Synthesis of carbon nanotubes on diamond-like carbon by the hot filament plasma-enhanced chemical vapor deposition method

Carbon nanotubes (CNTs) have attracted considerable attention as possible routes to device miniaturization due to their excellent mechanical, thermal, and electronic properties. These properties show great potential for devices such as field emission displays, transistors, and sensors. The growth of CNTs can be explained by interaction between small carbon patches and the metal catalyst. The metals such as nickel, cobalt, gold, iron, platinum, and palladium are used as the catalysts for the CNT growth. In this study, diamond-like carbon (DLC) was used for CNT growth as a nonmetallic catalyst layer. DLC films were deposited by a radio frequency (RF) plasma-enhanced chemical vapor deposition (RF-PECVD) method with a mixture of methane and hydrogen gases. CNTs were synthesized by a hot filament plasma-enhanced chemical vapor deposition (HF-PECVD) method with ammonia (NH₃) as a pretreatment gas and acetylene (C₂H₂) as a carbon source gas. The grown CNTs and the pretreated DLC films were observed using field emission scanning electron microscopy (FE-SEM) measurement, and the structure of the grown CNTs was analyzed by high resolution transmission scanning electron microscopy (HR-TEM). Also, using energy dispersive spectroscopy (EDS) measurement, we confirmed that only the carbon component remained on the substrate.     

Direct production of carbon nanotubes decorated with Cu2O by thermal chemical vapor deposition on Ni catalyst electroplated on a copper substrate

Carbon nanotubes (CNTs) decorated with Cu₂O particles were grown on a Ni catalyst layer deposited on a Cu substrate by thermal chemical vapor deposition from liquid petroleum gas. Ni catalyst nanoparticles with different sizes were produced in an electroplating system at 45 °C using the corrosive effect of H₂SO₄ which was added to solution. These nanoparticles provide the nucleation sites for CNT growth avoiding the need for a buffer layer. The surface morphology of the Ni catalyst films and CNT growth over this catalyst was studied by scanning electron microscopy (SEM). High temperature surface segregation of the Cu substrate into the Ni catalyst layer and its exposition to O₂ at atmospheric environment, during the CNTs growth, lead to the production of CNTs decorated with about 6 nm Cu₂O nanoparticles. We used SEM to study the surface characteristics of Ni catalyst films and characteristic of grown CNTs. Raman spectroscopy, transmission electron microscopy (TEM), electron diffraction (EDX), X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) revealed the formation of CNTs. The selected area electron diffraction pattern, EDX, and XPS studies show that these CNTs were decorated with Cu₂O nanoparticles. This way of fabrication is the easiest and lowest cost method.     

The effects of hydrogen plasma pretreatment on the formation of vertically aligned carbon nanotubes

The effects of H₂ plasma pretreatment on the growth of vertically aligned carbon nanotubes (CNTs) by varying the flow rate of the precursor gas mixture during microwave plasma chemical vapor deposition (MPCVD) have been investigated in this study. Gas mixture of H₂ and CH₄ with a ratio of 9:1 was used as the precursor for synthesizing CNTs on Ni-coated TiN/Si(1 0 0) substrates. The structure and composition of Ni catalyst nanoparticles were investigated by using scanning electron microscopy (SEM) and cross-sectional transmission electron microscopy (XTEM). Results indicated that, by manipulating the morphology and density of the Ni catalyst nanoparticles via changing the flow rate of the precursor gas mixture, the vertically aligned CNTs could be effectively controlled. The Raman results also indicated that the intensity ratio of the G and D bands (I_D/I_G) is decreased with increasing gas flow rate. TEM results suggest H₂ plasma pretreatment can effectively reduce the amorphous carbon and carbonaceous particles and, thus, is playing a crucial role in modifying the obtained CNTs structures.     

Aligned growth and alignment mechanism of carbon nanotubes by hot filament chemical vapor deposition

Carbon nanotubes (CNTs) growth on Inconel sheets was carried out using hot filament chemical vapor deposition (HFCVD) in a gas mixture of methane and hydrogen. Scanning electron microscopy, transmission electron microscopy and field electron emission (FEE) measurement were applied to study the structure and FEE properties of the deposited CNTs. The effect of bias voltage and substrate surface roughness on the growth of vertically aligned carbon nanotubes was investigated. Well-aligned CNTs were synthesized by bias enhanced HFCVD. The results show that a bias of −500 V generates the best alignment. It has been observed that at the early growth stage, aligned and non-aligned CNTs are growing simultaneously on the unscratched sheets, whereas only aligned CNTs are growing on the scratched sheets. The results indicate that tip growth is not necessary for the electric field to align the CNTs, and larger catalyst particles created by scratching before the heat treatment can induce alignment of CNTs at the early growth stage. In addition, tree-like CNTs bundles grown on the scratched substrates exhibit better FEE performances than dense carbon nanotube forest grown on the unscratched substrates due to the reduced screen effect.     

Growth of multiwalled carbon nanotube arrays by chemical vapour deposition over iron catalyst and the effect of growth parameters

Multiwalled carbon nanotube (CNT) arrays were grown by catalytic thermal decomposition of acetylene, over Fe-catalyst deposited on Si-wafer in the temperature range 700-750 °C. The growth parameters were optimized to obtain dense arrays of multiwalled CNTs of uniform diameter. The vertical cross-section of the grown nanotube arrays reveals a quasi-vertical alignment of the nanotubes. The effect of varying the thickness of the catalyst layer and the effect of increasing the growth duration on the morphology and distribution of the grown nanotubes were studied. A scotch-tape test to check the strength of adhesion of the grown CNTs to the Si-substrate surface reveals a strong adhesion between the grown nanotubes and the substrate surface. Transmission electron microscopy analysis of the grown CNTs shows that the grown CNTs are multiwalled nanotubes with a bamboo structure, and follow the base-growth mechanism.     

Matchstick-like carbon nanotube synthesis and structure

Matchstick-like carbon nanotubes (CNTs) have been synthesized by catalytic pyrolysis of thiophene, using a mixture of cobalt nitrate and calcium nitrate as a catalyst. The nanotubes thus grown are aligned, straight, and short, and have spherical heads at their tips. High resolution transmission electron microscopy, selected area electron diffraction, and energy dispersive X-ray spectroscopy results indicate that the spherical heads of the matchstick-like CNTs are crystalline Co₉S₈ nanoparticles and the CNTs have herringbone-type graphite structure. The effect of temperature on the formation of the matchstick-like CNTs has been investigated. A simple growth model is proposed to describe the growth process of the matchstick-like CNTs. PACS 81.05.Uw; 61.46 Fg; 81.15.Gh; 68.37.Hk; 68.37.Lp     

Synthesis and characterization of carbon nanotubes on carbon microfibers by floating catalyst method

In this paper, carbon nanotubes were synthesized on carbon microfibers by floating catalyst method with the pretreatment of carbon microfibers at the temperature of 1023 K, using C₂H₂ as carbon source and N₂ as carrier gas. The morphology and microstructure of carbon nanotubes were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The composition of carbon nanotubes was determined by energy dispersive X-ray spectroscopy (EDX). The results showed that the surface of treated carbon microfibers was thickly covered by carbon nanotubes with diameters of about 50 nm. EDX image indicated that the composition of carbon nanotubes was carbon. In comparison with the sample grown on untreated carbon microfibers surface, it was found that after carbon microfibers were boiled in the solution of sulfur acid and nitric acid (VH₂SO₄:VHNO₃ = 1:3) and immersed in the solution of iron nitrate and xylene, carbon nanotubes with uniform density can be grown on carbon microfibers surface. Based on the results, we concluded that the pretreatment of carbon microfibers had great effect on the growth of carbon nanotubes by floating catalyst method.     

Fabrication and characterization of suspended single-walled carbon nanotubes

Suspended single-walled carbon nanotubes (SWCNTs) between SiO₂ pillars via a direct lithographic route using a simple mixture of catalyst precursor [Co(III) acetylacetonate, Co(acac)₃] and conventional electron beam resist (ma-N2403) were fabricated. The catalytic electron beam resist (Cat-ER) layer plays dual roles as a catalyst and a resist layer for the growth and alignment of CNTs, respectively. The structure of the grown nanotube was characterized by Raman spectroscopy (633 nm laser excitation). Nanotubes grown from Cat-ER with Co(acac)₃ show the typical Raman spectra of SWCNTs which are characterized by the strong tangential bands near to 1590 cm⁻¹ and radial breathing modes (RBMs) in the low frequency region (<300 cm⁻¹). The calculated diameter of the probed nanotubes individually corresponds to the range 0.86-1.77 nm.     

Hot filament CVD of Fe-Cr catalyst for thermal CVD carbon nanotube growth from liquid petroleum gas

A hot filament chemical vapor deposition (HFCVD) method was used to prepare Fe-Cr thin film on Si substrate. The produced layers were used as catalysts for growing carbon nanotubes (CNTs) from liquid petroleum gas (LPG) at 825 °C by thermal CVD (TCVD) method. To characterize the obtained catalysts or CNTs, X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Raman spectroscopy were used. CNTs were grown on HFCVD derived Fe-Cr catalyst with the LPG as carbon source successfully. It was found that an annealing process on catalysts enhances the surface concentration of Cr atoms and reduces the sizes of catalyst particles. The grown CNTs on annealed sample were morphologically denser with smaller diameters compared to the as deposited one. In addition, the effect of filament temperature on CNTs was investigated. By increasing the filament temperature from 850 to 1050 °C the surface density and diameters of CNTs were improved.     

Synthesis of well-aligned carbon nanotubes by inductively coupled plasma chemical vapor deposition

Uniform and well-aligned carbon nanotubes (CNTs) have been grown using a high density inductively coupled plasma chemical vapor deposition (ICP-CVD) system. A gas mixture of methane-hydrogen was used as the source and Ni as the catalyst for the CNT growth. The effect of process parameters, such as inductive RF power, DC bias voltage and CH₄/H₂ ratio, on the growth characteristics of CNTs was investigated. It was found that both plasma intensity and ion flux to the substrate, as controlled by the inductive RF power and DC bias voltage, respectively, can greatly affect the growth of CNTs. The relative importance of the generation of ions and the subsequent transport of ions to the substrate as serial process steps are considered as the two underlying factors in determining the growth characteristics of CNTs. PACS 81.05.Uw; 81.07.De; 81.15.Gh     

Aerosol formation of Sea-Urchin-like nanostructures of carbon nanotubes on bimetallic nanocomposite particles

With the advantage of continuous production of pure carbon nanotubes (CNTs), a new simple aerosol process for the formation of CNTs was developed. A combination of conventional spray pyrolysis and thermal chemical vapor deposition enabled the formation unusual sea-urchin-like carbon nanostructures composed of multi-walled CNTs and metal composite nanoparticles. The CNTs formed were relatively untangled and uniform with a diameter of less than ~10 nm. The key to the formation of CNTs in this way was to create a substrate particle containing both a catalytic and non-catalytic component, which prevented coking. The density of the CNTs grown on the spherical metal nanoparticles could be controlled by perturbing the density of the metal catalysts (Fe) in the host non-catalytic metal particle matrix (Al). Mobility size measurement was identified as a useful technique to real-time characterization of either the catalytic formation of thin carbon layer or CNTs on the surface of the metal aerosol. These materials have shown unique properties in enhancing the thermal conductivity of fluids. Other potential advantages are that the as-produced material can be manipulated easily without the concern of high mobility of conventional nanowires, and then subsequently released at the desired time in an unagglomerated state.     

Monitoring structural defects and crystallinity of carbon nanotubes in thin films

We report the influence of catalyst formulation and reaction temperature on the formation of carbon nanotube (CNT) thin films by the chemical vapour deposition (CVD) method. Thin films of CNTs were grown on Fe-Mo/Al₂O₃-coated silicon wafer by thermal decomposition of methane at different temperatures ranging from 800 to 1000°C. The electron microscopic investigations, SEM as well as HRTEM, of the as-grown CNT thin films revealed the growth of uniform multi-walled CNTs in abundance. The intensity ratio of D-band to G-band and FWHM of G-band through Raman measurements clearly indicated the dependency of structural defects and crystallinity of CNTs in thin films on the catalyst formulation and CVD growth temperature. The results suggest that thin films of multi-walled CNTs with negligible amount of defects in the nanotube structure and very high crystallinity can be obtained by thermal CVD process at 925°C.     

微量水对碳纳米管形貌的影响及其机理研究

利用介质阻挡放电等离子体化学气相沉积技术,在蒸镀有25nm Ni催化剂层的Si基片上,以CH₄和H₂作为反应气体,在973K下制备了碳纳米管,并研究了微量水的引入对碳纳米管形貌的影响.场发射扫描电子显微镜结果表明,不加水时,制备出的碳纳米管直径不均匀,分布在40—90nm之间,呈链节状的结构;加入少量水时,制备出的碳纳米管直径比较均匀,集中在70nm左右,表面为瘤状结构;当水的流量进一步增加时,得到的碳纳米管表面光滑,出现了枝状结构.原位测量了加水前后等离子体区的发射光谱,分析了微量水的引入对于碳纳米管形貌变化的影响机理. 关键词： 碳纳米管 介质阻挡放电 水 发射光谱     

Acetic acid effects on enhancement of growth rate and reduction of amorphous carbon deposition on CNT arrays along a growth window in a floating catalyst reactor

The mm-long carbon nanotube (CNT) arrays were grown in a floating catalyst reactor, using xylene-ferrocene and a small amount of acetic acid as the feed. The CNT arrays deposited on a quartz substrate at several positions along the reactor were extensively characterized using Raman spectroscopy, scanning electron microscopy, X-ray diffraction, high-resolution transmission electron microscopy, and optical microscopy. Various characterization methods consistently reveal that the acetic acid additive to the feed alleviates deposition of amorphous carbon layer, which gradually thickens CNTs along the reactor. The acetic acid also resulted in a higher growth rate along the so-called growth window, where CNT arrays are deposited on the quartz substrate. High-performance liquid chromatography of extracted byproducts (PAHs) confirmed the presence of some polycyclic aromatic hydrocarbons. The solid weight of PAHs decreased upon addition of ferrocene as the catalyst precursor, as well as of acetic acid to xylene feed. The results suggest that primary light products of xylene pyrolysis can be competitive reactants for both catalytic and subsequent pyrolytic reactions. They may also be more efficient feeds for CNT growth than xylene itself.     

HIGH-YIELD PRODUCTION OF MULTI-WALLED CARBON NANOTUBES BY CATALYTIC DECOMPOSITION OF BENZENE VAPOR

Multi-walled carbon nanotubes (CNTs) have been synthesized on γ-Al₂O₃ supported unitary, binary or trinity metal (Fe, Co, Ni) catalysts with benzene as carbon source in the range of 600 to 810 ℃. The growth of CNTs was carried out in a fixed bed flow reactor and the quality of carbon deposits was characterized by transmission electron microscopy. The preparation was optimized and the high-yield production of CNTs has been achieved for three mixture catalysts with the yield of high-quality CNTs higher than 200% within 60 min, reaching a maximum of 278% for 1.51 mmol/g Fe-1.51 mmol/g Co/γ-Al₂O₃ catalyst. This provides a good alternative for future large scale and low cost production of CNTs for applications.     

Large scale intercalated growth of short aligned carbon nanotubes among vermiculite layers in a fluidized bed reactor

Short aligned carbon nanotubes (CNTs) were intercalated grown among vermiculite layers from ethylene using a simple fluidized bed chemical vapor deposition (CVD) process. The length of CNTs ranged from 0.5 to 1.5 μm after a synthesizing duration of 1-5 min at 650 °C. The as-grown CNTs vertically aligned to the vermiculite layers were with the mean outer and inner diameter of 6.7 and 3.7 nm, respectively. A CNT yield of 0.22 g/g_cat was obtained for a 5-min growth. Those indicated that the fluidized bed CVD was an effective way for mass production of short CNTs.     

Field emission properties of carbon nanotube film using a spray method

We fabricated carbon nanotube (CNT) emitters by a spray method using a CNT suspension with ethanol. Indium with a low melting pointing metal or indium tin oxide (ITO) was deposited on the glass substrate. The CNTs were sprayed on these layers and thermally annealed. The sprayed CNTs on an ITO were obtained a high emission current density, field enhancement factor, and a uniform emission pattern than the sprayed CNTs on an ITO layer. We found that the sprayed emitters on the indium layer had good field emission characteristics because of the strong adherence between the metal layer and CNTs.     

Synthesis and field emission properties of carbon nanotubes grown in ethanol flame based on a photoresist-assisted catalyst annealing process

Carbon nanotubes (CNTs) have been grown directly on a Si substrate without a diffusion barrier in ethanol diffusion flame using Ni as the catalyst after a photoresist-assisted catalyst annealing process. The growth mechanism of as-synthesized CNTs is confirmed by scanning electron microscopy, high resolution transmission-electron microscopy and energy-dispersive spectroscopy. The photoresist is the key for the formation of active catalyst particles during annealing process, which then result in the growth of CNTs. The catalyst annealing temperature has been found to affect the morphologies and field electron emission properties of CNTs significantly. The field emission properties of as-grown CNTs are investigated with a diode structure and the obtained CNTs exhibit enhanced characteristics. This technique will be applicable to a low-cost fabrication process of electron-emitter arrays.     

Superior capacitive characteristics of RuO2 nanorods grown on carbon nanotubes

Carbon nanotubes (CNTs) were used as the electric double layer capacitor (EDLC) material and were synthesized by using thermal chemical vapor deposition (TCVD). To enhance the EDLC capacity, the ruthenium dioxide (RuO₂) nanorods were grown on CNTs by using metal organic chemical vapor deposition (MOCVD). The synthesized CNTs were the principal part and template, and the RuO₂ nanorods were grown outwardly from CNTs. The increase of effective specific area between electrode and electrolyte played an important role in enhancing the capacitance. Different concentrations of KOH were used as electrolyte to measure the capacitance to find the variation of capacitance. Moreover, the RuO₂/CNT composites demonstrated a stable cycle life. The results showed that the RuO₂/CNT composites were a promising supercapacitor device material.     

Synthesis of carbon nanotubes on Ni-alloy and Si-substrates using counterflow methane–air diffusion flames

We have conducted an experimental study to investigate the synthesis of multi-walled carbon nanotubes (CNTs) in counterflow methane–air diffusion flames, with emphasis on effects of catalyst, temperature, and the air-side strain rate of the flow on CNTs growth. The counterflow flame was formed by fuel (CH₄ or CH₄ + N₂) and air streams impinging on each other. Two types of substrates were used to deposit CNTs. Ni-alloy (60% Ni + 26% Cr + 14% Fe) wire substrates synthesized curved and entangled CNTs, which have both straight and bamboo-like structures; Si-substrates with porous anodic aluminum oxide (AAO) nanotemplates synthesized well-aligned, self-assembled CNTs. These CNTs grown inside nanopores had a uniform geometry with controllable length and diameter. The axial temperature profiles of the flow were measured by a 125 μm diameter Pt/10% Rh–Pt thermocouple with a 0.3 mm bead junction. It was found that temperature could affect not only the success of CNTs synthesis, but also the morphology of synthesized CNTs. It was also found, against previous general belief, that there was a common temperature region (1023–1073 K) in chemical vapor deposition (CVD) and counterflow diffusion flames where CNTs could be produced. CNTs synthesized in counterflow flames were significantly affected by air-side strain rate not through the residence time, but through carbon sources available for CNTs growth. Off-symmetric counterflow flames could synthesize high-quality CNTs because with this configuration carbon sources at the fuel side could easily diffuse across the stagnation surface to support CNTs growth. These results show the feasibility of using counterflow flames to synthesize CNTs for particular applications such as fabricating nanoscale electronic devices.