Controllable fabrication of SnO2-coated multiwalled carbon nanotubes by chemical vapor deposition

A simple and efficient approach for coating multiwalled carbon nanotubes (MWCNTs) with size-controllable SnO₂ nanoparticles by chemical vapor deposition has been developed using tin hydride (SnH₄) gas as the source of SnO₂ at 550 °C. The size and coverage of SnO₂ nanoparticles can be adjusted by simply controlling the deposition time and the flow rate of the SnH₄/N₂ mixture gas during the CVD procedure. In addition, by using the MWCNTs as a sacrificial template, a kind of one-dimensional chain-like SnO₂ nanostructure has been synthesized by increasing the deposition temperature to 730 °C. This technique may provide a good way to produce tunable SnO₂-MWCNT composites.     

Diameter control of carbon nanotubes by changing the concentration of catalytic metal ion solutions

We have developed a simple new method to control the diameter of carbon nanotubes (CNTs) using catalytic nanoparticle arrays fabricated by filling the pores of well-ordered porous anodic aluminum oxide (AAO) templates with a metal ion solution. Fe ion solution was used to fill the pores in which Co had been deposited electrochemically, and then the template was dried naturally on a magnet. After this process, the pores were widened in NaOH solution. Well-graphitized multi-walled CNTs were grown from almost all the pores and were very long in length and homogeneous in diameter. We were able to control the diameter of CNTs, simply, by changing the concentration of iron ion solution. For example, the average outer diameters of the CNTs are 7 ± 1.5, 13 ± 1, and 17 ± 1 nm when the concentrations of Fe ion in their mother solutions were 1.0 × 10⁻³, 3.0 × 10⁻³, and 6.0 × 10⁻³ M, respectively. The inner diameters of these CNTs corresponded to the calculated diameters of Fe nanoparticles by assuming that all Fe ions contained in each pore are reduced to a single nanoparticle. This means that homogeneous nanoparticles are made in each pore. Our new method could be used to fabricate homogeneous nanoparticles from most metal ion solutions.     

Growth of multiwalled carbon nanotubes during the initial stages of aerosol-assisted CCVD

We report a study of the initial stages of growth of aligned multiwalled carbon nanotubes (MWNT) synthesised by catalytic chemical vapour deposition (CCVD) of liquid aerosol obtained from toluene/ferrocene solution. A special experimental procedure has been developed to stop the process after short durations (30 s to 2 min). Two different pyrolysis temperatures are considered: 800 and 850 °C. Both scanning and transmission electron microscopy (SEM, TEM) coupled to energy-dispersive X-ray (EDX) analyses are used in order to determine the location of catalyst particles and to examine their chemical nature, morphology and size distribution when nanotubes start to grow. During the early stages (30 s), we observe the formation of a layer of catalyst particles on silicon substrates before the growth of nanotubes. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements indicate the occurrence of iron oxide (γ-Fe₂O₃ or Fe₃O₄). In addition, XPS analysis reveals the formation of graphite-like carbon, demonstrating that iron oxide particles catalyse the decomposition of toluene vapour. SEM and TEM observations show that these particles are most often located at the nanotube root, suggesting a base growth mechanism responsible for the formation of aligned nanotube when prolonging growth time (2 min).     

Growth and electrical characterization of high-aspect-ratio carbon nanotube arrays

The remarkable properties of carbon nanotubes (CNTs) make them attractive for microelectronic applications, especially for interconnects and nanoscale devices. In this paper, we describe a microelectronics compatible process for growing high-aspect-ratio CNT arrays with application to vertical electrical interconnects. A lift-off process was used to pattern catalyst (Al₂O₃/Fe) islands to diameters of 13 or 20 μm. After patterning, chemical vapor deposition (CVD) was involved to deposit highly aligned CNT arrays using ethylene as the carbon source, and argon and hydrogen as carrier gases. The as-grow CNTs were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the CNTs have high purity, and form densely-aligned arrays with controllable array size and height. Two-probe electrical measurements of the CNT arrays indicate a resistivity of ∼0.01 Ω cm, suggesting possible use of these CNTs as interconnect materials.     

Observations of novel carbon nanotubes with multiple hollow cores

Usually carbon nanotubes (CNTs) containing only one hollow core are obtained from the catalytic decomposition of hydrocarbons when hydrocarbon gases flow straight into the reaction tube. However, unusual carbon nanotubes with multiple hollow cores were observed when the gas-feed method was changed in an attempt to increase CNT production yield using a floating catalyst method. The fraction of multicored carbon nanotubes can be as high as 60%. The formation of such an unusual structure is ascribed to the introduction of pentagon and heptagon defects to the CNTs in the growth process, owing to the change of gas-feed method. This finding enriches the family of CNTs and could be helpful in understanding the CNT formation mechanism.     

Diameter and morphology dependence on experimental conditions of carbon nanotube arrays grown by spray pyrolysis

A systematic study on the controlled growth of large areas of aligned multi-wall carbon nanotube arrays, from ferrocene-benzene precursor, and of nanotube junctions from ferrocene-thiophene precursor, without hydrogen addition, using an injection CVD method easy to scale up for industrial production is reported.A detailed study is presented of how the synthesis parameters such as growth temperature, active solution flow rate, catalyst concentration or sulfur addition can control the properties and morphology of the grown nanotube mat. Nanotube junctions with considerable yield can be grown with our method by adding sulfur to the synthesis process. The sulfur addition also results in growth of carbon nanocones (CNC) in the lower temperature regime of the furnace. Observation of single-wall carbon nanotubes in our STM investigations provides further indication that under properly chosen conditions SWCNTs can be grown with similar continuous processes.     

Fabrication and characterization of carbon nanotube arrays using sandwich catalyst stacks

A novel synthesis of carbon nanotubes for field-emitter arrays with a uniform field emission current is reported. Microwave plasma chemical vapor deposition and a unique structure of a sandwich catalyst stack are used to grow vertically aligned carbon nanotubes with a high density, uniform length and diameter. After being etched in a H₂/N₂-microwave plasma, the overall field emission current density from the prepared emitter arrays is 1.2 A/cm² at an electric field of 6.5 V/μm with stable and uniform emission characteristics. The threshold field is 3.2 V/cm, defined at an emission current density of 10⁻⁶ A/cm².     

Influence of electric field and emission current on the configuration of nanotubes in carbon nanotube layers

The influence of applied electric field (E_av) and emission current (I_FE) on the configuration of conical layers carbon nanotubes (CLNTs) grown by CVD on the edge of Ni foil has been investigated. TEM profile imaging revealed a high concentration of nanotubes near the foil edge surface, whereas on the nanotube layers’ outer surfaces single, non-oriented nanotubes with open ends free of catalytic particles, were observed. After sufficient electric field application many nanotubes became oriented towards the anode, but one or two of them were found to be always a few microns more extended. In situ SEM investigation showed that below E_av = 3.2–3.9 V/μm, emission was achieved at the expense of originally existing free nanotube ends. Configuration changes began at larger electric fields. On the observed foil edge length (14.6–17.8 μm, with an edge thickness of 200 μm) one or two nanotubes extended towards the anode and probably became the main emitters. Upon further increasing the field to E_av = 5.7–8 V/μm and at an emission current I_FE = 2 × 10⁻⁵ A these tubes disappeared (or essentially shortened). At E_av = 8 V/μm and higher and at an exposure time up to 40 min, several tens of extended nanotubes appeared, with one or two extended well beyond the others. This nanotube configuration pattern is connected with electrostatic screening between the nanotubes. Our interpretation of the data suggests that in the investigated range of E_av and I_FE, a limited number of nanotubes are emitting and these nanotubes are constantly changing as E_av, I_FE and exposure time increase.     

CVD growth of carbon nanotube bundle arrays

Recent discovery of enhanced field emission current intensity from arrays of bundles of carbon nanotubes (CNT) has prompted this investigation of the growth of CNT bundle arrays by metal-catalyzed chemical vapor deposition (CVD), in order to understand and control the growth of these arrays. CNT bundle array growth has been characterized as a function of array geometric parameters: the CNT bundle diameter and inter-bundle spacing. We find that CNT bundle array growth varies significantly with bundle size and spacing, which we suggest is due to the formation of a volatile molecular byproduct of ethylene decomposition that enhances CNT growth in areas with high concentrations of metal catalyst. We have also studied and optimized CNT growth with respect to a variety of CVD process parameters, in order to control the length of the resultant CNT bundles. We find that the length of the CNT can be reliably controlled by varying either the reaction time or the gas pressure. Such control over CNT bundle length will be crucial in the incorporation of these bundle arrays into high-intensity electron field emission devices.     

Continuous deposition of carbon nanotubes on a moving substrate by open-air laser-induced chemical vapor deposition

Continuous deposition of carbon nanotubes under open-air conditions on a moving fused quartz substrate is achieved by pyrolytic laser-induced chemical vapor deposition. A CO₂ laser is used to heat a traversing fused quartz rod covered with bimetallic nanoparticles. Pyrolysis of hydrocarbon precursor gas occurs and subsequently gives rise to rapid growth of a multi-wall carbon nanotube forest on the substrate surface. A “mushroom-like” nanotube pillar is observed, where a random orientation of carbon nanotubes is located at the top of the pillars while the growth is more aligned near the base. The typical carbon nanotube deposition rate achieved in this study is approximately 50 μm/s. At high power laser irradiation, various carbon microstructures are formed as a result of excessive formation of amorphous carbon on the substrate. High-resolution transmission and scanning electron microscopy, and X-ray energy-dispersive spectrometry are used to investigate the deposition rate, microstructure, and chemical composition of the deposited carbon nanotubes.     

Structural studies of oriented carbon nanotubes in alumina channels using high energy X-ray diffraction

Structural studies of multi-wall carbon nanotubes prepared by template pyrolytic carbon deposition from thermal decomposition of propylene at 800 °C inside channels of an alumina membrane have been performed using X-ray diffraction. The two-dimensional diffraction pattern of the deposited carbon nanotubes, recorded directly within the alumina template using an image plate detector, exhibits two dark arcs corresponding to the (0 0 2) graphitic reflection. The anisotropic scattering distribution indicates alignment of the nanotubes. The diffracted intensity was measured for the powdered samples after removing the alumina membrane using a point detector. A maximum scattering vector of K_max = 20 Å⁻¹ yielded the radial distribution function, providing evidence that the investigated nanotubes form a distorted hexagonal network that implies the presence of five-membered rings.