Carbon fractals grown from carbon nanotips by plasma-enhanced hot filament chemical vapor deposition

Carbon nanomaterials with different structures were prepared in a custom-designed plasma-enhanced hot filament chemical vapor deposition system using methane, hydrogen and nitrogen. They were investigated by scanning electron microscopy (SEM) and micro-Raman spectroscopy. The SEM images show that the smooth carbon nanotips are formed under a high bias current and the carbon fractals can grow from the tips of the carbon nanotips under a low bias current. The results of micro-Raman spectroscopy indicate that the graphitization of the carbon nanomaterials was improved by ion bombardment. Combined the ion bombardment, electric field enhancement and electron emission mechanisms, the formation model of the carbon fractals was suggested.     

Field emission properties and synthesis of carbon nanotubes grown by rf plasma-enhanced chemical vapor deposition

Plasma-enhanced chemical vapor deposition (PECVD) method was employed to grow the Fe-catalyzed carbon nanotubes (CNTs). The grown CNTs with a uniform diameter in the range of about 10-20 nm and the typical lengths beyond 1 μm resulted in a very high aspect ratio. The Raman and TEM results showed that the grown CNTs contained a large amount of carbonaceous particles and crystal defects, such as pentagon-heptagon pair defects. XPS measurement indicated that the CNTs had CH covalent bonds. Field emission characteristics exhibited the low turn-on threshold field of 2.75 V/μm and the maximum emission current density of 7.75 mA/cm² at 6.5 V/μm. The growth mechanism of CNTs and the effects of hydrogen plasma on their structure were discussed.     

A chemical kinetic model for chemical vapor deposition of carbon nanotubes

Carbon nanotubes (CNTs) are classified among the most promising novel materials due to their exceptional physical properties. Still, optimal fabrication of carbon nanotubes involves a number of challenges. Whatever be the fabrication method, a process optimization can be evolved only on the basis of a good theoretical model to predict the parametric influences on the final product. The work reported here investigates the dependence of the deposition parameters on the controllable parameters for carbon nanotube growth during Chemical vapor deposition (CVD), through a chemical kinetic model. The theoretical model consisted of the design equations and the energy balance equations, based on the reaction kinetics, for the plug flow and the batch reactor, which simulate the CVD system. The numerical simulation code was developed in-house in a g++ environment. The results predicted the growth conditions for CNT: the deposition temperature, pressure and number of atoms, which were found to be influenced substantially by the initial controllable parameters namely the temperature, volumetric flow rate of the carbon precursor, and the reaction time. An experimental study was also conducted on a CVD system developed in the laboratory, to benchmark the computational results. The experimental results were found to agree well with the theoretical predictions obtained from the model.     

化学气相沉积法制备定向碳纳米管阵列

以二茂铁和二甲苯分别作为催化剂和碳源，采用一种无模板的化学气相沉积法，使用单温炉设备，成功地制备了高度定向的碳纳米管阵列.分别用扫描电子显微镜、透射电子显微镜和电子能量散射谱、拉曼光谱对碳纳米管阵列进行形貌观察和表征, 并研究了不同工艺参数对碳纳米管阵列形貌的影响.结果表明：在生长温度为800℃，催化剂浓度为0.02g/mL，抛光硅片上容易获得高质量的定向碳纳米管阵列，在此优化条件下生长的定向碳纳米管的平均生长速率可达25μm/min.     

Synthesis of carbon nanotubes by ECR plasma-assisted chemical vapor deposition

Carbon nanotubes have been grown using an electron cyclotron resonance (ECR) plasma source at a substrate temperature of 500 °C. Methane has been used as the source gas. A network of carbon nanotubes has been observed in scanning electron microscopy. Transmission electron microscopy revealed that the structure consists of straight, Y-junction and ring-like nanotubes. Further, electron diffraction of the nanotubes confirms a graphite crystal structure. PACS 81.16.He; 68.37.Lp; 68.37.Hk; 85.35.Kt; 75.75.+a     

Influence of growth duration on size and morphology of boron nitride nanotubes grown via chemical vapor deposition technique

Boron nitride nanotubes are synthesized on Si substrate via a chemical vapor deposition technique with different growth durations. Field emission scanning electron microscopy micrographs show a clear influence of growth duration on size and morphology of the synthesized nanotubes. It reveals that the diameter of the tubes decreases and length increases with an increase in growth duration. Total diameter of the tube has been reduced up to 31% and length increased up to 30% with an increase of 20 min growth duration. As a result, morphology of nanotubes has also been changed from curve like to straight. Transmission electron microscope confirms the tubular structure of the synthesized nanotubes with an interlayer spacing of 0.34 nm that corresponds to d₍₀₀₂₎ plane of hexagonal boron nitride and its crystalline nature. Energy dispersive X-ray spectroscopy indicates the presence of magnesium particles in the synthesized samples that refers to its catalytic growth. X-ray photoelectron spectroscopy confirms the elemental compositions of the sample. Raman spectra reveal a peak shift of 5.48 cm⁻¹ towards higher region of wavelength that corresponds to E_2g mode of vibration in hexagonal boron nitride. This result also confirms the structural change in the synthesized boron nitride nanotubes with respect to the growth duration.     

Catalyst patterning methods for surface-bound chemical vapor deposition of carbon nanotubes

We present three different catalyst preparation and patterning techniques for plasma-enhanced chemical vapor deposition of carbon nanostructures from acetylene and ammonia mixtures. The different merits and potential areas of application are highlighted for each technique as compared to the benchmark of e-beam-lithography patterning. Maskless, focused ion beam written Pt can nucleate aligned carbon nanofibers, thereby allowing a sub-100 nm lateral resolution on non-planar substrate geometries combined with an in-situ monitoring. Ion beam milling additionally enables the pre-shaping and marking of the substrate, which is shown for the growth of individual nanofibers on the apex of commercial scanning probe tips. Pulsed electrochemical deposition was used to form Ni and Fe catalyst islands of controlled size and density. This is also demonstrated on complex substrate geometries such as carbon cloth. Nanocontact printing was employed to deposit a highly purified Co colloid in regular patterns with feature sizes down to 100 nm onto silicon wafers for low cost patterning over large areas. We analyze the catalyst restructuring upon exposure to elevated temperatures for each technique and relate this to the nucleated nanofiber dimensions and array densities. The flexibility in catalyst and substrate material allows a transfer of our achievements to catalyst-assisted growth of nanostructures in general facilitating their hierarchical device integration and future application. PACS 81.16.Rf; 81.16.Hc; 61.46.+w     

Growth kinetics of low temperature single-wall and few walled carbon nanotubes grown by plasma enhanced chemical vapor deposition

Single-wall, double walled or few walled nanotubes (FWNT) are grown by electron cyclotron resonance plasma enhanced chemical vapor deposition (ECR-PECVD) at temperature as low as 600 °C. Most of these structures are isolated and self-oriented perpendicular to the substrate. The growth mechanism observed for single-wall and few walled (less than seven walls) nanotubes is the “base-growth” mode. Their grow kinetics is investigated regarding two parameters namely the growth time and the synthesis temperature. It is shown that nucleation and growth rate is correlated with the number of walls into FWNT. It also provides an evidence of a critical temperature for FWNT synthesis.     

Substrate preparation techniques for direct investigation by TEM of single wall carbon nanotubes grown by chemical vapor deposition

We have investigated and evaluated different TEM sample preparation techniques for studying carbon single-walled nanotube (C-SWNT) nucleation and growth, issued from CVD processes when the catalyst is supported on a substrate. This kind of study requires means to observe individual and isolated tubes. It implies using synthesis conditions able to produce only a low density of tubes and to thin the substrate to electron transparency, to observe the nanotubes and the catalytic particles from which they have grown in their native state. We have tested two approaches, depending if the substrate is thinned after or before the synthesis. The low tube density requirement led us to exclude all the techniques where the substrate is thinned to electron transparency after the synthesis. We have shown, that, with this last approach, all TEM preparation techniques dramatically suffer from a lack of control of thin areas with respect to the location of the tubes, which is unknown. However we have demonstrated that the suitable approach is to perform synthesis directly on transparent substrates presenting several holes. We have tested the capabilities and the potentialities of these supports for studying the size distribution and composition of the catalytic particles, the nucleation mode, the diameter and helicity of the tubes. These results are very promising and represent an important step for performing specific nanoscale TEM analyses necessary for the study of the growth mechanism of nanotubes on substrates.     

Preparation of carbon nanosheets deposited on carbon nanotubes by microwave plasma-enhanced chemical vapor deposition method

Carbon nanosheets were synthesized by microwave plasma-enhanced chemical vapor deposition method on carbon nanotubes substrate which was treated by hydrogen plasma. The results showed that the diameters of carbon nanotubes first got thick and then “petal-like” carbon nanosheets were grown on the outer wall of carbon nanotubes. The diameters of carbon nanotubes without and with carbon nanosheets were 100-150 and 300-500 nm, respectively. Raman spectrum indicated the graphite structure of carbon nanotubes/carbon nanosheets. The hydrogen plasma treatment and reaction time greatly affected the growth and density of carbon nanosheets. Based on above results, carbon nanosheets/carbon nanotubes probably have important applications as cold cathode materials and electrode materials.     

Synthesis of multiwall carbon nanotubes by chemical vapor deposition of ferrocene alone

Multiwall carbon nanotubes (MWNTs) filled with Fe nanoparticles (NPs) have been synthesized by thermal chemical vapor deposition of ferrocene alone as the precursor. The MWNTs were grown at different temperatures: 980 and 800 ^°C. Characterization of as-prepared MWNTs was done by scanning and transmission electron microscopy, and X-ray diffraction. The transmission electron microscopy study revealed that Fe NPs encapsulated in MWNTs grown at 980 and 800 ^°C are spherical and rod shaped, respectively. Room-temperature vibrating sample magnetometer studies were done on the two samples up to a field of 1 T. The magnetization versus magnetic field loop reveals that the saturation magnetization for the two samples varies considerably, almost by a factor of 4.6. This indicates that Fe is present in different amounts in the MWNTs grown at the two different temperatures.     

Understanding the nucleation mechanisms of carbon nanotubes in catalytic chemical vapor deposition

The nucleation of carbon caps on small nickel clusters is studied using a tight binding model coupled to grand canonical Monte Carlo simulations. It takes place in a well defined carbon chemical potential range, when a critical concentration of surface carbon atoms is reached. The solubility of carbon in the outermost Ni layers, that depends on the initial, crystalline or disordered, state of the catalyst and on the thermodynamic conditions, is therefore a key quantity to control the nucleation.     

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     

Graphene oxides and carbon nanotubes embedded in polyacrylonitrile-based carbon nanofibers used as electrodes for supercapacitor

This study investigates the use of graphene oxides (GOs) and carbon nanotubes (CNTs) embedded in polyacrylonitrile-based carbon nanofibers (GO–CNT/CNF) as electrodes for the supercapacitor. GO–CNT/CNF was prepared by electrospinning, and was subsequently stabilized and activated. The specific capacitance of GO–CNT/CNF is 120.5 F g⁻¹ in 0.5 M Na₂SO₄ electrolyte, which is higher than or comparable to the specific capacitances of carbon-based materials in neutral aqueous electrolyte, as prepared in this study. GO–CNT/CNF also exhibits a superior cycling stability, and 109% of the initial specific capacitance after 5000 cycles. The high capacitance of GO–CNT/CNF could be attributed to the edge planes and the functional groups of GO, the highly electrical conductivity of CNT, and the network structure of the electrode.     

Structure and magnetic properties of FeCo nanoparticles encapsulated in carbon nanotubes grown by microwave plasma enhanced chemical vapor deposition

Plasma enhanced chemical vapor deposition is a simple technique for preparing magnetic nanoparticles encapsulated in carbon nanotubes. We employed alloy catalysts when growing carbon nanotubes to control the composition and magnetic properties of encapsulated nanoparticles. Single-crystal nanoparticles were successfully encapsulated in carbon nanotubes, and their crystal structure varied depending on the composition of the alloy catalysts. The coercive force of nanoparticles also varied according to the composition of the catalysts.     

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.     

Effect of sulfur on the growth of carbon nanotubes by detonation-assisted chemical vapor deposition

Thiophene was introduced as an additive in detonation-assisted chemical vapor deposition to investigate the effect of sulfur on the growth of carbon nanotubes. The results reveal that sulfur promoted the growth of hollow tubes, instead of bamboo-like carbon nanotubes without sulfur addition. Structural characterization of products indicates that the dynamic reshaping of the catalyst assisted bamboo-like carbon nanotube growth and the bamboo knots preferentially nucleated on the Ni-graphite step edges. It is suggested that sulfur suppressed the bamboo knot growth through blocking the step sites. The findings are important for understanding of nanotube growth mechanism and the role of sulfur often involved in catalytic reactions.     

Effect of temperature on growth and structure of carbon nanotubes by chemical vapor deposition

The effect of temperature on growth and structure of carbon nanotubes (NTs) using chemical vapor deposition (CVD) has been investigated. Iron embedded silica was used to grow NTs in large quantity at various temperatures from 600 to 1050 °C with gas pressure fixed at 0.6 and 760 Torr, respectively. The growth and structure of the NTs are strongly affected by the temperature. At low gas pressure, the NTs are completely hollow at low temperature and bamboo-like structure at high temperature. While at high gas pressure, all the NTs are bamboo-like structure regardless of temperature. The diameter of NTs increases significantly with temperature. At low gas pressure the diameter gets bigger by mainly increasing the number of graphene layers of the wall of NTs, whereas at high gas pressure the diameter gets bigger by increasing both the number of graphene layers of the wall and the inner diameter of the NTs. This result indicates that the growth temperature is crucial in synthesizing NTs with different structures. The findings here are important for realizing controlled growth of NTs for their applications in different fields. Received: 20 November 2001 / Accepted: 21 November 2001 / Published online: 4 March 2002     

Controllable growth of individual, uniform carbon nanotubes by thermal chemical vapor deposition

We report on the controllable growth of individual, uniform carbon nanotubes using thermal chemical vapor deposition (CVD). We performed a detailed study of the various factors influencing the growth of single nanotubes. In particular, we investigated the role played by catalyst layer thickness, catalyst dot size, deposition temperature, and gas source pressure on the growth process of straight, single nanotubes. Straight, individual nanotubes with uniform diameter can be obtained by decomposition of 0.1 mbar of acetylene at a temperature of 800 °C over a 5 nm thick nickel film that is patterned into square dots with dimensions below 500 nm. We compare the performance of thermal CVD and of plasma enhanced CVD for growing individual nanotubes.     

Synthesis of multi-walled carbon nanotubes using CoMnMgO catalysts through catalytic chemical vapor deposition

The Co Mg O and Co Mn Mg O catalysts are prepared by a co-precipitation method and used as the catalysts for the synthesis of carbon nanotubes（CNTs） through the catalytic chemical vapor deposition（CCVD）. The effects of Mn addition on the carbon yield and structure are investigated. The catalysts are characterized by temperature programmed reduction（TPR） and X-ray diffraction（XRD） techniques, and the synthesized carbon materials are characterized by transmission electron microscopy（TEM） and thermo gravimetric analysis（TG）. TEM measurement indicates that the catalyst Co Mg O enclosed completely in the produced graphite layer results in the deactivation of the catalyst. TG results suggest that the Co Mn Mg O catalyst has a higher selectivity for CNTs than Co Mg O. Meanwhile, different diameters of CNTs are synthesized by Co Mn Mg O catalysts with various amounts of Co content, and the results show that the addition of Mn avoids forming the enclosed catalyst, prevents the formation of amorphous carbon, subsequently promotes the growth of CNTs, and the catalyst with decreased Co content is favorable for the synthesis of CNTs with a narrow diameter distribution.The Co Mn Mg O catalyst with 40% Co content has superior catalytic activity for the growth of carbon nanotubes.