma-enhanced chemical vapor deposition (MPECVD) method, which has been regarded as one of the most promising candidates for the synthesis of CNTs due to the vertical alignment, the low temperature and the large area growth. We had used methane (CH₄) and hydrogen (H₂) gas for the growth of CNTs. 10-nm-thick Ni catalytic layer were deposited on the Ti-coated glass substrate by RF magnetron sputtering method. In this work, we report the low-temperature growing properties of the CNTs on glass substrate with a MPECVD. We have pretreated the Ni/Ti/glass catalytic layer in different microwave power (600, 700, 800, and 900 W) and grown the CNTs in the same microwave power (800 W). SEM (Scanning electron microscopy) images of the Ni catalytic layer shows the diameter and density variation to be dependent with the pretreatment conditions. Raman spectroscopy of CNTs shows that the synthesized CNTs were multi-wall CNTs.     

Decoration of carbon nanotubes with nearly monodisperse MFe2O4 (MFe2O4, M = Fe, Co, Ni) nanoparticles

Magnetic monodisperse ferrite MFe₂O₄ (M = Fe, Co, Ni) nanoparticles have been successfully deposited on carbon nanotubes (CNTs) by in situ high-temperature hydrolysis and inorganic polymerization of metal salts and CNTs in polyol solution. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectrometry (EDS) and vibrating sample magnetometer (VSM) investigations were used to characterize the final products. The influencing factors for formation of CoFe₂O₄ nanoparticles along CNTs have also been discussed briefly. The main advantage of this synthetic strategy is that it is beneficial for the fabrication of magnetic CNTs with a compact layer of nanoparticles and could be extended to prepare series of ferrite/CNTs nanocomposites via the substitution of metal cations.     

Effect of Co-Mo catalyst preparation and CH4/H2 flow on carbon nanotube synthesis

Abstract

Supported Co-Mo catalysts with a given ratio of metals were prepared from polyoxomolybdate Mo₁₂O₂₈(μ₂-OH)₁₂{Со(H₂O)₃}₄ using impregnation and combustion methods. Effects of the type of catalyst and the ratio and flow of methane and hydrogen gases on the structure of carbon nanotubes (CNTs) synthesized by catalytic chemical vapor deposition (CCVD) method were studied using transmission electron microscopy and Raman spectroscopy. The catalyst prepared by combustion method yielded mainly individualized CNTs, while the CNTs were highly entangled or bundled when impregnation method was used. In both cases, addition of hydrogen to methane led to reduction of the CNT yield. The samples synthesized using two different catalysts and the same CH₄/H₂ ratio and flow of gases were tested in electrochemical capacitors. A higher specific surface area of the CNTs grown over impregnation-prepared catalyst caused a better performance at scan rates from 2 to 1000?mV/s.