Preparation of high yield multi-walled carbon nanotubes by microwave plasma chemical vapor deposition at low temperature

Vertically-aligned carbon nanotubes(CNTs) with multi-walled structure were successfully grown on a Fe-deposited Si substrate at low temperature below 330°C by using the microwave plasma chemical vapor deposition of methane and carbon dioxide gas mixture. This is apparently different from the conventional reaction in gas mixtures of hydrogen and methane, hydrogen and acetylene, and hydrogen and benzene ... etc. High quality carbon nanotubes were grown at lower temperature with CO₂ and CH₄ gas mixture than those used by the previous. After deposition, the microstructure morphology of carbon nanotubes was observed with scanning electron microscope and high-resolution transmission electron microscope. The characteristics of carbon nanotubes were analyzed by laser Raman spectroscopy. The results showed the variation of the flow rate ratio of CH₄/CO₂ from 28.5 sccm/30 sccm to 30/30 sccm and the DC bias voltage from –150 V to –200 V, at 300 W microwave power, 1.3–2.0 kPa range of total gas pressure, and substrate temperatures between 300°C and 350°C. Vertically aligned carbon nanotubes with the diameter of about 15 nm and multi-walled structure were illustrated by SEM and HRTEM. However, the highest yield of carbon nanotubes of about 50% was obtained at low temperature below 330°C by MPCVD for the CH₄/CO₂ gas mixture with properly controlled parameters.     

Growth and microstructures of carbon nanotube films prepared by microwave plasma enhanced chemical vapor deposition process

Well-aligned carbon nanotubes (CNTs) were grown on iron coated silicon substrates by microwave plasma enhanced chemical vapor deposition. Effect of plasma composition on the growth and microstructures of CNTs were investigated by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and optical emission spectroscopy. Morphology and microstructure of nanotubes were found to be strongly dependent on the plasma composition. Aligned bamboo-shaped nanotubes consisting of regular cone shaped compartments were observed for C₂H₂/NH₃/N₂ and C₂H₂/NH₃/H₂ gas mixtures. Randomly oriented or no nanotubes growth were observed in C₂H₂/H₂ and C₂H₂/N₂ gas mixtures respectively. CNTs grown in nitrogen rich plasma had more frequent short compartments while compartment length increased with decreasing nitrogen concentration in the plasma. Raman spectroscopy of CNTs samples revealed that CNTs prepared in nitrogen rich plasma had higher degree of disorder than those in low nitrogen or nitrogen free plasma. In-situ optical emission spectroscopy investigations showed that CN and H radicals play very important role in both the growth and microstructure of CNTs. Microstructure of CNTs has been correlated as a function of CN radical concentration in the plasma. It is suggested that presence of nitrogen in the plasma enhances the bulk diffusion of carbon through the iron catalyst particles which causes compartment formation. Based on our experimental observations, growth model of nanotubes under different plasma composition has been suggested using base growth mechanism.     

Field emission characteristics of fast grown nanocrystalline diamond/amorphous carbon composite films by microwave plasma-enhanced chemical deposition method

This study synthesized the nanocrystalline diamond/amorphous carbon (NCD/a-C) composite films by the microwave plasma-enhanced chemical vapor deposition (MPCVD) system with Ar/CH₄/N₂ mixtures. A localized rectangular-type jet-electrode with high density plasma was used to enhance the formation of NCD/a-C films, and a maximum growth rate of 105.6 µm/h was achieved. The content variations of sp² and sp³ phases via varying nitrogen gas flow rates were investigated by using Raman spectroscopy. The NCD/a-C film which synthesized with 6% nitrogen concentration and no hydrogen plasma etching treatment possessed a low turn-on electric field of 3.1 V/µm at the emission current of 0.01 µA.     

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.     

Selective growth of well-aligned carbon nanotubes by APCVD

Well-aligned good-quality carbon nanotube (CNT) array was grown on silicon substrate by atmospheric pressure chemical vapor deposition (APCVD) through SiO₂ masking. First, the patterned substrate was pretreated with NH₃ and then CNTs were synthesized at 800 °C using Ni as the catalyst, acetylene (C₂H₂) as the carbon source material and N₂ as the carrier gas. Effects of the NH₃-pretreatment time, the flow ratio of [C₂H₂]/[NH₃] and the CNT growth time on the qualities of CNT array were analyzed in detail. It was found that good-quality CNTs with an average length of around 15 μm could be grown by pretreating the Si substrate with NH₃ for 10 min and then conducting the CNT growth with a flow ratio of [C₂H₂]/[NH₃] = 30/100. Furthermore, the field emission property of CNT array was investigated using a diode structure. It was found that the turn-on electric field decreased with increasing CNT length. The turn-on electric field as low as about 2 V/μm with an emission current density of 10 μA/cm² was achieved for a CNT-array diode with the tube length near 18 μm. For the same device, the emission current density could be elevated to 10 mA/cm² with the applied voltage of 3.26 V/μm.     

Effects of methane flow rate on the optical properties and chemical bonding of germanium carbon films deposited by reactive sputtering

Amorphous hydrogenated germanium carbon (a-Ge_1−xC_x:H) films were prepared by radio frequency (RF) reactive magnetron sputtering of a pure Ge (111) target in a CH₄ + H₂+Ar mixture and their composition, optical properties, chemical bonding were investigated as a function of gas flow rate ratio of CH₄/(Ar + H₂). The results showed that the deposition rate first increased and then decreased as gas flow rate ratio of CH₄/(Ar + H₂) was increased from 0.125 to 0.625. And the optical gap of the a-Ge_1−xC_x:H films increased from 1.1 to 1.58 eV accompanied with the increase in the carbon content and the decrease in the relative content of Ge–C bonds of the films as the CH₄ flow rate ratio was increased, while refractive index of the films decreased and the absorption edge shifted to high energy. Through the analysis of X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy, it was found that the formation of Ge–C bonds in the films was promoted by low CH₄ flow rate which is connected with relatively high H₂ concentration and Ge content. Especially in low CH₄ concentration, the formation of sp²-hybridised C–C bonds was suppressed considerably both due to the etching effect on weak bonds of H and the fact that chemical bonding for germanium can be only sp³ hybridization.     

Synthesis of carbon coatings employing a plasma torch from an argon-acetylene gas mixture at reduced pressure

Amorphous hydrogenated carbon films (a-C:H) were formed on Si (1 1 1) wafers from an argon-acetylene gas mixture at a reduced pressure of 1000 Pa using a direct current (DC) plasma torch discharge. The Ar/C₂H₂ gas volume ratio varied from 1:1 to 8:1, the distance between plasma torch exit and the samples 0.04-0.095 m. The DC plasma torch technique allows the production of thick (∼90 μm) coatings at 0.3 μm/s growth rates. Raman spectra shape, D and G peak positions and the intensity ratio (I_D/I_G) show an increase of sp³ bond fraction with decreasing acetylene flow in argon plasma. Reflectance of the coatings deposited at Ar/C₂H₂=8:1 is high (∼97%) and slightly increases with increasing distance between samples and plasma torch exit.     

Controlled density of vertically aligned carbon nanotubes in a triode plasma chemical vapor deposition system

We report on the growth mechanism and density control of vertically aligned carbon nanotubes using a triode plasma enhanced chemical vapor deposition system. The deposition reactor was designed in order to allow the intermediate mesh electrode to be biased independently from the ground and power electrodes. The CNTs grown with a mesh bias of + 300 V show a density of ∼ 1.5 μm^− 2 and a height of ∼ 5 μm. However, CNTs do not grow when the mesh electrode is biased to − 300 V. The growth of CNTs can be controlled by the mesh electrode bias which in turn controls the plasma density and ion flux on the sample.     

Effect of hydrogen plasma pretreatment on growth of carbon nanotubes by MPECVD

We have grown carbon nanotubes (CNTs) with a microwave (μW) 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 use methane (CH₄) and hydrogen (H₂) gas for the growth of CNTs. Ni catalytic layer (10 nm thick) were deposited on the Ti-coated Si substrate by RF magnetron sputtering method. In this work, we report the effects of pretreatment μW power on the growth of CNTs. We have pretreated the Ni catalytic layer in different μW power (600, 700, and 800 W) and grown same μW power (800 W). Scanning electron microscopy (SEM) images show Ni catalytic layer diameter and density are varied dependent with their pretreatment conditions. Raman spectroscopy of CNTs shows that I_D/I_G ratios and G-peak positions vary with pretreatment conditions.     

Theoretical investigation of methane adsorption onto boron nitride and carbon nanotubes

Methane adsorption onto single-wall boron nitride nanotubes (BNNTs) and carbon nanotubes (CNTs) was studied using the density functional theory within the generalized gradient approximation. The structural optimization of several bonding configurations for a CH₄ molecule approaching the outer surface of the (8,0) BNNT and (8,0) CNT shows that the CH₄ molecule is preferentially adsorbed onto the CNT with a binding energy of −2.84 kcal mol⁻¹. A comparative study of nanotubes with different diameters (curvatures) reveals that the methane adsorptive capability for the exterior surface increases for wider CNTs and decreases for wider BNNTs. The introduction of defects in the BNNT significantly enhances methane adsorption. We also examined the possibility of binding a bilayer or a single layer of methane molecules and found that methane molecules preferentially adsorb as a single layer onto either BNNTs or CNTs. However, bilayer adsorption is feasible for CNTs and defective BNNTs and requires binding energies of −3.00 and −1.44 kcal mol⁻¹ per adsorbed CH₄ molecule, respectively. Our first-principles findings indicate that BNNTs might be an unsuitable material for natural gas storage.     

Effects of applied power on hydrogenated amorphous carbon (a-C:H) film deposition by low frequency (60 Hz) plasma-enhanced chemical vapor deposition (PECVD)

Hydrogenated amorphous carbon (a-C:H) films were deposited onto glass substrates using low frequency (60 Hz) plasma-enhanced chemical vapor deposition and the effects of the applied power on a-C:H films deposition were investigated. During deposition, the electron temperature and the density of CH₄-H₂ plasma were 2.4-3.1 eV and about 10⁸ cm⁻³, respectively. The main optical emission peak of the carbon species observed in the CH₄-H₂ plasma is shown to be excited carbon CH* at 431 nm. The sp³/sp² ratio, band gap, hydrogen content, and refractive index of a-C:H films gradually increased up to a power of 25 W and then saturated at higher power. This tendency is similar to the variation of plasma parameters with varying applied power, thereby indicating that a strong relationship exists between the properties of the films and the plasma discharge.     

Optical measurement in carbon nanotubes formation by pulsed laser ablation

Carbon nanotubes (CNTs) were produced by laser ablation of a graphite composite target in argon and nitrogen ambient gas. To investigate the effect of nitrogen gas on CNTs formation, the plasma plume was examined using optical emission spectroscopy. The vibrational temperature of C₂ molecules was estimated by fitting of a Swan band spectrum. The temperature in N₂ ambient gas is lower than that in Ar ambient gas. In a nitrogen atmosphere, the spectrum intensity of C₂ Swan band was enhanced and CN violet system was also observed. Soot collected in the reaction tube was observed using FE-SEM and TEM. The soot deposited in the nitrogen gas contained more bundled CNTs than those in Ar ambience.     

Lamellar Fe/Al2O3 catalyst for high-yield production of multi-walled carbon nanotubes bundles

The lamellar Fe/Al₂O₃ catalysts were prepared by sol-gel method, and then with these prepared catalysts, carbon nanotubes (CNTs) were synthesized by catalytic chemical vapor deposition (CCVD) method using C₂H₂ as precursor. The as-prepared CNTs and Fe/Al₂O₃ catalysts were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy and Raman spectrum. The results proved that the as-prepared CNTs actually existed in bundles. And the growth of CNTs bundles should be attributed to the lamellar catalysts, which supported the bottom growth mechanism of CNTs. The transition metal of Mo was not introduced in catalysts to produce CNTs bundles, which was different with others’ results.     

Structural characterization of a mechanically milled carbon nanotube/aluminum mixture

The structural evolution of carbon nanotubes (CNTs) during mechanical milling was investigated using SEM, TEM, XRD, XPS and Raman spectroscopy. The study showed that milling of the CNTs alone introduces defects but preserves the tubular structure. When milling the CNTs with aluminum (Al) powder in order to produce a composite, Raman spectroscopy has shown that most of the nanotubes are destroyed. During sintering of the CNT/Al milled mixture, the carbon atoms available from the destruction of the nanotubes react with the Al to form aluminum carbide (Al₄C₃). The effect of milling on the Al matrix was also studied.     

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.     

Characterization of metal-modified and vertically-aligned carbon nanotube films for functionally enhanced gas sensor applications

Carbon nanotube (CNT) networked films have been grown by radiofrequency plasma enhanced chemical vapour deposition (RF-PECVD) technology onto low-cost alumina substrates, coated by nanosized Fe-catalyst for growing CNTs, to perform chemical detection of hazardous gases, at an operating sensor temperature in the range 25-150 °C. The morphology and structure of the CNT networks have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. The carbon nanotubes were “forest-like” with ropes vertically-aligned to the substrate surface. A dense network of bundles of multiple tubes consisting of multi-walled carbon nanostructures appears with a maximum length of 7-10 μm and single-tube diameter varying in the range of 5-35 nm. Surface functionalizations of the vertically-aligned CNT networks with nominally 5 nm thick Pt-, Ru- and Ag-nanoclusters, prepared by magnetron sputtering, provide higher sensitivity for significantly enhanced gas detection of NO₂, H₂, ethanol and toluene up to a low limit of sub-ppm level. The measured electrical conductance of the functionalized CNTs upon exposures of a given oxidizing and reducing gas is modulated by a charge transfer model with p-type semiconducting characteristics. Functionalized CNT gas sensors exhibited better performances compared to unmodified CNTs, making them highly promising candidates for environmental air monitoring applications, at ppb-level of toxic gas detection.     

Characteristics of nano-crystalline diamond films prepared in Ar/H2/CH4 microwave plasma

Characteristics of nano-crystalline diamond (NCD) thin films prepared with microwave plasma chemical vapor deposition (CVD) were studied in Ar/H₂/CH₄ gas mixture with a CH₄ gas ratio of 1-10% and H₂ gas ratio of 0-15%. From the Raman measurements, a pair of peaks at 1140 cm^− 1 and 1473 cm^− 1 related to the trans-polyacetylene components peculiar to nano-crystalline diamond films was clearly observed when the H₂ gas ratio of 5% was added in Ar/H₂/CH₄ mixture. With an increase of H₂ gas content up to 15%, their peaks decreased, while a G-peak at roughly 1556 cm^− 1 significantly increased. The degradation of NCD film quality strongly correlates with the decrease of C₂ optical emission intensity with the increase of hydrogen gas contents. From the surface analysis with atomic force microscopy (AFM), it was found that grain sizes of NCD films were typically of 10-100 nm in case of 5% H₂ gas addition.     

Influence of Fe nanoparticles diameters on the structure and electron emission studies of carbon nanotubes and multilayer graphene

In this paper we report the effect of Fe film thickness on the growth, structure and electron emission characteristics of carbon nanotubes (CNTs) and multilayer graphene deposited on Si substrate. It is observed that the number of graphitic shells in carbon nanostructures (CNs) varies with the thickness of the catalyst depending on the average size of nanoparticles. Further, the Fe nanoparticles do not catalyze beyond a particular size of nanoclusters leading to the formation of multilayer graphene structure, instead of carbon nanotubes (CNTs). It is observed that the crystallinity of CNs enhances upon increasing the catalyst thickness. Multilayer graphene structures show improved crystallinity in comparison to CNTs as graphitic to defect mode intensity ratio (I_D/I_G) decreases from 1.2 to 0.8. However, I_2D/I_G value for multilayer graphene is found to be 1.1 confirming the presence of at least 10 layers of graphene in these samples. CNTs with smaller diameter show better electron emission properties with enhancement factor (γ_C = 2.8 × 10³) in comparison to multilayer graphene structure (γ_C = 1.5 × 10³). The better emission characteristics in CNTs are explained due to combination of electrons from edges as well as centers in comparison to the multilayer graphene.     

Theoretical investigation of methane adsorption onto boron nitride and carbon nanotubes

Abstract

Methane adsorption onto single-wall boron nitride nanotubes (BNNTs) and carbon nanotubes (CNTs) was studied using the density functional theory within the generalized gradient approximation. The structural optimization of several bonding configurations for a CH₄ molecule approaching the outer surface of the (8,0) BNNT and (8,0) CNT shows that the CH₄ molecule is preferentially adsorbed onto the CNT with a binding energy of ?2.84 kcal mol^?1. A comparative study of nanotubes with different diameters (curvatures) reveals that the methane adsorptive capability for the exterior surface increases for wider CNTs and decreases for wider BNNTs. The introduction of defects in the BNNT significantly enhances methane adsorption. We also examined the possibility of binding a bilayer or a single layer of methane molecules and found that methane molecules preferentially adsorb as a single layer onto either BNNTs or CNTs. However, bilayer adsorption is feasible for CNTs and defective BNNTs and requires binding energies of ?3.00 and ?1.44 kcal mol^?1 per adsorbed CH₄ molecule, respectively. Our first-principles findings indicate that BNNTs might be an unsuitable material for natural gas storage.     

Improvement of mechanical properties in aluminum/CNTs nanocomposites by addition of mechanically activated graphite

Carbon nanotubes reinforced aluminum nanocomposite was prepared by ball milling route. CNTs were initially mixed with mechanically amorphized graphite. Specimens were analyzed by X-ray diffractometry and Raman spectroscopy. Crystallite size and dislocation density were calculated by modified Warren–Averbach method. Carbide formation was semi-quantitatively investigated via Raman spectroscopy. A band located in 950 cm⁻¹ was considered to be corresponded to Al₄C₃. Hardness of the samples was also evaluated using a Vickers micro-hardness tester. The hardness strengthening contributions were modeled to evaluate interfacial bonding between CNTs and the aluminum matrix. In specimens, including amorphized graphite, hardening was due to both work hardening and second phase strengthening otherwise, only due to work hardening. It was deducted that the amorphized graphite has a major role for mechanical properties improvement. This seems to be due to the formation of aluminum carbide at the interface which consequently increases adhesion of CNTs to aluminum.