Synthesis of phosphorus doped carbon nanotubes using chemical vapor deposition

Phosphorous-doped carbon nanotubes (PCNTs) was prepared via two-step methodology employing chemical vapor deposition, by using available starting materials and catalyst. First, CNTs was produced from acetylene gas at 750 ºC and then, PCNTs have been prepared with total yield of 44% by recooking of the prepared CNT with Ph₃P at 600 ºC. The product was characterized with FESEM, TEM and EDS analyses, which confirmed its nanotube shape and the presence of phosphorous atom. The high thermal stability of the product was obtained from TGA analysis, showing only 16.5% weight loss up to 890 ºC. The Raman spectrum of the product showed the I_D/I_G ration equal to 0.84. Moreover, the catalytic potency of the product has been examined in ORR electrochemical reaction using CV and LSV diagrams. The results confirmed appropriate catalytic activity and high stability of the product for this process.     

Catalytic chemical vapor deposition of carbon nanotubes using Ni-La-O precursors

Carbon nanotubes (CNT) are synthesized by catalytic chemical vapor deposition with different compositions of Ni-La-O catalyst precursors obtained by citric acid complexometry. Only two compounds: LaNiO₃ (perovskite-type crystal structure, hexagonal system) and La₂NiO₄ (spinel-type crystal structure, orthorhombic system) in the obtained Ni-La-O catalyst precursors have the ability to grow CNT. Moreover, CNT obtained with the two different crystal structure catalyst precursors have different characteristics: different yield, pattern and oxidation resistance performance.     

Patterning polyethylene oligomers on carbon nanotubes using physical vapor deposition

Periodic patterning on one-dimensional (1D) carbon nanotubes (CNTs) is of great interest from both scientific and technological points of view. In this letter, we report using a facile physical vapor deposition method to achieve periodic polyethylene (PE) oligomer patterning on individual CNTs. Upon heating under vacuum, PE degraded into oligomers and crystallized into rod-shaped single crystals. These PE rods periodically decorate on CNTs with their long axes perpendicular to the CNT axes. The formation mechanism was attributed to "soft epitaxy" growth of PE oligomer crystals on CNTs. Both SWNTs and MWNTs were decorated successfully with PE rods. The intermediate state of this hybrid structure, MWNTs absorbed with a thin layer of PE, was captured successfully by depositing PE vapor on MWNTs detached from the solid substrate, and was observed using high-resolution transmission electron microscopy. Furthermore, this hybrid structure formation depends critically on CNT surface chemistry: alkane-modification of the MWNT surface prohibited the PE single-crystal growth on the CNTs. We anticipate that this work could open a gateway for creating complex CNT-based nanoarchitectures for nanodevice applications.     

Hot-wire chemical vapor deposition of carbon nanotubes

Hot-wire chemical vapor deposition (HWCVD) has been employed for the continuous gas-phase generation of both carbon multi-wall and single-wall nanotube (MWNT and SWNT) materials. Graphitic MWNTs were produced at a very high density at a synthesis temperature of 600 °C. SWNTs were deposited at a much lower density on a glass substrate held at 450 °C. SWNTs are typically observed in large bundles that are stabilized by tube–tube van der Waals’ interactions. However, transmission electron microscopy analyses revealed only the presence of isolated SWNTs in these HWCVD-generated materials.     

Structure control of carbon nanotubes using radio-frequency plasma enhanced chemical vapor deposition

Carbon nanotube structures such as tube diameter, growth site, and formation density are controlled using radio-frequency (RF, 13.56 MHz) plasma enhanced chemical vapor deposition (RF-PECVD) method. We have produced uniformly well-aligned multi-walled carbon nanotubes (MWNTs) grown over the large scale area and linearly arrayed MWNTs grown in a selected area without any highly-sophisticated patterning process. In our RF-PECVD experiment, furthermore, individually grown single-walled carbon nanotubes (SWNTs) or their thin bundles are synthesized for the first time within the scope of the PECVD methods. These results indicate that PECVD method provides the high potential for the further development of nano-technology.     

Supercritical carbon dioxide-assisted deposition of tin oxide on carbon nanotubes

This work demonstrates a versatile and effective method for uniform deposition of SnO₂ on the surfaces of CNTs. The obtained SnO₂–CNT nanohybrids were morphologically and structurally characterized by different techniques. Detailed transmission electron microscopy (TEM) observation revealed that SnO₂ nanoparticles may cover the tube surfaces or be encapsulated into the tube channels by manipulating experimental conditions. The loading density of SnO₂ on CNTs is tunable by varying the initial weight ratio of the precursor to CNTs. This simple and clean method offers a flexible avenue for further exploring the properties and applications of the as-synthesized CNT composites.     

Selective deposition of catalyst nanoparticles using the gravitational force for carbon nanotubes interconnect

The photolithography process has generally been used for the making of catalyst layers used for the synthesis of CNTs due to its comparative ease. However, this method results in the formation of undesirable catalyst particles, which deteriorate the quality of the devices. Therefore, we tried to form a catalyst layer without using any lift-off or wet etching process, especially for the formation of carbon nanotube interconnects. After spin coating the samples, which were previously fabricated with several vias, with an iron-acetate solution, the catalyst layer was pulled down into the bottom of the holes through the force of gravity. We were able to remove the catalyst layer which was coated over undesirable areas, by TMAH (tetramethylammonium hydroxide, N(CH₃)₄OH) treatment. After the catalyst deposition process, we synthesized CNTs and observed them by scanning electron microscopy (SEM).     

Nanopumping using carbon nanotubes

A new "nanopumping" effect consisting of the activation of an axial gas flow inside a carbon nanotube by producing Rayleigh traveling waves on the nanotube surface is predicted. The driving force for the new effect is the friction between the gas particles and the nanotube walls. A molecular dynamics simulation of the new effect was carried out showing macroscopic flows of atomic and molecular hydrogen and helium gases in a carbon nanotube.     

Controlling electron-beam-induced carbon deposition on carbon nanotubes by Joule heating

Electron-beam-induced deposition (EBID) of carbon on the surface of carbon nanotubes was well controlled by passing different electrical currents through the nanotubes. The control is due to Joule heating and the temperature of the carbon nanotubes was estimated. The deposition rate was found to increase and then decrease with the temperature and was maximized at about 310?K and approached zero at about 400?K. The method can be used to control the deposition rate of EBID in nanowelding and nanofabrication and to eliminate amorphous carbon contamination in in situ study of nanostructures.     

改进化学气相沉积法在炭纤维表面生长碳纳米管(英文)

采用一种改进的化学气相沉积法在炭纤维表面制备碳纳米管。为了提高炭纤维表面的润湿性能,炭纤维在浸渍之前先在CVD设备中在真空下973 K的高温处理,然后在硝酸和浓硫酸体积比为3∶1的混合酸中酸处理30 min。而改进的化学气相沉积法关键在于让催化剂的还原步骤和碳纳米管的生长步骤同时进行。这样通过减小过渡金属元素与炭纤维之间的接触时间从而降低了它们之间的相互扩散,在确保了炭纤维本身的力学性能下降程度明显小于用普通化学气相法制备的情况下生长出长且茂密的碳纳米管阵列。另外,经过对工艺参数的优化发现当用乙醇作溶剂,Fe(NO3)3.9H2O溶度为100 mmol/L,氢气和碳源气体比值为4/1,而生长时间为30 min时得到最好的碳纳米管阵列。     

Reactor length-scale modeling of chemical vapor deposition of carbon nanotubes

Chemical Vapor Deposition (CVD) of carbon nanotubes from a gas mixture consisting of methane (carbon precursor) and hydrogen (a carrier gas) in the presence of cobalt, nickel or iron catalytic particles in a cylindrical reactor is modeled at the reactor length-scale by solving a continuum-based coupled boundary-layer laminar-flow hydrodynamics, heat-transfer, gas-phase chemistry and surface chemistry problem. The model allows determination of the gas-phase fields for temperature, velocity, and various species as well as the surface-species coverages and the carbon deposition rate. Various available experimental and theoretical assessments are used to construct the necessary database for gas-phase and surface chemistry and gas-phase transport parameters. A reasonably good agreement is found between the model predicted and the experimentally measured carbon nanotubes deposition rates over a relatively large range of processing conditions.     

Diameter controlled chemical vapor deposition synthesis of single-walled carbon nanotubes

In this study, we systematically investigated the influence of catalyst preparation procedures on the mean diameter of single-walled carbon nanotubes (SWNTs) synthesized by the alcohol catalytic chemical vapor deposition (ACCVD) process. It was found that the SWNT diameter is dependent upon both reduction temperature and time, with lower reduction temperature and/or shorter reduction time resulting in smaller diameter SWNTs. The morphology of the SWNTs also changed from vertically aligned to randomly oriented when the reduction temperature was below 500 degrees C. We also found that introducing a small amount of water during the catalyst reduction stage significantly decreased the mean diameter of the SWNTs. Lastly, we report on the use of a new binary catalyst system in which rhodium was combined with cobalt. This new Co/Rh combination produced SWNTs of smaller diameter than the conventional Co/Mo catalyst.     

Structure of multiwalled carbon nanotubes grown by chemical vapor deposition

Carbon nanotubes have been grown by chemical vapor deposition at 650°C in an argon atmosphere using a butane-propane mixture and a nickel catalyst and have been characterized by scanning and transmission electron microscopy and Raman spectroscopy. The results indicate that the multiwalled nanotubes have an imperfect graphite-like structure with a conical supramolecular configuration. A phenomenological technique is proposed for statistical analysis of the state of carbon nanotubes in measurements of the intensity of the defect zone D in their Raman spectra.     

化学气相沉积法制备多壁碳纳米管

以带程序升温装置的管式电阻炉为实验装置,采用化学气相沉积法,在一定的工艺条件下裂解二茂铁与双鸭山精煤的混合物制备出多壁碳纳米管.采用透射电镜、Raman光谱以及X射线衍射技术对碳纳米管产物进行表征,同时研究了碳纳米管的生长机理.     

Role of carbon atoms in plasma-enhanced chemical vapor deposition for carbon nanotubes synthesis

The role of carbon atoms in a dc plasma-enhanced chemical vapor deposition for carbon nanotubes (CNTs) synthesis was investigated. It was observed that at 1.33 kPa pressure of CH₄ gas in plasma, a high value of the ratio between the intensities of the graphite peak (G peak) and the disorder peak (D peak) in the Raman spectrum corresponds to the maximum value of the excited C number density in the vicinity of the Si substrate. It was found that a CH₄ gas pressure higher than 1.33 kPa leads to an increase of the relative density of the C₂, C₃ molecules and the clusters, and to a decrease of the C excited atom number density in plasma. The presence of a high amount of sp²-graphite in the composition of CNTs observed in Raman spectrum was also confirmed by the measurement of the IR-active G peak at 1584 cm^- 1 in the transmission spectrum.     

非晶碳包覆碳纳米管复合结构电泳沉积及其场发射性能研究

利用电泳法在镀镍的聚酰亚胺薄膜上制备了非晶碳包覆碳纳米管复合结构柔性冷阴极.利用扫描电镜观察了结构形貌.并对其场发射性能进行了研究.结果显示,该复合结构柔性冷阴极具有较低的开启电场和较高的发射电流密度.     

Fabrication and characteristics of field emitter using carbon nanotubes directly grown by thermal chemical vapor deposition

We experimentally present the effects of vertical alignment and density of carbon nanotubes on the emission current level. For practical display application, we have fabricated the triode type emitter using directly grown nanotubes as emission tip, and characterized their basic field emission properties. The triode type emitter exhibited a turn-on voltage of 37 V and an anode current density of 1.7 μA with gate voltage at 47 V. The vertical alignment of nanotubes does not play a key role in improving the emission properties in triode type nanotubes emitter.     

Large-scale synthesis of BN nanotubes using carbon nanotubes as template

Boron nitride nanotubes (BN-NTs) were synthesized in large scale by the reaction of NaBH₄ and NH₄Cl in the temperature range of 500-600 °C for 10-18 h, where carbon nanotubes (CNTs) were mixed together with the reactants to serve as template. Pure BN-NTs were obtained by oxidizing the product at about 800 °C in air atmosphere. The structure and morphology of the product with a surface area of 106.635 m²/g were characterized by X-ray diffraction, transmission electron microscopy, Fourier transformation infrared spectroscopy, and thermogravimetric analysis. Large scale preparation of BN-NTs could be realized by this simple and effective route.     

Dispersion of carbon nanotubes using organic solvents

Phenyl ethyl alcohol was used for fast and stable dispersion of carbon nanotubes. This solvent, more effective than ethanol and toluene, allows easy dispersion of carbon nanotubes for TEM characterization. For TEM grids prepared at high dilution, it is possible to observe each tube separately. Applying that solvent, it was possible to measure the length, the diameter and the solubility of different carbon nanotubes samples.