Growth of vertically aligned arrays of carbon nanotubes for high field emission

Vertically aligned multi-walled carbon nanotubes have been grown on Ni-coated silicon substrates, by using either direct current diode or triode plasma-enhanced chemical vapor deposition at low temperature (around 620 °C). Acetylene gas has been used as the carbon source while ammonia and hydrogen have been used for etching. However densely packed (∼ 10⁹ cm^− 2) CNTs were obtained when the pressure was ∼ 100 Pa. The alignment of nanotubes is a necessary, but not a sufficient condition in order to get an efficient electron emission: the growth of nanotubes should be controlled along regular arrays, in order to minimize the electrostatic interactions between them. So a three dimensional numerical simulation has been developed to calculate the local electric field in the vicinity of the tips for a finite square array of nanotubes and thus to calculate the maximum of the electron emission current density as a function of the spacing between nanotubes. Finally the triode plasma-enhanced process combined with pre-patterned catalyst films (using different lithography techniques) has been chosen in order to grow regular arrays of aligned CNTs with different pitches in the micrometer range. The comparison between the experimental and the simulation data permits to define the most efficient CNT-based electron field emitters.     

Structural and photoluminescence characterization of vertically aligned multiwalled carbon nanotubes coated with ZnO by magnetron sputtering

Zinc oxide (ZnO) nanostructures are very attractive in various optoelectronic applications such as light emitting devices. A fabrication process of these ZnO nanostructures which gives a good crystalline quality and being compatible with that of micro-fabrication has significant importance for practical application. In this work ZnO films with different thicknesses were deposited by RF-sputtering on vertically aligned multiwalled carbon nanotube (MWCNTs) template in order to obtain ZnO nanorods. The obtained hybrid structures (ZnO/MWCNTs) were characterized by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and time resolved photoluminescence spectroscopy (PL). Results show that the ZnO/MWCNTs have a nanorod structure like morphology with a good crystalline quality of the deposited ZnO on the MWCNTs. PL measurements reveal an enhancement of the band edge signal of ZnO/MWCNTs which is three times of magnitude higher compared to the ZnO film deposited on silicon. Moreover, the intensity enhancement varies as function of the ZnO thickness. Such hybrid structures are promising for optoelectronic application, such as blue-violet sources.     

Vertically aligned multiwalled carbon nanotubes for pressure, tactile and vibration sensing

We report a simple method for the micro-nano integration of flexible, vertically aligned multiwalled CNT arrays sandwiched between a top and bottom carbon layer via a porous alumina (Al(2)O(3)) template approach. The electromechanical properties of the flexible CNT arrays have been investigated under mechanical stress conditions. First experiments show highly sensitive piezoresistive sensors with a resistance decrease of up to ～35% and a spatial resolution of <1?mm. The results indicate that these CNT structures can be utilized for tactile sensing components. They also confirm the feasibility of accessing and utilizing nanoscopic CNT bundles via lithographic processing. The method involves room-temperature processing steps and standard microfabrication techniques.     

Structural modifications and enhanced Raman scattering from multiwalled carbon nanotubes grown on titanium coated silicon single crystals

Multiwalled carbon nanotubes (MWCNTs) were grown on 10 nm iron (Fe) film by microwave plasma enhanced chemical vapor deposition using titanium (Ti) film as an interlayer. The Ti interlayer of thickness 5 nm-20 nm was sandwiched between Fe and silicon (Si) using thermal evaporation. Enhanced Raman response was observed in MWCNTs with increasing Ti interlayer thickness. This was related with the plasmonic effects occurring at the interface of the CNTs and the metallic support in a three layer system (Ti-Fe-CNTs). The increase in the G mode optical strength is attributed to surface enhanced resonance Raman scattering. Moreover, the increase in the D-mode and 2D-mode intensity is explained on the basis of double resonance effects. The crystallinity in the samples was calculated using I_D/I_G ratio. It was found that that I_D/I_G ratio decreases in three layer system with increasing Ti interlayer thickness as compared to a two layer (Fe-CNTs) system as reported earlier.     

Reproducible fabrication of robust, renewable vertically aligned multiwalled carbon nanotube/epoxy composite electrodes

We describe the reproducible fabrication of robust, vertically aligned multiwalled carbon nanotube (VACNT)/epoxy composite electrodes. The electrodes are characterized by cyclic voltammetry, impedance spectroscopy, and scanning electron and atomic force microscopies. Low background currents are obtained at the electrodes, and common redox probe molecules and NADH show excellent voltammetric behavior. When electrode performance deteriorates due to fouling, the electrode surfaces can be reproducibly renewed by mechanical polishing followed by O(2) plasma treatment. The electrochemical performance of the electrodes is maintained after more than 100 cycles of use and renewal.     

Synthesis of vertically aligned carbon nanotube arrays by injection method in CVD

The well aligned multiwalled carbon nanotube arrays were synthesized by injecting the acetonitrile-ferrocene solution at regular intervals of time. The carbon nanotube arrays were deposited on quartz substrate which is placed at the centre of the CVD reactor in quartz tube. The injection method in chemical vapor deposition allows-excellent control of the catalyst to carbon ratio which facilitates the better growth of aligned carbon nanotubes. The effect of various reaction parameters such as growth temperature, catalyst concentration, gas flow rate, growth time and substrate surface on growth of carbon nanotubes have been studied. It was observed that the diameter of carbon nanotubes increases with increase in catalyst concentration and temperature of the synthesis. The SEM analysis reveals that the average growth rate of carbon nanotube film synthesis was about 1.1 microm/min when the synthesis time was one hour.     

High-performance electronics using dense, perfectly aligned arrays of single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) have many exceptional electronic properties. Realizing the full potential of SWNTs in realistic electronic systems requires a scalable approach to device and circuit integration. We report the use of dense, perfectly aligned arrays of long, perfectly linear SWNTs as an effective thin-film semiconductor suitable for integration into transistors and other classes of electronic devices. The large number of SWNTs enable excellent device-level performance characteristics and good device-to-device uniformity, even with SWNTs that are electronically heterogeneous. Measurements on p- and n-channel transistors that involve as many as approximately 2,100 SWNTs reveal device-level mobilities and scaled transconductances approaching approximately 1,000 cm(2) V(-1) s(-1) and approximately 3,000 S m(-1), respectively, and with current outputs of up to approximately 1 A in devices that use interdigitated electrodes. PMOS and CMOS logic gates and mechanically flexible transistors on plastic provide examples of devices that can be formed with this approach. Collectively, these results may represent a route to large-scale integrated nanotube electronics.     

环己烷浮游催化法制备超长碳纳米管阵列

采用非芳香烃类环己烷作为碳源,通过浮游法实现了超长垂直碳纳米管(Carbon nanotube,CNT)阵列的生长。研究表明:浮游催化过程中反应温度、催化剂前体补给速度、进料速度、生长气氛等因素对CNT阵列的生长影响显著。在直径为25mm的石英反应器中,反应温度、催化剂前体二茂铁的补给速度、碳源环己烷的补给速度、反应气氛分别控制在820℃、0.24mg/min、0.12mL/min、640mL/min(H2/Ar=1∶15)的生长窗口内,实现了CNT阵列的快速协同生长。在单因素考察的基础上,通过对宏观参数的调变,可以制备出长度达5.0mm的CNT阵列。所获得的CNT取向一致,长径比大于105,纯度达到96.7%。     

Growth of vertically aligned carbon nanofibers from nickel nanodot arrays produced from diblock copolymer thin film templates

Diblock copolymers of polystyrene and poly(methyl methacrylate) are utilized in a thin film to create a nanoscale template, which is used to deposit a nanoscale array of nickel nanodots. Systematic experiments show that this process must be optimized to successfully transfer the order of the diblock copolymer template to the resultant nickel nanodot array. It is found that the amount of nickel deposited dramatically impacts the fidelity of the final nanodot array, with a thickness ratio for copolymer:metal of 8:1 found to be optimal. The results also indicate that the method by which the surface is neutralized for the diblock domain alignment impacts the amount of nickel nanodots that remain on the surface after template removal. Finally, the nanoscale array of nickel nanodots is utilized to successfully grow vertically aligned carbon nanofibers from 18 nm and 40 nm diameter nickel dots.     

Oxygen plasma assisted end-opening and field emission enhancement in vertically aligned multiwall carbon nanotubes

This paper highlights the changes in micro-structural and field emission properties of vertically aligned carbon nanotubes (VACNTs) via oxygen plasma treatment. We find that exposure of very low power oxygen plasma (6 W) at 13.56 MHz for 15–20 min, opens the tip of vertically aligned CNTs. Scanning electron microscopy and transmission electron microscopy images were used to identify the quality and micro-structural changes of the nanotube morphology and surfaces. Raman spectra showed that the numbers of defects were increased throughout the oxygen plasma treatment process. In addition, the hydrophobic nature of the VACNTs is altered significantly and the contact angle decreases drastically from 110° to 40°. It was observed that the electron field emission (EFE) characteristics are significantly enhanced. The turn-on electric field (ETOE) of CNTs decreased from ∼0.80 V μm⁻¹ (untreated) to ∼0.60 V μm⁻¹ (oxygen treated). We believe that the open ended VACNTs would be immensely valuable for applications such as micro/nanofluidic based filtering elements and display devices.     

Preferential syntheses of semiconducting vertically aligned single-walled carbon nanotubes for direct use in FETs

We have combined fast heating with plasma enhanced chemical vapor deposition (PECVD) for preferential growth of semiconducting vertically aligned single-walled carbon nanotubes (VA-SWNTs). Raman spectroscopic estimation indicated a high yield of up to 96% semiconducting SWNTs in the VA-SWNT array. The as-synthesized semiconducting SWNTs can be used directly for fabricating FET devices without the need for any postsynthesis purification or separation.     

In situ electrostatic assembly of CdS nanoparticles onto aligned multiwalled carbon nanotubes in aqueous solution

A simple method is described for the electrostatic assembly of CdS nanoparticles onto oxidized aligned multiwalled carbon nanotubes (MWCNTs) in aqueous solution. The method is convenient to control and allows the formation of a stable, water-soluble suspension of CdS/aligned-MWCNT heterostructures. The prepared CdS/aligned-MWCNT heterostructures are characterized by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), energy dispersive x-ray spectroscopy (EDS), x-ray diffraction (XRD) and Fourier transform infrared spectrometry (FT-IR). The fluorescence and UV absorption spectral properties of the hybrid material demonstrate electron transfer from CdS nanoparticles to aligned-MWCNTs, which implies its potential applications in photovoltaic cells, photocatalysis, and solar energy conversion.     

Random networks and aligned arrays of single-walled carbon nanotubes for electronic device applications

Singled-walled carbon nanotubes (SWNTs), in the form of ultrathin films of random networks, aligned arrays, or anything in between, provide an unusual type of electronic material that can be integrated into circuits in a conventional, scalable fashion. The electrical, mechanical, and optical properties of such films can, in certain cases, approach the remarkable characteristics of the individual SWNTs, thereby making them attractive for applications in electronics, sensors, and other systems. This review discusses the synthesis and assembly of SWNTs into thin film architectures of various types and provides examples of their use in digital electronic circuits with levels of integration approaching 100 transistors and in analog radio frequency (RF) systems with operating frequencies up to several gigahertz, including transistor radios in which SWNT transistors provide all of the active functionality. The results represent important steps in the development of an SWNT-based electronics technology that could find utility in areas such as flexible electronics, RF analog devices and others that might complement the capabilities of established systems. This article is published with open access at Springerlink.com     

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.     

Fabrication and characterization of vertically aligned carbon nanotubes on silicon substrates using porous alumina nanotemplates

An ethylene-air laminar diffusion flame successfully provided silicon substrates of anodic aluminum oxide (AAO) template with vertically oriented well-aligned carbon nanotubes. Field emission scanning electron microscopy (SEM) showed that open-tipped carbon nanotubes consisting of tube elements with the same length and diameter uniformly coated the template. High-resolution transmission electron microscopy (TEM) analyses revealed these nanotubes to be multiwalled carbon nanotubes, some well graphitized. It was found that cobalt catalyst particles, but not the porous aluminum templates, helped the growth of carbon nanotubes through graphitization and bonding of carbon nanotubes to the silicon substrates.     

Guided growth of large-scale, horizontally aligned arrays of single-walled carbon nanotubes and their use in thin-film transistors

A convenient process for generating large-scale, horizontally aligned arrays of pristine, single-walled carbon nanotubes (SWNTs) is described. The approach uses guided growth, by chemical vapor deposition (CVD), of SWNTs on miscut single-crystal quartz substrates. Studies of the growth reveal important relationships between the density and alignment of the tubes, the CVD conditions, and the morphology of the quartz. Electrodes and dielectrics patterned on top of these arrays yield thin-film transistors that use the SWNTs as effective thin-film semiconductors. The ability to build high-performance devices of this type suggests significant promise for large-scale aligned arrays of SWNTs in electronics, sensors, and other applications.     

Theoretical and experimental studies of Schottky diodes that use aligned arrays of single-walled carbon nanotubes

We present theoretical and experimental studies of Schottky diodes that use aligned arrays of single-walled carbon nanotubes. A simple physical model, taking into account the basic physics of current rectification, can adequately describe the single-tube and array devices. We show that for as-grown array diodes, the rectification ratio, defined by the maximum-to-minimum-current-ratio, is low due to the presence of metallic-single-walled nanotube (SWNT) shunts. These tubes can be eliminated in a single voltage sweep resulting in a high rectification array device. Further analysis also shows that the channel resistance, and not the intrinsic nanotube diode properties, limits the rectification in devices with channel length up to 10 μm.     

Microstructural and optical properties of nanocrystalline ZnO deposited onto vertically aligned carbon nanotubes by physical vapor deposition

Nanocrystalline ZnO films with thicknesses of 5 nm, 10 nm, 20 nm, and 50 nm were deposited via magnetron sputtering onto the surface of vertically aligned multi-walled carbon nanotubes (MWCNTs). The ZnO/CNTs heterostructures were characterized by scanning electron microscopy, high resolution transmission electron microscopy, and X-ray diffraction studies. No structural degradation of the CNTs was observed and photoluminescence (PL) measurements of the nanostructured ZnO layers show that the optical properties of these films are typical of ZnO deposited at low temperatures. The results indicate that magnetron sputtering is a viable technique for growing heterostructures and depositing functional layers onto CNTs.     

Effect of interface, height and density of long vertically aligned carbon nanotube arrays on their thermal conductivity: an experimental study

The ever-growing need to dissipate larger amounts of heat from components and structures requires the development of novel materials with superior thermal conductivity. Aligned carbon nanotube arrays that are integrated in composite materials and structures may prove useful in increasing heat transfer through their thickness. Theoretical studies have shown the potential of carbon nanotubes to reach a thermal conductivity of 6600 Wm(-1)K(-1). Experimental results on the arrays however have shown much lower thermal conductivity values. A study was conducted to better understand heat conduction in mm-long carbon nanotube arrays and to experimentally determine their thermal conductivity. Emphasis was placed on the effect of various parameters including the height and density of the array and the thermal resistance at the array interface. A method was devised to measure the thermal conductivity of the array relying on Fourier's law while maintaining a steady state one-dimensional heat flow. The study reveals that the taller the array and the higher its density, the larger the thermal conductivity of the array. Quantitative data is also provided on the effect of various interface materials and their deposition technique on the thermal conductivity of the arrays.     

Structural and proactive safety aspects of oxidation debris from multiwalled carbon nanotubes

The removal of oxidation debris from the oxidized carbon nanotube surface with a NaOH treatment is a key step for an effective functionalization and quality improvement of the carbon nanotube samples. In this work, we show via infrared spectroscopy and ultrahigh resolution and accuracy mass spectrometry that oxidation debris obtained from HNO(3)-treated multiwalled carbon nanotubes is a complex mixture of highly condensed aromatic oxygenated carbonaceous fragments. We have also evaluated their cytotoxicity by using BALB/c 3T3 mouse fibroblasts and HaCaT human keratinocytes as models. By knowing the negative aspects of dissolved organic carbon (DOC) to the water quality, we have demonstrated the removal of these carbon nanotube residues from the NaOH solution (wastewater) by using aluminium sulphate, which is a standard coagulant agent used in conventional drinking water purification and wastewater treatment plants. Our results contribute to elucidate the structural and proactive safety aspects of oxidation debris from oxidized carbon nanotubes towards a greener nanotechnology.